Vitamin E, a potent antioxidant, is a necessary and complex micronutrient for cows. During the transition period, vitamin E deficiency (VED) is among the highest prevalent micronutrient deficits in dairy cows. It may eventually result in oxidative stress and immunological malfunction, and it increases the risk of peripartum disorders. At present, detailed data on blood metabolites in VED cows are limited. Consequently, the purpose of this research was to examine the alterations in the serum metabolic profile of VED cows throughout the early postpartum period. Using comprehensive 1H nuclear magnetic resonance (1H NMR), the alterations in serum metabolic activities of VED cows were analyzed. In total, 28 multiparous Holstein cows were assigned according to serum α-tocopherol (α-Toc) concentrations into a normal (α-Toc ≥ 4 μg/mL, n = 14) and VED (α-Toc < 3 μg/mL, n = 14) groups at 21 days postpartum, and their blood samples were collected for biochemical and 1H NMR analyses. A t-test on independent samples as well as multivariate statistics were used to assess the findings. In comparison with normal cows, VED cows showed significantly worse body condition scores, milk yield, and dry matter intake (p < 0.05). Significantly higher levels of serum non-esterified fatty acids, aspartate aminotransferase, low-density lipoprotein, and malonaldehyde were found in VED-affected cows, as well as lesser concentrations of serum albumin, high-density lipoprotein, and total antioxidant capacity in comparison with normal cows (p < 0.01), while other vitamins and minerals concentrations showed no distinction between the groups (p > 0.05). Furthermore, 24 upregulated serum metabolites were identified under VED conditions. The metabolomics pathway analysis of these metabolites demonstrated that a global metabolic response to VED in cows was represented by changes in 11 metabolic pathways, comprising energy, carbohydrate, and amino acid metabolism. These outcomes suggest that VED cows were more likely to experience a negative energy balance characterized by alterations of common systemic metabolic processes and develop oxidative stress, inflammation, and ultimately liver injury. This study provides the first evidence of metabolic changes in cows with VED.

Malignant Pleural Mesothelioma (MPM) is an aggressive cancer associated to asbestos exposure. MPM pathogenesis has been related both to oxidative stress, evoked by and in response to asbestos fibers exposure, and the Epithelial Mesenchymal Transition (EMT), an event induced by oxidative stress itself and related to cancer proliferation and metastasis. Asbestos related primary oxidative damage is counteracted in the lung by various redox-sensitive factors, often hyperactivated in some cancers. Among these redox-sensitive factors, Apurinic-apyrimidinic endonuclease 1 (APE-1)/Redox effector factor 1 (Ref-1) has been demonstrated to be overexpressed in MPM and lung cancer, but the molecular mechanism has not yet fully understood. Moreover, asbestos exposure has been associated to induced EMT event, via some EMT transcription factors, such as Twist, Zeb-1 and Snail-1, in a possible crosstalk with oxidative stress and inflammation events. To demonstrate this hypothesis, we inhibited/silenced Ref-1 in MPM cells: as a consequence, both EMT (Twist, Zeb-1 and Snail-1) markers and cellular migration/proliferation were significantly inhibited. Take as a whole, these results show, for the first time, a crosstalk between oxidative stress and EMT in MPM carcinogenesis and invasiveness, so improving the knowledge to better address a preventive and therapeutic approach against this aggressive cancer.

A new Pd(II) complex of the previously reported ligand N,N′-bis[(2,2′-dihydroxybiphen-3-yl)methyl]-N,N′-dimethylethylenediamine (L) was obtained from a DMF/H2O mixture. It differs from a Pd(II) complex of L previously obtained by sole DMF. The roles in the solid state assembly of solvent molecules and molecular conformation (driven by specific transition metal ions) were studied by comparing six complexes of L containing different metal centers (Ni(II), Cd(II), Cu(II), Pd(II)). Hirshfeld surface analysis, 2D fingerprint plots and energy frameworks calculations were used to investigate the intermolecular interactions within the crystal packing of the six complexes. As suggested by interaction energies, Pd(II) and Ni(II) complexes arrange to form ribbons, while Cd(II) and Cu(II) complexes form 3D networks. Interactions between complexes and solvent molecules in the previous Pd(II) complex are replaced by complex-complex interactions in the new Pd(II) complex, while BuOH and MeOH are interchangeable in the interactions within the crystal packing of the two Ni(II) complexes. Finally, solvent molecules are not involved in the crystal packing of the Cu(II) complex. The present study suggested that the solid state assembly of these systems is mainly driven by the molecular conformation, that depends in turn by the metal ion involved, while the solvent only plays a minor role.

Drivers of L3 automated vehicles (AVs) are not required to continuously monitor the AV system. However, they must be prepared to take over when requested. Therefore, it is necessary to design an in-vehicle environment that allows drivers to adapt their levels of preparedness to the likelihood of control transition. This study evaluates ambient in-vehicle lighting that continuously communicates the current level of AV reliability, specifically on how it could influence drivers' take-over performance and mental workload (MW). We conducted an experiment in a driving simulator with 42 participants who experienced 10 take-over requests (TORs). The experimental group experienced a four-stage ambient light display that communicated the current level of AV reliability, which was not provided to the control group. The experimental group demonstrated better take-over performance, based on lower vehicle jerks. Notably, perceived MW did not differ between the groups, and the EEG indices of MW (frontal theta power, parietal alpha power, Task-Load Index) did not differ between the groups. These findings suggest that communicating the current level of reliability using ambient light might help drivers be better prepared for TORs and perform better without increasing their MW.

In this work, we analytically describe a superconducting transition in a non-equilibrium state taking into account many-body interactions; the obtained transition temperatures indicate the presence of superconductivity at room temperatures.First, we consider many-body interactions and discuss the case of locally thermal equilibrium with many-body interactions; in this section, we derive statistical equations that describe many-body interactions at locally thermal equilibrium state. Then, the same theory is used to derive a many-body statistical equation that is expanded to include the case of non-equilibrium states; in this case a transition temperature is derived. Moreover, a wave function of an Einstein–Podolsky–Rosen pair (EPR pair) is calculated according to the Lorentz conservation, and a specific condensation is observed and the Meissner effect is found to be present.Furthermore, considering the Lorentz conservations, relativistic energy, and Boltzmann statistics, algorithms are presented to calculate charge density, current density, and internal local energy. We note that these calculations do not require a specific code but instead utilize the software Microsoft Excel.We present plots showing the charge density and current density vs. the applied electric potential, which demonstrate the practical applicability of the theory. Moreover, internal local energy was found to be close to zero for sufficiently large electric potentials at room temperature.In the discussion section, the universally induced superconducting current is derived, which can be employed as the renewable energy.This paper describes non-equilibrium and EPR-pair type superconductivity, with the complete consideration of many-body interactions.

This study aims to better understand students who attend the Basic Vocational Training Cycles (FPB) regarding the measures to ensure diversity. This quantitative research project approximates the perception of students concerning their passage through their previous studies and their satisfaction and goals after finishing the school year. The sample con-sists of 352 students from Cordoba (Spain). A questionnaire has been used which follows the CIPP model. After the exploratory factor analysis was completed with the different groups of items and their descriptive analysis, various tests were carried out to consider the hypotheses (Pearson's correlation (r), one-factor analysis of variance and repeated ANOVA measures). The results indicate that the educational interest of the students is ac-ademic and professional. Likewise, there is no relationship detected between the appear-ance of socio-professional goals and average academic levels and the attributions with re-spect to repetitions of previous courses, although these goals vary depending on the satis-faction shown by the students with respect to the cycles. We conclude that the course of the FPB influences the adoption of decisions regarding academic-professional projects.

Azobenzene-containing molecules may associate with each other in systems such as self-assembled monolayers or micelles. The interaction between azobenzene units leads to a formation of exciton states in these molecular assemblies. Apart from local excitations of monomers, the electronic transitions to the exciton states may involve charge transfer excitations. Here, we perform quantum chemical calculations and apply transition density matrix analysis to quantify local and charge transfer contributions to the lowest electronic transitions in azobenzene dimers of various arrangements. We find that the transitions to the lowest exciton states of the considered dimers are dominated by local excitations, but charge transfer contributions become sizable for some of the lowest ππ* electronic transitions in stacked and slip-stacked dimers at short intermolecular distances. In addition, we assess different ways to partition the transition density matrix between fragments. In particular, we find that the inclusion of the atomic orbital overlap has a pronounced effect on quantifying charge transfer contributions if a large basis set is used.

We propose a chemical language processing model to predict polymers’ glass transition temperature (Tg) through a polymer language (SMILES, Simplified Molecular Input Line Entry System) embedding and recurrent neural network. This model only receives the SMILES strings of polymer’s repeat units as inputs and considers the SMILES strings as sequential data at the character level. Using this method, there is no need to calculate any additional molecular descriptors or fingerprints of polymers, and thereby, being very computationally efficient and simple. More importantly, it avoids the difficulties to generate molecular descriptors for repeat units containing polymerization point `*’. Results show that the trained model demonstrates reasonable prediction accuracy on unseen polymer’s Tg. Besides, this model is further applied for high-throughput screening on an unlabeled polymer database to identify high-temperature polymers that are desired for applications in extreme environments. Our work demonstrates that the SMILES strings of polymer’s repeat units can be used as an effective feature representation to develop a chemical language processing model for predictions of Tg. The framework of this model is general and can be used to construct structure-property relationships for other polymer’s properties.

The energy crisis and environmental problems are becoming more and more severe due to the long-term consumption of fossil fuels. Therefore, energy conversion devices with high energy density and environmental friendliness (such as fuel cells, metal-air batteries, etc.) have been ex-pected to be reliable alternatives to traditional fossil energy. However, due to the inevitable use of precious metals as the electrode catalysts for these devices, the popularization of these alternatives is seriously hindered. Transition metal nitrides (TMNs) exhibit similar surface and adsorption properties to noble metals since the atomic distance between metal atoms increases and the d-band center of metal atoms downshift after the nitrogen atoms enter the metal lattice. TMNs have become one of the best electrode materials to replace noble metal electrocatalysts in energy storage and conversion devices. In this review, the latest development in the electrocatalytic ap-plication of TMNs nanocrystalline is covered. Firstly, we briefly discuss the structure and activity origin of TMNs and introduce the common physical and chemical methods for the preparation of TMNs. Subsequently, we illustrate the applications of unary TMNs and multivariate TMNs in oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Finally, we summarize the challenges and problems of TMNs encountered at the present stage, and expect its future de-velopment.

Nearly one third of men will incur biochemical recurrence after treatment for localized prostate cancer. Androgen deprivation therapy (ADT) is the therapeutic mainstay, however almost all patients will eventually transition to a castrate resistant state (castrate resistant prostate cancer, CRPC). Subjects with CRPC generally develop symptomatic metastatic disease (mCRPC) and incur mortality several years later. Prior to metastatic disease, men acquire non-metastatic CRPC (nmCRPC) which lends the unique opportunity for intervention to delay disease progression and symptoms. This review addresses current therapies for nmCRPC, as well as novel therapeutics and pathway strategies targeting men with nmCRPC.

In this work, effects of 20 transition element additives on the interfacial adhesion energy and electronic structure of Al (111)/6H-SiC (0001) interfaces have been studied by first principles method. For clean Al (111)/6H–SiC (0001) interfaces, both Si-terminated and C-terminated interfaces have covalent bond characteristics. The C-terminated interface has stronger binding energy, which is mainly due to the stronger covalent bond formed by the larger charge transfer between C and Al. The results show that the introduction of many transition elements, such as 3d transitional group Mn, Fe, Co, Ni, Cu, Zn and 4d transitional group Tc, Ru, Rh, Pd, Ag, can improve the interfacial adhesion energy of the Si-terminated Al (111)/6H-SiC (0001) interface. However, for the C-terminated Al (111)/6H-SiC (0001) interface, only the addition of Co element can improve the interfacial adhesion energy. Bader charge analysis shows that the increase of interfacial binding energy is mainly attributed to more charge transfer.

The diversification of life-histories is mediated by cooperation, innovations of biological information, modularity, and heterochrony in developmental processes. These processes are defined, contextualized, and exemplified, studying the evolution of coloniality (i.e. life-history involving modularization of the multicellular individual) in the family of benthic tunicates Styelidae. This study proposes that in these colonial tunicates there is an inter-generational division of labor, where one generation is feeding, a second is developing by morphogenetic processes, and a third is aging by programmed cell death and phagocytosis. The communication system developed in these colonies is mediated, by changes in proportion, location, and gene expression of specialized blood cells. Colonial life-history in animals is related to the reduction of individual size; development of extra-corporeal tissues to interconnect zooids; the inter-generational division of labor; and the reduction of zooid’s individuality. Processes analogous with the widely accepted major evolutionary transitions (METs), suggesting that coloniality could be studied as a MET. The understanding of colonial life-histories could provide information about key mechanisms for life diversification.

Despite great strides being achieved in improving cancer patients’ outcomes through better therapies and combinatorial treatment, several hurdles still remain due to therapy resistance, cancer recurrence and metastasis. Drug resistance, culminating in relapse and metastatic disease continue to be associated with fatal disease. Cancer stem cells (CSCs) are a subpopulation of cancer cells known to be resistant to therapy and cause metastasis. Whilst the debate on whether CSCs are the origins of the primary tumor rages on, CSCs have been further characterised in many cancers with data illustrating that CSCs display great abilities to self-renew, withstand therapies due to enhanced epithelial to mesenchymal (EMT) properties, enhanced expression of ABC membrane transporters, activation of several survival signaling pathways and increased immune evasion DNA repair mechanisms. CSCs also display great heterogeneity with the consequential lack of specific CSC markers presenting a great challenge to their targeting. In this updated review we re-visit CSCs within the tumor microenvironment (TME) and present novel treatment strategies targeting CSCs. These promising strategies include targeting CSCs-specific properties using small molecule inhibitors, immunotherapy, microRNA mediated inhibitors, epigenetic methods as well as targeting CSC niche-microenvironmental factors and differentiation. Lastly, we present recent clinical trials undertaken to try to turn the tide against cancer by targeting CSC-associated drug resistance and metastasis.

Solar green roofs, namely rooftops functionalized with properly selected living vegetation and photovoltaic modules, achieve an ideal symbiotic relationship in which promotion of biodiversity and onsite renewable energy production are both enhanced whereas the roof provides a wide range of environmental, health, aesthetic and economic benefits. This study provides a unified outlook of this eminent sustainable technology at the dawn of its uptake across the world, especially in polluted urban areas.

We numerically study surface models defined on hexagonal disks with a free boundary. 2D surface models for planer surfaces have recently attracted interest due to the engineering applications of functional materials such as graphene and its composite with polymers. These 2D composite meta-materials are strongly influenced by external stimuli such as thermal fluctuations if they are sufficiently thin. For this reason, it is very interesting to study the shape stability/instability of thin 2D materials against thermal fluctuations. In this paper, we study three types of surface models including Landau-Ginzburg (LG) and Helfirch-Polyakov models defined on triangulated hexagonal disks using the parallel tempering Monte Carlo simulation technique. We find that the planer surfaces undergo a first-order transition between the smooth and crumpled phases in the LG model and continuous transitions in the other two models. The first-order transition is relatively weaker compared to the transition on spherical surfaces already reported. The continuous nature of the transition is consistent with the reported results, although the transitions are stronger than that of the reported ones.

Zirconium based bulk metallic glasses are industrially valuable materials which commercial market grows rapidly. Surface modification of these metallic glasses by high-intensity lasers is relatively new and costly treatment promising great advantages over classical surface processing methods. In this work we perform the case study of surface modification of Zr$_{46}$Cu$_{36.8}$Ag$_{9.2}$Al$_8$ metallic glass by high-intensity millisecond laser beam. Our results suggest chemical deposition of atmospheric oxygen and nitrogen in the laser-melted surface area and its surroundings. Zirconium nitride layer was detected in the middle of laser-irradiated area. Nanocrystals embedded in the amorphous matrix were also formed on the surface. Overall, our findings suggest possibilities for improvement of mechanical characteristics of the studied metallic glass.

(1) Background: The aim of this investigation is to determine the effect of archwires’ deflection on the temperature transitions driving the austenite to martensite transformation (and vice versa) and the force released by NiTi and CuNiTi orthodontic wires. (2) Methods: Round cross-section archwires have been investigated. The calorimetric approach has been used for measuring transition temperatures occurring in the unstressed (e.g. undeflected) state of the wires. Static Thermo-mechanical analysis in a temperature controlled wet environment has been performed in the range of temperature between 5°C and 55°C for measuring temperature transitions occurring in highly deflected archwires in conjunction with the force released by these wires. (3) Results: Plateau forces investigated in Part I and those reported in the literature describes the wire’s behaviour only at deflection levels close to the end point of the force plateau extension detected at 37°C. Upon heating or cooling, the austenite finish (Af) transition temperature and the martensite start (Ms) temperature largely depends on the deflection level for both NiTi and CuNiTi. (4) Conclusions: The plateau force levels at 37°C, broadly reported in the literature, only represent the lower boundary force that a superelastic wire releases at 37°C above its elastic limit. For both NiTi and CuNiTi, plateau force levels at 37°C can be predicted by the static TMA profile matching the end point of the force plateau extension. Transition temperatures in largely deflected wires are significantly higher than those determined through the calorimetric approach.

Inverse gas chromatography at infinite dilution was used to determine the surface thermodynamic properties of silica particles and PMMA adsorbed on silica, and more particularly, to quantify the London dispersive energy γsd, the Lewis acid γs+ and base γs- polar surface energies of PMMA/silica composites as a function of the temperature and the recovery fraction θ of PMMA. The polar acid–base surface energy γsAB and the total surface energy of the different composites were then deduced as a function of the temperature. In this paper, the Hamieh thermal model was used to quantify the surface thermodynamic energy of poly methyl methacrylate (PMMA) adsorbed on silica particles at different recovery fractions. A comparison of the new results was carried out with those obtained by applying other molecular models of the surface areas of organic molecules adsorbed on the different solid substrates. An important deviation of these molecular models from the thermal model was proved. The determination of γsd, γs+, γs-, and γsAB of PMMA in both bulk and adsorbed phases showed an important non-linearity variation of these surface parameters as a function of the temperature. The presence of maxima in the curves of γsd(T) highlighted the second order transition temperatures in PMMA showing beta-relaxation, glass transition and liquid-liquid temperatures. These three transition temperatures depended on the adsorption rate of PMMA on silica. The proposed method gave a new relation between the recovery fraction of PMMA and its London dispersive energy showing an important effect of the temperature on the surface energy parameters of adsorption of PMMA on silica. A universal equation relating γsd(T,θ) of the systems PMMA/silica to the recovery fraction and the temperature was proposed.

Endothelial function is regulated by a myriad of complex pathways. In our previous study, the expression of miR-378a-3p was shown to inhibit endothelial autophagy and impair endothelial function. However, the mechanism underlying the effect of miR-378a-3p in endothelial cells remains to be elucidated. By employing an in silico approach, Protein Disulfide Isomerase 4 (PDIA-4) was identified as a target of miR-378-3p; however, its’ role in endothelial cells is not known. We here report that endothelial cell-specific loss of PDIA-4 leads to impaired autophagic flux accompanied by loss of endothelial function and apoptosis. Endothelial cell-specific loss of PDIA-4 also induced marked changes in endothelial cells’ architecture, accompanied with the loss of endothelial markers and gain of mesenchymal markers consistent with endothelial-to-mesenchymal transition (EndMT). Loss of PDIA-4 activates TGF-signaling, and inhibition of TGF-signaling inhibits EndMT in PDIA-4 silenced endothelial cells in vitro. Our findings help elucidate the role of PDIA-4 in endothelial autophagy and endothelial function and provide a potential target to modulate and/or limit autophagy and EndMT in (patho-)physiological conditions.

Transitioning to clean cooking fuels is not only part of achieving SDG7, but also makes a significant contribution to mitigating climate change by reducing carbon emissions. The paper contradicts the conventional wisdom that electricity is too expensive to cook with. The paper explores the energy required to cook dishes using different technologies and fuels by analysing data from Cooking Diaries and Controlled Cooking tests conducted under the MECS programme. Electric pressure cookers (EPCs) use least energy when compared with electric hotplates, and a detailed description of how the EPC works explains why this should be. The paper draws out distinctions between African and Asian dishes, notably the impact of energy intensive dishes prepared mostly in Africa. Standard efficiency based approaches to comparing the performance of stoves are not appropriate to modern electric cooking devices so an alternative approach based on specific energy consumptions is proposed e.g. charcoal stoves use 15 times as much energy as EPCs to cook African dishes. Energy ratios provide a basis for estimating carbon emission reductions associated with transitioning to modern cooking fuels. Historical costs show that the cost of cooking with an EPC can be only 20% of the cost of cooking with charcoal, which highlights the potential for modern, energy efficient electric cooking devices to defy the conventional wisdom of the energy ladder.

This paper aims at addressing the exploitation of solid-state carriers for hydrogen storage, with attention paid both to the technical aspects, through a wide review of the available integrated systems, and to the social aspects, through a preliminary overview of the connected impacts from a gender perspective. As for the technical perspective, carriers to be used for solid-state hydrogen storage for various applications can be classified into two classes: metal and complex hydrides. Related crystal structures and corresponding hydrogen sorption properties are reviewed and discussed. Fundamentals of thermodynamics of hydrogen sorption evidences the key role of the enthalpy of reaction, which determines the operating conditions (i.e. temperatures and pressures). In addition, it rules the heat to be removed from the tank during hydrogen absorption and to be delivered to the tank during hydrogen desorption. Suitable values for the enthalpy of hydrogen sorption reaction for operating conditions close to ambient (i.e. room temperature and 1-10 bar of hydrogen) are close to 30 kJ·molH2 1. The kinetics of hydrogen sorption reaction is strongly related to the microstructure and to the morphology (i.e. loose powder or pellets) of the carriers. Usually, kinetics of hydrogen sorption reaction is rather fast, and the thermal management of the tank is the rate determining step of the processes. As for the social perspective, various scenarios for the applications in different socio-economic contexts of solid-state hydrogen storage technologies are described. As it occurs with the exploitation of other renewables innovative technologies, a wide consideration of the social factors connected to these processes is needed to assess the extent to which a specific innovation might produce positive or negative impacts in the recipient socio-economic system and to explore the potential role of the social components and dynamics in fostering the diffusion of the innovation itself. Attention has been addressed to the gender perspective, in view of the enhancement of hydrogen-related energy storage systems, intended both in terms of the role of women in triggering the exploitation of hydrogen-based storage as well as to the impact of this innovation in their current conditions, at work and in daily life.

A quite energetic seismic excitation consisting of one main and additional three distinctive earthquake clusters that occurred in the transition area between the Kefalonia Transform Fault Zone (KTFZ) and the continental collision between Adriatic and Aegean microplates, is thoroughly studied after high–precision aftershocks’ relocation. The activated fault segments are in an area where historical and instrumental data have never claimed the occurrence of a catastrophic (M>6.0) earthquake. The relocated seismicity initially defines an activated structure extending from the northern segment of the Lefkada branch of KTFZ with the same NNE–SSW orientation and dextral strike-slip faulting and then keeping the same sense of motion its strike becomes NE–SW and its dip direction NW. This provides unprecedented information on the link between the KTFZ and the Collision front and sheds more light on the regional geodynamics. The earthquake catalog, which is specially compiled for this study, starts one year before the occurrence of the Mw5.4 mainshock and adequately provides the proper data source for investigating the temporal variation of the b–value, which might be used for discriminating foreshock and aftershock behavior.

Sector coupling is one of the emerging topics in recent energy and climate change policy discussions. It can play a significant role in creating the pathway of a renewable-based energy system in the European energy sector. The North Sea region is very likely to play a key role in the transition to a sustainable energy system. Though different energy modelling approaches allow a versatile use, they lead to the problem of an unclear understanding of specific aspects of sector coupling, and the relevance of existing tools and techniques to model and analyze such a system. This paper is aimed at providing a comprehensive understanding of sector coupling and its incorporation in energy system models. Followed by a thorough literature review on sector coupling and energy system modelling, the paper outlines an approach to select an appropriate tool based on the specific rationales of the research. The paper also presents ‘Oemof’ as an open model tool to address the complex challenges of energy systems. The conclusions from the literature review provide a detailed understanding of the concept of sector coupling and indicate that it can be advantageous from the viewpoints of decarbonization, flexibility, network optimization, and system efficiency. To solve the coupling barriers, diversified techno-socio-economic circumstances should be taken into account through the use of model collaboration. It is also demonstrated how a list of appropriate tools for model collaboration can be picked up methodologically from an available wide range of models. Finally, ‘Oemof’ is hypothesized as a progressive tool to design a sector-coupled and renewable-based energy system in the North Sea region.

In addition to the canonical loss-of-function mutations, mutations in proteins may additionally result in gain-of-function through the binary activation of cryptic ‘structural capacitance elements’. Our previous bioinformatic analysis allowed us to propose a new mechanism of protein evolution - structural capacitance – that arises via the generation of new elements of microstructure upon mutations that cause a disorder-to-order (DO) transition in previously disordered regions of proteins. Here we propose that the DO transition is a necessary follow-on from expected early codon-anticodon and tRNA acceptor stem-amino acid usage, via the accumulation of structural capacitance elements - reservoirs of disorder in proteins. We develop this argument further to posit that structural capacitance is an inherent consequence of the evolution of the genetic code.

To gain insight into the differences between onshore and offshore atmospheric turbulence, 2 pressure fluctuations were measured for offshore wind under different environmental conditions. 3 A durable piezo-electric sensor was used to sample turbulent pressure data at 50 kHz. Offshore 4 measurements were performed at 100 m height on Germany’s FINO3 offshore platform in the 5 German Bight together with additional meteorological data provided by Deutscher Wetterdienst 6 (DWD). The statistical evaluation revealed that the stability state in the atmospheric boundary has a 7 large impact on turbulent fluctuations. Therefore, we used higher statistical properties (described 8 by so-called shape factors) to the stability state. Data was classified to be either within the unstable, 9 neutral or stable stratification. We found that in case of stable stratification, the shape factor is 10 mostly close to zero, indicating that a thermally stable environment produces closer-to Gaussian 11 distributions. Non-Gaussian distributions were found in unstable and neutral boundary layer states 12 and an occurrence probability was estimated. Possible impact on laminar-turbulent transition on the 13 blade is discussed with application of so-called laminar aerofoils on wind turbine blades. Use of a 14 cut-off frequency to separate load and aerodynamic turbulence is proposed.

The study examines the effects of transitioning to hydrogen production in the National Capital Region (NCR) and Palawan Province, Philippines, focusing on technology, environment, and stakeholder impact. The research, conducted through a July 2022 survey, aimed to assess public awareness, knowledge, risk perception, and acceptance of hydrogen and its environmentally friendly variant, green hydrogen, infrastructure. Disparities were found between urban NCR and rural Palawan, with lower awareness in Palawan. Safety concerns were highlighted, with NCR respondents generally considering hydrogen production safe, while Palawan respondents had mixed feelings, particularly regarding nuclear-based hydrogen generation. The report emphasizes the potential ecological advantages of hydrogen technology but highlights potential issues concerning water usage and land impacts. It suggests targeted public awareness campaigns, robust safety assurance programs, regional pilot projects, and integrated environmental plans to facilitate the seamless integration of hydrogen technology into the Philippines' energy portfolio. This collective effort aims to help the country meet climate action obligations, foster sustainable development, and enhance energy resilience.

The draconian regulation required by the inherent instability of cognitive phenomena -- gene expression, immune function, cancer suppression, wound healing, animal consciousness, machine intelligence, network stabilization, institutional cognition, and their many and varied composites -- can be viewed through the lens of the asymptotic limit theorems of both information and control theories. Here, we explore the dynamics and sometimes highly punctuated failures of the regulation of cognition under increasing `noise'. The approach parallels, and indeed generalizes, the Data Rate Theorem of control theory, extending the theorem's requirement of a minimum channel capacity necessary for stabilization of an inherently unstable system. Various models are explored across different basic underlying probability distributions characteristic of the system under study, and across different hierarchical scales, finding the addition of adaptive -- learned -- regulation greatly extends the reach of innate -- e.g., AI-driven or otherwise pre-programmed -- regulation. This work points toward the construction of new statistical tools for the analysis of observational and empirical data across a wide spectrum of inherent pathologies and adversarial challenges afflicting a wide variety of cognitive processes.

The term sustainable energy is very familiar to all of us yet its exact definition or meaning has so far been vague. To date the widely adopted definition of sustainable energy has been inspired by the definition of sustainable development formulated more than 30 years ago in the Our Common Future - the UN’s Report of the World Commission on Environment and Development. The current definition conceals the true spirit of the Report and this has some ramifications. It raises the question as to whether we have put too much emphasis on attaining the future dimension of sustainability in the middle of the situation where the energy survivability is in fact the real issue in many parts of the world. In this paper the role of energy in sustaining livelihoods of low income communities is discussed. Existing definition of sustainable energy that the whole world seems to have embraced is looked at critically and its downsides exposed. The identified pillars of sustainable energy and the associated issues is discussed and the need for an additional pillar, i.e. affordability is discussed and called for. This paper will argue that global definition of sustainable energy seems inappropriate and should be jettisoned and a more realistic definition should be formulated, adopted and embraced at local (i.e. national or regional) level taking into account local attributes and factors. The current push for a transition from the reliance on conventional energy sources to ‘cleaner’ energy sources (generally associated with renewable energy) has further exacerbated the issue of energy affordability that has made the conditions even more dire for so many groups of the world population. In the midst of this situation, those who push for a rushed energy transition seem to be those who also produce unsustainably high carbon footprint but who can easily offset their carbon foot-print through the ‘net-zero’ concept.

The COST Action ‘PED-EU-NET’, JPI Urban Europe, IEA EBC Annex 83 and EERA JP Smart Cities can be considered as the main promoters and pioneer initiatives of the research on Positive Energy Districts (PEDs), that collaborated to develop a tool called 'PED Database'. The tool aims to map, filter, sort, and compare PED experiences, providing a balanced overview of the technological and non-technological solutions adopted in different PED projects and case studies around Europe and beyond. The paper aims to present the collaborative step-by-step process leading to the PED DB implementation, describing the adopted methodology, the current results and potentials of the online version platform and introducing its future possible developments towards a more user-friendly and stakeholders-tailored tool.

HSF1 is a well-known Heat Shock Protein expression regulator in response to stress. It also regulates processes important for growth, development, or tumorigenesis. Here, we studied the HSF1 influence on the phenotype of non-tumorigenic human mammary epithelial (MCF10A and MCF12A) and several triple-negative breast cancer cell lines. MCF10A and MCF12A differ by HSF1 levels, morphology, growth in the matrigel, expression of epithelial (CDH1) and mesenchymal (VIM) markers (MCF10A are epithelial cells, MCF12A resemble mesenchymal cells). HSF1 down-regulation led to reduced proliferation rate and spheroid formation in matrigel by MCF10A cells, while it did not affect the MCF12A proliferation but led to CDH1 up-regulation and the formation of better-organized spheroids. HSF1 overexpression in MCF10A resulted in reduced CDH1 and increased VIM expression, and the acquisition of elongated fibroblast-like morphology. The above results suggest that elevated levels of HSF1 may direct mammary epithelial cells toward a mesenchymal phenotype while lowering HSF1 could reverse the mesenchymal phenotype to an epithelial one. Therefore, HSF1 may be involved in the remodeling of mammary gland architecture over the female lifetime. Moreover, HSF1 levels positively correlated with the invasive phenotype of triple-negative breast cancer cells, and their growth was inhibited by the HSF1 inhibitor, DTHIB.

By making periodic thru-holes in a suspended film, the phonon system can be modified. Motivated by the BCS theory, the technique -- so-called phonon engineering -- was applied to a metallic niobium sheet. It was found that its electrical resistance dropped to zero at 175 K, and the zero-resistance state persisted up to 290 K in the subsequent warming process. Despite the initial motivation, neither these high transition temperatures nor the phase transition with thermal hysteresis can be accounted for by the BCS theory. Therefore, we abandon the BCS theory. Instead, it turns out that the metallic holey sheet is partly oxidized to form a niobium-oxygen square lattice, which has points of resemblance to a copper-oxygen plane, the fundamental component of cuprate high-T_c superconductors. Therefore, the pairing mechanism underlying this study should be related to that of cuprate high-T_c superconductors, which we may not yet understand. In addition to the electrical results of zero resistance, the holey sheet exhibited a decrease in magnetization upon cooling, i.e., the Meissner effect. Moreover, the remnant magnetization was clearly detected at 300 K, which can only be attributed to persistent currents flowing in a superconducting sample. Thus, this study meets the established criteria for a conclusive demonstration of true superconductivity. Finally, the superconducting transition with the unambiguous thermal hysteresis is discussed. According to Halperin, Lubensky, and Ma, or HLM for short, any superconducting transition must always be first order with thermal hysteresis because of the intrinsic fluctuating magnetic field. The HLM theory is very compatible with the highly oriented system harboring two-dimensional superconductivity.

Mitochondrial dysfunction plays a pivotal role in numerous complex diseases. Understanding the molecular mechanisms by which the “powerhouse of the cell” turns into the “factory of death” is an exciting yet challenging task that can unveil new therapeutic targets. The mitochondrial matrix protein CyPD is a peptidylprolyl cis-trans isomerase involved in the regulation of the permeability transition pore (mPTP). The mPTP is a multi-conductance channel in the inner mitochondrial membrane whose dysregulated opening can ultimately lead to cell death and whose involvement in pathology has been extensively documented over the past few decades. Moreover, several mPTP-independent CyPD interactions have been identified, indicating that CyPD could be involved in the fine regulation of several biochemical pathways. To further enrich the picture, CyPD undergoes several post-translational modifications that regulate both its activity and interaction to its clients. Here, we will dissect what is currently known about CyPD and critically review the most recent literature about its involvement in neurodegenerative disorders, focusing on Alzheimer’s Disease and Parkinson’s Disease, supporting the notion that CyPD could serve as a promising therapeutic target for the treatment of such conditions. Notably, significant efforts have been made to develop CyPD-specific inhibitors, which hold promise for the treatment of such complex disorders.

We investigate the evolution of gravitational waves through discontinuous evolution (transition) of the Hubble expansion rate H(z) at a sudden cosmological singularity which may be due to a transition of the value of the gravitational constant. We find the evolution of the scale factor and the gravitational wave waveform through the singularity by imposing the proper boundary conditions. We also use existing cosmological data and mock data of future gravitational wave experiments (the ET) to impose current and anticipated constraints on the magnitude of such a transition. We show that mock data of the Einstein Telescope can reduce the uncertainties by up to a factor of 3 depending on the cosmological parameter considered.

A cross-sectional study was applied to investigate the influence of food systems and food environments on food choices and nutrition transition of households in Limpopo province, South Africa. A sample of 429 households were systematically selected using a paper selection draw from three districts. Food systems, food environments, food choices, and nutritional measurements of the households and informants were assessed, using a validated questionnaire. Most of the household informants responsible for food procurement were females (80.4%). There was a significant association (p < 0.001) between proximity to food stores and dietary diversity of the households. Staple foods were available in almost all surveyed households (95.6%). More than half of the households (59.8%) had home gardens in their yards. Almost half of the households (48.4%) had a low Dietary Diversity Score. The study revealed that 46.0% of households were food secure. Over a third (36.2%) of households’ informants were obese and 32.5% were diabetic. The mean total blood cholesterol was 3.69 ± 0.74 mmol/L. A high percentage of both females (89.6%) and males (91.5%) had normal haemoglobin levels. Most of the informants had normal systolic blood pressure levels (63%), with just over half who had high diastolic levels (57%). The 25 coping strategies were applied during food shortages periods. Even though the food environments provided both obesogenic and protective foods, the consumption of unhealthy foods was high.

Proteomic analysis revealed the preservation of many proteins in the “Heslington brain” (which is at least 2,600-year-old brain tissue uncovered within the skull excavated in 2008 from a pit in Heslington, Yorkshire, England). Five of these proteins (“main proteins”), heavy, medium, and light neurofilament proteins (NFH, NFM, and NFL), glial fibrillary acidic protein (GFAP), and myelin basic (MBP) protein are engaged in the formation non-amyloid protein aggregates, such as intermediate filaments and myelin sheath. We used a wide spectrum of bioinformatics tools to evaluate the prevalence of functional disorder in several related sets of proteins, such as “main proteins” and their 44 interactors, as well as all other protein identified in the Heslington brain. These analyses revealed that all five “main proteins”, half of their interactors and almost one third of the Heslington brain proteins are expected to be mostly disordered. Furthermore, most of the remaining proteins are expected to contain sizable disordered regions. This is in contrary the expected substantial (if not complete) elimination of the disordered proteins from the Heslington brain. Therefore, it seems that the intrinsic disorder of NFH, NFM, NFL, GFAP, and MBP, their interactors and many other proteins might play a crucial role in preserving the Heslington brain by forming tightly folded brain protein aggregates, in which different parts are glued together via the disorder-to-order transitions.

Three-Dimensional mesoporous TiO2 scaffolds of anatase phase possess inherent eximious optical behavior that are beneficial in designing photoelectrodes for solar energy conversion applications. However, substantial efforts have been devoted in maximizing the UV and/or visible light absorption efficiency, and suppressing the annihilation of photogenerated charged species in pristine mesoporous TiO2 structure for improved solar illumination conversion efficiencies. This study provides the fundamental insights into Mxene functionalized mesoporous TiO2 as photoelectrode for the first time. This novel combination of Mxene functionalized TiO2 electrodes with and without TiCl4 treatments have been successfully optimized to intensify the process of photon absorption, charge segregation and photocurrent, resulting in superior photoelectrode performance. The photocurrent measurements of prepared photoelectrodes are significantly enhanced upon increased contents of Mxene due to improved absorption efficiency within the visible region as verified by UV–Vis absorption spectroscopy. Moreover, as evident through structural analysis, the anatase phase of TiO2 is well grown due to increased contents of Mxene and post-deposition heat treatments. Consequently, an appreciable coverage of well-developed grains on FTO surface observed in SEM images. Thereby, the newly fabricated conductive mesoporous TiO2 photoelectrodes are potential candidates for photoinduced energy conversion and storage purposes.

The Heisenberg {\it ab initio} theory of magnetization is developed to apply for multilayer nanoparticles. The theory is based on distribution and partition functions modification with account the difference between exchange integral and closest neighbour numbers, that change the system of resulting transcendental equation for magnetization and its reversal to form either a paramagnetic type curve or hysteresis loops patterns. The equations are obtained within the Heisenberg partition function construction by Heitler diagonalization of energy matrix via irreducible representations of permutation symmetry group. A combination with the Gauss distribution gives the explicit expression for the partition function in the asymptotic limit] at large spin range in terms of transcendent function. The exchange integral, as a parameter of the equation of state (material equation) is evaluated from Curie temperature value by means of a formula derived within the presented theory. Methods of data processing from the simultaneous solution of the material equation system are proposed. The multi-valued function of hysteresis loop is found by combination of graphical approach and special procedure for elimination of mistaken peaks and prolapses of the patterns. The theory and computation methods are applied to spherical particles with separate surface layers consideration. The contribution of the surface layers, that are specified by number of closest neighbors and exchange integrals into overall magnetization, is studied for two-layer and three-layer models, that are discussed and compared graphically.

One of the most used markers of cancer stem cells in several cancers, including colorectal cancer and breast cancer, is CD44. CD44 is a glycoprotein that traverses the cell membrane and binds to many ligands including hyaluronan resulting in activation of signaling cascades. Several reports have shown conflicting data on the expression of CD44 and that the expression depends on modes of investigations and subtypes of cancers. In addition, the correlation between CD44 expression and drug resistance, immune infiltration, EMT, metastasis and patients prognosis in several cancer types remains unclear. This study investigated CD44 expression in several cancers and explored its relationship with tumorigenesis using various publicly available databases, including The Cancer Genome Atlas, GEPIA, Oncomine, Genomics of Drug Sensitivity in Cancer and Tumor Immune Estimation Resource. Our analysis reveals that CD44 is differentially expressed in different cancers. CD44 expression is significantly associated with cancer patients’ survival in gastric, pancreatic and colorectal cancers. In addition, CD44 expression is closely linked with immune infiltration and immune suppressive features in pancreatic, colon adenocarcinoma and stomach cancer. High CD44 expression was significantly correlated with the expression of drug resistance-, EMT- and metastasis- linked genes. Tumors expressing high CD44 have higher mutation burden and afflict older patients than tumors expressing low CD44. Cell lines expressing high CD44 are more resistant to anti-cancer drugs compared to those expressing low CD44. Protein-protein interaction investigations and functional enrichment analysis showed that CD44 interacts with gene products related to cell-substrate adhesion, migration, platelet activation, and cellular response to stress. KEGG pathway analysis revealed that these genes play key roles in biological adhesion, cell component organization, locomotion, G-α-signaling and the response to stimulus. Overall, this investigation reveals that CD44 play significant roles in tumorigenesis, can be used as a prognostic biomarker in several cancers and can be therapeutically targeted in cancer therapy.

The FOLFOX scheme, based on the association of 5-fluorouracil and oxaliplatin, is the most frequently indicated chemotherapy scheme for patients diagnosed with metastatic colorectal cancer. Nevertheless, development of chemoresistance is one of the major challenges associated with this disease. It has been reported that epithelial-mesenchymal transition (EMT) is implicated in microRNA-driven modulation of tumor cells response to 5-fluorouracil and oxaliplatin. Besides, from pharmacogenomic research it is known that overexpression of genes encoding dihydropyrimidine dehydrogenase (DPYD), thymidylate synthase (TYMS), methylenetetrahydrofolate reductase (MTHFR), the DNA repair enzymes ERCC1, ERCC2, and XRCC1, and the phase 2 enzyme GSTP1 impair the response to FOLFOX. It has been observed that EMT is associated with overexpression of DPYD, TYMS, ERCC1, and GSTP1. In this review we investigated the role of miRNAs as EMT promotors in tumor cells, and its potential effect on upregulation of DPYD, TYMS, MTHFR, ERCC1, ERCC2, XRCC1 and GSTP1 expression, which would lead to resistance of CRC tumor cells to 5-fluorouracil and oxaliplatin. This constitutes a potential mechanism of epigenetic regulation involved in late-onset of acquired resistance in mCRC patients under FOLFOX chemotherapy. Expression of these biomarkers microRNA could serve as tools for personalized medicine, and as potential therapeutic targets in the future.

Transition metal complexes have historically played a pivotal role in creating vibrant pigments utilized across artistic mediums such as ceramics, paintings, and glass mosaics. Despite their extensive historical use, our understanding of the mechanisms governing transition metal complex behavior has predominantly emerged in recent times, leaving numerous aspects of this process ripe for exploration. These complexes exhibit striking color variations under diverse conditions when employed in pigment formulations. This review utilizes a bottom-up scientific approach, spanning from microscopic to macroscopic scales, to unravel the molecular origins of the colors generated by transition metal complexes in pigments and ceramic glazes. Advanced spectroscopy techniques and computational chemistry play pivotal roles in this endeavor, highlighting the significance of understanding and utilizing analytical data effectively, with careful consideration of each technique's specific application. Furthermore, the review investigates the influence of processing conditions on color variations, providing valuable insights for artists and manufacturers aiming to enhance the precision and quality of their creations while mitigating environmental impact.

Non-normal mode stability analysis has long been employed to study linear transient characteristics of wall bounded shear flows. However, the application of this approach to investigate shear flows with stratified thermal conditions (STCF) has received limited attention. This paper examines thermal effects on Taylor-Couette flow. The results in this study indicate the possibility of a subcritical bifurcation in stratified Taylor-Couette flow.

The present study was aimed at revealing the influence of the mechanical stress induced by water molecules adsorption on the composition of crystalline phases in the ZrO2–3mol%Y2O3-nanoparticles. Three basic methods have been used to determine the phase transition: neutron diffraction, Raman microspectroscopic scanning, and X-ray diffraction. The fact of phase-structural β → α transformation and the simultaneous presence of two polymorphic structural modifications (β is the phase of the tetragonal syngony and α of monoclinic syngony in nanosized particles (9nm)) under normal physical conditions was established by these methods. Satisfactory consistency was achieved between the results obtained using different techniques.

Epithelial-mesenchymal transition (EMT) networks are essential in acquiring the drug resistance and cancer malignant features in cancer stem cells (CSCs). In this regard, gene expression profiles in diffuse- and intestinal-type gastric cancer (GC) have been analyzed to reveal the network pathways in EMT and CSCs, since the diffuse-type GC has much more mesenchymal features than intestinal-type GC that has the intestinal features. The study results revealed that the activation state of several canonical pathways related to cell cycle regulation was altered. The canonical pathway on Cell cycle: G1/S checkpoint regulation was activated in diffuse-type GC, and canonical pathways on Cell cycle control of chromosomal replication and Cyclins and cell cycle regulation were activated in intestinal-type GC. Canonical pathway related to Role of BRCA1 in DNA damage response was activated in intestinal-type GC, where BRCA1, which is related to G1/S phase transition was up-regulated in intestinal-type GC. Several microRNAs (miRNAs), including mir-10, mir-17, mir-19, mir-194, mir-224, mir-25, mir-34, mir-451, and mir-605, were identified to have direct relationships of RNA-RNA interaction in Cell cycle: G1/S checkpoint regulation pathway. Additionally, cell cycle regulation may be altered in EMT conditions. The alterations in activation states of the pathways related to cell cycle regulation in diffuse- and intestinal-type GC would indicate the significance of cell cycle regulation in EMT.

For the better part of a century researchers across disciplines have sought to explain the crystallography of the elemental transition metals: hexagonal close packed, body centered cubic, and face centered cubic in a form similar to that used to rationalize the structure of organic molecules and inorganic complexes. Pauling himself tried with limited success to address the origins of transition metal stability. These early investigators were handicapped, however, by incomplete knowledge regarding the structure of metallic charge density. Here we exploit modern approaches to charge analysis to first comprehensively describe transition metal charge density. Then, we use topological partitioning and quantum mechanically rigorous treatments of kinetic energy to account for the structure of the density as arising from the interactions between metallic tetrahedra. We argue that the crystallography of the early transition metals results from charge transfer from the so called “octahedral” to “tetrahedral holes” while the face centered cubic structure of the late transition metals is a consequence of antibonding interactions that increase octahedral hole kinetic energy.

The activity of the mitochondrial Permeability Transition Pore, mPTP, a highly regulated multi-component mega-channel, is enhanced in aging and in aging-driven degenerative diseases. mPTP activity accelerates aging by releasing large amounts of cell-damaging Reactive Oxygen Species, Ca2+ and NAD+. The various pathways that control the channel activity, directly or indirectly, can therefore either, inhibit, or accelerate aging, retards, or enhance the progression of aging-driven degenerative diseases, and determine lifespan and healthspan. Autophagy, a catabolic process that removes and digests damaged proteins and organelles protects the cell against aging and disease. However, the protective effect of autophagy depends on mTORC2/SKG1 inhibition of mPTP. Autophagy is inhibited in aging cells. Mitophagy, a specialized form of autophagy, which retards aging by removing mitochondrial fragments with activated mPTP, is also inhibited in aging cells, and this inhibition leads to increased mPTP activation, which is a major contributor to neurodegenerative diseases, such as Alzheimer’s and Parkinson’s Diseases. The Increased activity of mPTP in aging turns autophagy/mitophagy into a destructive process leading to cell aging and death. Several drugs and lifestyle modifications that enhance healthspan and lifespan enhance autophagy and inhibit the activation of mPTP. Therefore, elucidating the intricate connections between pathways that activate and inhibit mPTP, in the context of aging and degenerative diseases, could enhance the discovery of new drugs and lifestyle modifications that slow aging and degenerative disease.

The design of more efficient photosensitizers is a matter of great importance in the field of cancer treatment by means of photodynamic therapy. One of the main processes involved in the activation of apoptosis in cancer cells is the oxidative stress on DNA once a photosensitizer is excited by light. As a consequence, it is a matter of great relevance to investigate in detail the binding modes of the chromophore with DNA, and the nature of the electronically excited states that participate in the induction of DNA damage, for example, charge-transfer states. In this work, we investigate the electronic structure of the anthraquinone photosensitizer intercalated into a double-stranded poly(dG-dC) decamer model of DNA. First, the different geometric configurations are analyzed by means of classical molecular dynamics simulations. Then, the excited states for the most relevant poses of anthraquinone inside the binding pocket are computed by an electrostatic-embedding quantum mechanics/molecular mechanics approach, where anthraquinone and one of the nearby guanine residues are described quantum mechanically to take into account intermolecular charge-transfer states. The excited states are characterized as monomer, exciton, excimer and charge-transfer states based on the analysis of the transition density matrix, and each of these contributions to the total density of states and absorption spectrum is discussed in terms of the stacking interactions. These results are relevant as they represent the footing for future studies on the reactivity of anthraquinone derivatives with DNA and give insights on possible geometrical configurations that potentially favor the oxidative stress of DNA.

We have investigated the influence of the relative proportions of glass formers in a series of lithium alumino-borosilicate glasses with respect to electrical conductivity () and glass transition temperature (Tg) as functions of glass structure, as determined by Raman spectroscopy. The ternary lithium alumino-borate glass exhibits the highest  and lowest Tg among all the compositions of the glass series, 30Li2O•3Al2O3• (67-x) B2O3•xSiO2. However, as B2O3 is replaced by SiO2, a shallow minimum in  as well as a shallow maximum in Tg are observed near x = 27, where the Raman spectra indicate isolated diborate/tetraborate/orthoborate groups are being progressively replaced by danburite/reedmergnerite-like borosilicate network units. Overall, as the glasses become silica-rich,  is minimized, while Tg is maximized. In general, these findings show correlations among Tg, (sensitive to network polymerization),  (proportional to ionic mobility), and the different borate and silicate glass structural units as determined by Raman spectroscopy. X-ray diffraction analyses demonstrate the absence of appreciable crystallinity in the glasses investigated. However, scanning electron microscopy (SEM) images of HF-etched samples showed that glasses, and especially the borate-rich compositions comprise two distinct glassy phases. The isolated phase is 25-100 nm in diameter, dispersed evenly in a glassy matrix.

In this study, we considered the structural stability, electronic properties, and phonon dispersion of the cubic (c-ZrO₂), tetragonal (t-ZrO₂), and monoclinic (m-ZrO₂) phases of ZrO₂. We found that the monoclinic phase of zirconium dioxide is the most stable among the three phases in terms of total energy, lowest enthalpy, highest entropy, and other thermodynamic properties. The smallest negative modes were found for m-ZrO₂. Our analysis of the electronic properties showed that during the m–t phase transformation of ZrO₂, the Fermi level first shifts by 0.125 eV toward higher energies and then decreases by 0.08 eV in the t–c cross-section. The band gaps for c-ZrO₂, t-ZrO₂, and m-ZrO₂ are 5.140 eV, 5.898 eV, and 5.288 eV, respectively. Calculations based on the analysis of the influence of doping 3.23, 6.67, 10.35, and 16.15 mol. %Y₂O₃ onto the m-ZrO₂ structure showed that the enthalpy of m-YSZ decreases linearly, which accompanies further stabilization of monoclinic ZrO₂ and an increase in its defectiveness. In this case, the position of the Fermi level changes abruptly, and the energy gap decreases. It has been established that, not only for pure systems but including those doped with Y₂O₃, the main contribution to the formation of the conduction band is made by the p-states of electrons. The t-ZrO₂ (101) and t-YSZ (101) surface models were selected as optimal surfaces for water adsorption based on a comparison of their surface energies. An analysis of the mechanism of water adsorption on the surface of t-ZrO₂ (101) and t-YSZ (101) showed that H₂O on unstabilized t-ZrO₂ (101) is adsorbed dissociatively with an energy of -1.22 eV, as well as by the method of molecular chemisorption with an energy of - 0.69 eV and the formation of a hydrogen bond with a bond length of 1.01 Å. In the case of t-YSZ (101), water is molecularly adsorbed onto the surface with an energy of -1.84 eV. Dissociative adsorption of water occurs at an energy of -1.23 eV, near the yttrium atom. The obtained results complement the database of research works carried out in the field of the application of biocompatible zirconium dioxide crystals and ceramics in green energy generation and can be used in designing humidity-to-electricity converters and creating solid oxide fuel cells based on ZrO₂.

Family Phyllanthaceae is one of the largest segregates of the eudicot order Malpighiales and its species are herb, shrub, and tree, which are mostly distributed in tropical regions. Certain taxonomic discrepancies exist at genus and family level. Here, we report chloroplast genomes of three Phyllanthaceae species—Phyllanthus emblica, Flueggea virosa, and Leptopus cordifolius— and compare them with six others previously reported Phyllanthaceae chloroplast genomes. The species of Phyllanthaceae displayed quadripartite structure, comprising inverted repeat regions (IRa and IRb) that separate large single copy (LSC) and small single copy (SSC) regions. The length of complete chloroplast genome ranged from 154,707 bp to 161,093 bp; LSC from 83,627 bp to 89,932 bp; IRs from 23,921 bp to 27,128 bp; and SSC from 17,424 bp to 19,441 bp. Chloroplast genomes contained 111 to 112 unique genes, including 77 to 78 protein-coding, 30 transfer RNA (tRNA), and 4 ribosomal RNA (rRNA) that showed similarities in arrangement. The number of protein-coding genes varied due to deletion/pseudogenization of rps16 genes in Baccaurea ramiflora and Leptopus cordifolius. High variability was seen in number of oligonucleotide repeats while analysis of guanine-cytosine (GC) content, codon usage, amino acid frequency, simple sequence repeats analysis, synonymous and non-synonymous substitutions, and transition and transversion substitutions showed similarities in all Phyllanthaceae species. We detected a higher number of transition substitutions in the coding sequences than non-coding sequences. Moreover, the high number of transition substitutions was determined among the distantly related species in comparison to closely related species. Phylogenetic analysis shows the polyphyletic nature of the genus Phyllanthus which requires further verification. We also determined suitable polymorphic coding genes, including rpl22, ycf1, matK, ndhF, and rps15 which may be helpful for the reconstruction of the high-resolution phylogenetic tree of the family Phyllanthaceae using a large number of species in the future. Overall, the current study provides insight into chloroplast genome evolution in Phyllanthaceae.

The forest transition – or forest-area transition – has been put forward as a land-use concept by A.S. Mather in 1992 (The forest transition. Area 24, 367-379), to describe the historical trend generally observed in the forest area of developed countries, embodied in a V-shaped curve of the forest area over time, and that may serve as a paradigm to understand and anticipate deforestation in the developing world. Well in line with a geographical approach to forests, forest transition has thus been defined as one-dimensional, forest area being the reference state variable. From a forestry perspective, the analysis appears to be reductive, as forests are described by many other state variables than area, including forest growing stock, composition in tree species, or stand structure. Whether the drivers of forest transition (population dynamics, economic modes of production and consciousness, as classified by Mather) also impact these other forest state variables in a general way thus comes forth as a logical issue.From a deductive analysis of forest transition drivers, and from forest trends brought to light in Europe, France, and at other places in the world, we here argue that the forest transition concept can be extended to a multi-dimensional space of forest attributes, characterized by typical ideal dynamics. Cumulative impacts onto forests and irreversible losses in forest biodiversity over a forest transition are hence highlighted. Global change, as a parallel consequence of countries’ developing process, further appears as one additional albeit less coupled dimension of forest transition, as it modifies forest productivity and vitality over time. Since forest ecosystem services and forest profitability primarily depend on such attributes, we argue that the extension of the forest transition concept has significance for land-use change and forest protection issues. A prospect on future changes in the forests of developed countries with the European space as a benchmark is finally proposed that leads to extend the temporal significance of forest transition. Though poorly described, returning forests on abandoned agricultural lands are significant, and deserve greater attention.

In line with Pomeau’s conjecture about the relevance of directed percolation (DP) to turbulence onset/decay in wall-bounded flows, we propose a minimal stochastic model dedicated to the interpretation of the spatially intermittent regimes observed in channel flow before its return to laminar flow. Numerical simulations show that a regime with bands obliquely drifting in two stream-wise symmetrical directions bifurcates into an asymmetrical regime, before ultimately decaying to laminar flow. The model is expressed in terms of a probabilistic cellular automaton evolving von Neumann neighbourhoods with probabilities educed from a close examination of simulation results. It implements band propagation and the two main local processes: longitudinal splitting involving bands with the same orientation, and transversal splitting giving birth to a daughter band with orientation opposite to that of its mother. The ultimate decay stage observed to display one-dimensional DP properties in a two-dimensional geometry is interpreted as resulting from the irrelevance of lateral spreading in the single-orientation regime. The model also reproduces the bifurcation restoring the symmetry upon variation of the probability attached to transversal splitting, which opens the way to a study of the critical properties of that bifurcation, in analogy with thermodynamic phase transitions.

Previously, we demonstrated that IR triggers the invasion/migration of A549 cells via activation of an EGFR–p38/ERK–STAT3/CREB-1–EMT pathway. Here, we have demonstrated the involvement of a novel intracellular signaling mechanism in γ-ionizing radiation (IR)-induced migration/invasion. Expression of receptor-interacting protein (RIP) 1 was initially increased upon exposure of A549, a non-small cell lung cancer (NSCLC) cell line, to IR. IR-induced RIP1 is located downstream of EGFR and involved in the expression/activity of matrix metalloproteases (MMP-2 and MMP-9) and vimentin, suggesting a role in epithelial-mesenchymal transition (EMT). Our experiments showed that IR-induced RIP1 sequentially induces Src-STAT3-EMT to promote invasion/migration. Inhibition of RIP1 kinase activity and expression blocked induction of EMT by IR and suppressed the levels and activities of MMP-2, MMP-9, and vimentin. IR-induced RIP1 activation was additionally associated with stimulation of the transcriptional factor NF-κB. Specifically, exposure to IR triggered NF-κB activation and inhibition of NF-κB suppressed IR-induced RIP1 expression followed by a decrease in invasion/migration as well as EMT. Based on the collective results, we propose that IR concomitantly activates EGFR and NF-κB and subsequently triggers the RIP1–Src/STAT3–EMT pathway, ultimately promoting metastasis.

Causal relationships lie at the very core of our scientific description of biophysical phenomena. Nevertheless, observable facts such as chaotic dynamics, symmetry breaks, long-range collisionless neural interactions, zero-value energy singularities, particle/wave duality, ecological approaches to visual perception elude cause effect inductive explanations. We illustrate how simple topological claims, seemingly useless and far away from scientific inquiry (e.g., “given at least some wind on Earth, there must at all times be a cyclone or anticyclone somewhere”; “if one stirs to dissolve a lump of sugar in a cup of coffee, it appears there is always a point without motion”; “at any moment, there is always a pair of antipodal points on the Earth’s surface with equal temperatures and barometric pressures”) describe a real world, made of projections and mappings unsupplied with causality. Unavoidable, necessary, passive, spontaneous changes in systems’ shapes, dimensions and symmetries incarnate biophysical quantifiable counterparts of abstract mathematical concepts. Real features arising from topological mechanisms do not require causal powers to be produced, because are independent of exerted physical forces, energetic fields’ actions and thermodynamic constraints. Providing examples that shed novel interpretative light on phenomena such as double slit experiments, cellular mechanisms and brain function, we conclude as follows: countless scientific matters can be accessed through methodological weapons which not just break causality, replace temporal correlations and probabilistic a priori knowledge of previous cases, but also permit augments in available information devoid of entropy increases and energy losses.

Developing particles of different anisotropic shapes are the hot topic since decades as they guarantee some special features of properties not possible through other means. Again, controlling atoms to develop certain size and shape particle is a quite challenging job. In this study, gold particles of different shapes are developed via pulse-based electronphoton-solution interface process. Gold atoms of certain transition state develop monolayer assembly at solution surface around the light glow (known in argon plasma) being generated at bottom of copper capillary (known in cathode). The rate of uplifting gold atoms to solution surface is being controlled by forcing energy (travelling photons) pursuing electrons and high energy photons (in high density) entering to solution. Gold atoms dissociated from the precursor under dissipating heat energy into the solution supplied under propagating photons characteristic current through immersed graphite rod (known in anode). Placing packets of nano shape energy of tuned pulse protocol over compact monolayer assembly comprising transition state atoms develop tiny-sized particles of formed shape. On separation of joint tiny particles into two equilateral triangular-shaped tiny particles, exerting forces of surface format elongate atoms of one-dimensional arrays converting them into structures of smooth elements. Due to immersing level of force, such tiny-shaped particles pack from different zones at centre of light glow where they assembled structures of smooth elements for developing mono-layers of different shapes of particles. Developing one-dimensional particles deal assembling of structures of smooth elements of packing tiny-shaped particles from nearly rearward zones of reflection of north-south poles, whereas, developing multi-dimensional particles deal assembling of structures of smooth elements of packing tiny-shaped particles from the east-west poles and near regions. Depending on the number of assembled structures of smooth elements at point of nucleation, packing of tiny-shaped particles from different zones develop different shapes of the anisotropic particles. At fixed precursor concentration, increasing the process time results into develop particles of low aspect ratio. Under tuned parameters, developing mechanisms of particles exhibiting unprecedented features are discussed.

The broad emission bump in the electromagnetic spectra observed following the detection of gravitational waves created during the kilonova event of merger of two neutron stars in August 2017, GW170817, has been linked to the heavy elements of lanthanides (Z=57-71), and a new understanding of creation of heavy elements in the r-process. The initial spectral emission bump has a wavelength range of 3000 - 7000 \AA, thus covering the region of ultraviolet (UV) to optical (O) wavelengths, and is similar to those seen for lanthanides. Most lanthanides have large number of closely lying energy levels which introduce extensive sets of radiative transitions which often form broad region of lines of significant strength. The current study explores these broad features through photoabsorption spectroscopy of 25 lanthanides ions, Ho I-III, Er I-IV, Tm I-V, Yb I-VI and Lu I-VII. With excitations only to a few orbitals up beyond the ground configurations, we find most of these ions cover large number of bound levels with open $4f$ orbital and produce tens to about hundred thousands lines that may form one or multiple broad features in X-ray to UV, O, and infrared (IR) regions. Spectrum of each of 25 ions is presented indicating presence, shape and wavelength region of the features. Accuracy of atomic data to interpret the merger spectra has been a outstanding problem. The present study aims at providing improved atomic data for energies and transition parameters obtained using relativistic Breit-Pauli approximation implemented in the atomic structure code SUPERSTRUCTURE. The present data have been benchmarked with available experimental data for energies and transition parameters. The study finds that number of ions under the present study are possible contributors of the emission bump of GW170817. All atomic data will be made available online at NORAD-Atomic-Data database.

The temperature effect plays an important role for an accurate determination of the polar free energy, polar thermodynamic parameters, and enthalpic and entropic Lewis’s acid base properties of oxides, polymers and composites polymers/oxides. The adsorption of polymers on other solid surfaces is crucial in many industrial applications, coatings, paints, catalysis, colloids and adhesion processes. (1) Background: Inverse gas chromatography at infinite was used for the physico-chemical characterization of solid substrates by determining the thermodynamic parameters of adsorption of model organic solvents on solid surfaces such as polymers, metallic oxides, carbon fibers, pharmaceutical or 3D/4D printing substrates. (2) Methods: A new method based on the London dispersion equation was applied with a new parameter associating the deformation po-larizability and the harmonic mean of the ionization energies of solvent. More accurate values of the dispersive and polar interaction energies of the various organic solvents adsorbed on PMMA in bulk phase and PMMA/silica at different recovery fractions were obtained as well as the Lewis acid-base parameters and the transition temperatures of the different composites. (3) Results: This new methodology gave very interesting results on the behavior of PMMA adsorbed on silica. An important effect of the temperature and the recovery fraction on the various physicochemical and thermodynamic properties was highlighted. The variations of all interaction parameters showed the presence of three transition temperatures for the different PMMA adsorbed on silica with the various coverage rates with a shift of these temperatures for a recovery fraction of 31% (4) Con-clusions: An important variation of the polar enthalpy and entropy of adsorption, the Lewis ac-id-base parameters and the intermolecular separation distance as a function of the temperature and the recovery fraction of PMMA on silica.

The global energy transition is motivated largely by the need to combat climate change. Other reasons include limits to available fossil fuels, energy-related environmental impacts of many kinds, and societal goals such as equity and providing sustainable energy for the poor. This transition will significantly change the world both technically, economically and socially. It is taking shape with characteristics which prioritise certain types of policy, interventions and solutions, as well as certain actors and institutional forces. More fundamentally, it embodies underlying assumptions about what constitutes a desirable type of economy and society. Briefly stated, the energy transition is being geared to a conventional economic growth-focused type of development; including the not unchallenged concept of green growth. Not everyone, however, would agree on those priorities or the underlying assumptions. We point out various constraints and limitations which this approach places on the energy transition. Whilst much of the change being initiated is positive, we argue that different views, which lie closer to discourses such as strong sustainability (1), deep ecology (2) and ecological economics (3, 4) might prioritise differently and offer both necessary and desirable outcomes. Given the predominant focus on energy and climate, equally essential goals such as equity and eradication of poverty appear to be at particular risk of being missed. Building on examples and recent experience we argue that achieving global sustainable energy, not least the societal goals, remains unlikely within socio-political frameworks permeated by the imperatives of market-driven growth, the commodification of resources, and intense competitive dynamics. Technology and economics, the themes of this issue, have far-reaching societal implications and outcomes. We argue that it is essential that they be considered within the broad context discussed here.

The global transport sector of the world economy contributes about 15% of the Greenhouse Gas (GHGs) emissions in the world today. The University of Saskatchewan has pursued the green energy transition over the years. They have spearheaded diverse sustainability projects and agendas, due to the importance of curbing climate change and advancing sustainability. The transport system in the university campus is one area of focus where the Sustainability Office plans to introduce some innovations, as a way of curbing GHG emissions while also advancing sustainability practice in the university campus. The study carried out an economic benefit analysis on the campus fleet (consisting of 91 ICE vehicles) to determine if it is economically or financially feasible to transition from Internal Combustion Engine (ICE) or PVs (Petrol Vehicles) to Electric Vehicles (EVs). The analysis used RETScreen Expert software for analyzing renewable energy technology projects. The variables of Payback Period (PBP), cash flow projections, savings made from transitioning (fuel cost savings and energy cost savings), Benefit-Cost-ratio, GHG emission reduction potential, etc. were analyzed. The findings revealed that the GHG emission from the campus fleet will be reduced by 100% (this will result in the removal of about 298.1 tCO₂ from the environment). Also, the fleet manager will save approximately $129,049 (88.9%) in fuel costs. Apart from these, the return on investment will be achieved in year 5 (all things being equal), but can be reduced to year 2 if the vehicles are put into constant and active use (eliminating most idle times. Also, the Sustainability Office will be making a GHG reduction revenue of $14,906.

Sustainable and Responsible Design (SRD) harnesses design’s potential to address eco-social problems and in doing so challenge the status quo of design education by reframing the social and ecological consequences, boundaries and agencies of design. This critical and transdisciplinary approach frays the edges of traditional design disciplines with embedded and reflexive modes of learning. We describe characteristics of SRD education and present theories of learning to empower students in this complex terrain. The learning associated with SRD education is ecologically engaged, participative, critical, expansive and designerly. We recount case studies of our own experiences advancing sustainable and responsible undergraduate design education in the UK. We identify path constraints such as disciplinary fragility, appropriation, and power dynamics in the design school. The push for a revision of priorities generates tensions where there is often greenwashing rhetoric of sustainability and inclusivity. We describe strategies and tactics to address these tensions. We highlight the agency we have as educators and designers and argue that design education can only meaningfully participate in response to the challenges presented by climate change, other types of ecocide, and social problems when educators make substantive commitments to supporting sustainability literacies and design approaches that serve the interests of diverse stakeholders.

The Epithelial- Mesenchymal Transition (EMT) is a biological phenomenon associated with explicit phenotypic and molecular changes in cellular traits. Unlike the earlier-held popular belief of it being a binary process, EMT is now thought of as a landscape including diverse hybrid E/M phenotypes manifested by varying degrees of the transition. These hybrid cells can co-express both epithelial and mesenchymal markers and/or functional traits, and can possess the property of collective cell migration, enhanced tumor-initiating ability, and immune/targeted therapy-evasive features, all of which are often associated with worse patient outcomes. These characteristics of the hybrid E/M cells have led to a surge in studies that map their biophysical and biochemical hallmarks that can be helpful in exploiting their therapeutic vulnerabilities. This review discusses recent advances made in investigating hybrid E/M phenotype(s) from diverse biophysical and biochemical aspects by integrating live cell-imaging, cellular morphology quantification and mathematical modeling, and highlights a set of questions that remain unanswered about the dynamics of hybrid E/M states.

Bioenergetics, genetic coding, and catalysis are all difficult to imagine emerging without pre-existing historical context. That context is often posed as a “Chicken and Egg” problem; its resolution is concisely described by de Grasse Tyson: “the egg was laid by a bird that was not a chicken”. The concision and generality of that answer furnish no details—only an appropriate framework from which to examine detailed paradigms that might illuminate paradoxes underlying these three life-defining biomolecular processes. We examine experimental aspects here of five examples that all conform to the same paradigm. The paradox in each example is resolved by coupling if, and only if, conditions for two related transitions between levels. One drives, and each restricts fluxes through, or “gates” the other. That reciprocally-coupled gating, in which two gated processes constrain one another, maps onto the formal structure of “strange loops”. That mapping may help unite the axiomatic foundations of genetics, bioenergetics, and catalysis. As a physical analog for Gödel’s logic, biomolecular strange-loops provide a natural metaphor around which to organize these data, linking biology to the physics of information, free energy, and the second law of thermodynamics.

The first objective of this paper is to investigate the scaling behavior of liquid-vapor phase transition in FCC and BCC metals starting from the zero-temperature four-parameter formula for cohesive energy. The effective potentials between the atoms in the solid are determined using lattice inversion techniques as a function of scaling variables in the above formula. These potentials are split into repulsive and attractive parts as per the Weeks-Chandler-Anderson prescription, and used in the coupling-parameter expansion for solving the Ornstein-Zernike equation supplemented with an accurate closure. Thermodynamic quantities obtained via the correlation functions are used to obtain critical point parameters and liquid-vapor phase diagrams. Their dependence on the scaling variables in the cohesive energy formula are also determined. Equally important second objective of the paper is to revisit coupling parameter expansion for solving the Ornstein-Zernike equation. The Newton-Armijo non-linear solver and Krylov-space based linear solvers are employed in this regard. These methods generate a robust algorithm that can be used to span the entire fluid region, except very low temperatures. Accuracy of the method is established by comparing the phase diagrams with those obtained via computer simulation. Avoidance of the 'no-solution-region' of Ornstein-Zernike equation in coupling-parameter expansion is also discussed. Details of the method and the complete algorithm provided here would make this technique more accessible to researchers investigating thermodynamic properties of one component fluids.

Chronic rhinosinusitis is a common inflammatory disease of paranasal sinuses, which causes rhinorrhea, nasal congestion and hyposmia. The genetic predisposition or the exposure to irritants can sustain the inflammatory response and the development of nasal polyposis. Nasal polyps are benign and teardrop-shaped growths that project in the nasal cavities and originate from the ethmoid sinuses. This inflammatory process is associated with high expression of IL-5 cytokine and infiltration of eosinophils. Humanized monoclonal antibodies targeting IL-5 or its receptor, represent a therapeutic strategy in the treatment of nasal polyposis in combination with corticosteroids. The molecular pathogenesis of nasal polyps in CRS patients is associated to the epithelial-mesenchymal transition (EMT), a process in which epithelial cells lose their typical phenotype acquiring a mesenchymal phenotype. TGFβ/SMAD, ERK, and Wnt/β-catenin pathways are altered in EMT during the nasal tissue remodeling. miRNA and inhibitor molecules targeting these altered signaling pathways are able to interfere with EMT; which could lead to alternative therapies. Nasal polyps are an alternative source of mesenchymal stem cells which can be easily isolated from surgical biopsies. A molecular understanding of the biology of PO-MSCs will contribute to delineating inflammatory process underlying the development of nasal polyps.

Abstract: The conundrum of Latin American countries in the green transition unveils new opportunities and old structural problems. There is a clear advantage in the energy grid for Argentina, Brazil, and Mexico, coming mainly from hydropower, solar, and wind energy. In 2022, Brazil had the largest solar photovoltaic energy generation capacity in Latin America and the Caribbean, with over 24 gigawatts. Mexico ranked second, with some 9 gigawatts, and Chile ranked third, with a capacity of around 6 gigawatts. The window of opportunity for the industrialized Latin American countries resides chiefly in greening the natural resources industries and agriculture and husbandry, mainly for Brazil and Argentina. Latin America faces the dual challenge of promoting renewable energy and upgrading its value chains while managing the socioeconomic dynamics inherent in its developmental stages. It poses an enormous challenge for Latin American countries because of the phenomenon of "time compression" (Whittaker et al., 2020). Developing country's innovation and technology-intensive segments coexist with informal labor and low-skilled workers. Far from disappearing with economic growth, such coexistence becomes reinforced through an increasingly wide array of temporary and insecure jobs. Time compression condenses different stages of industrial and economic development within the same space and time, directly affecting the indicators related to the reduction of environmental impacts. Instead of locking in one path for this transition, Latin American countries had better not cling to panaceas but consider the threats, the risks, and the need to experiment with multiple paths and solutions simultaneously. However, this change implies the formation of a genuine developmental and environmental coalition guided by rigorous strategic considerations not captured by immediate interests.

One objective of this paper is to investigate bifurcation of solutions of Ornstein-Zernike equation in liquid state theory for the gas-liquid coexistence region of simple fluids. The analysis uses a discrete form of the Ornstein-Zernike equation in real space, together with a closure relation which provides nearly self consistent thermodynamic properties of fluids governed by interaction potentials like the Lennard-Jones potential. Accurate asymptotic forms of correlation functions are incorporated in the real space algorithm so as to mitigate the influence of cutoff length used in the discrete approximations. It is found that there is no spinodal on the vapor side on a sub-critical isotherm. But there are fold bifurcation points on the vapor and liquid sides together with a 'no-real-solution-region' in between. This is followed by a region of negative compressibility extending up to the spinodal on the liquid side. The emerging picture is quite similar to that in the case of the hypernetted-chain-closure. It is also found that complex solutions connect the physical solutions that exist outside the 'no-real-solution-region' as well as in region of negative compressibility. The second objective of the paper, in the light of bifurcation scenario, is to evolve an interpretation of the coupling-parameter expansion of correlation functions pertaining to the region of negative compressibility. It is shown that the expansion provides an accurate description of results of the restricted ensembles, implied in mean field theories and simulation methods. Bifurcation of singlet density to inhomogeneous distributions at a spinodal is also established using a simple equation, which uses the direct correlation function. Thus the paper reestablishes the fact that restriction to a homogeneous singlet density is the root cause of all inconsistencies found in the gas-liquid coexistence region.

This research aims to understand the Cambodian green economy transition and analyze its strengths, weaknesses, opportunities, and threats (SWOT). The research showed that Cambodia has been significantly transitioning its green economy since 2009 as evidenced by the National Green Growth Roadmap. Cambodia also established the National Council for Green Growth in 2012 and upgraded it to the National Council for Sustainable Development in 2015 in alignment with 2030 Agenda for Sustainable Development of the United Nations. The members of the Council are from all the government’s ministries and relevant inter-ministerial councils/committees, which are significant for policymaking. All governors of the capital and provincial administrations are also its members, which are significant for supporting and implementing the works at the subnational levels. Under the structure of the Council’s Secretariat, Department of Green Economy is playing an important role in promoting green economic development in Cambodia by looking at national policies and strategic plans, undertaking projects, and mobilizing resources. Through coordination between this Department and UNIDO, Cambodia in 2022 became a Member of the United Nations Partnership for Action on Green Economy. The findings showed that Cambodia is transitioning its green economy at the right time, especially the new government’s Pentagonal Strategy strongly supported this green economy transition with a clear and strong political commitment. The national inter-ministerial council for sustainable development is also very significant for cross sectoral policy-making and implementing levels, inclusively for promoting green economic development.

Municipal Solid Waste Management (MSWM) struggles with significant policy and operational challenges, particularly concerning recyclables collection routes and fleet composition. Within the European Union, phasing out traditional fuel-based vocational vehicles, like garbage trucks, in favor of zero-emission alternatives is mandatory to achieve sustainable development objectives. Integrating electric solid waste collection vehicles into municipal fleets presents challenges due to differences in range, capacity, and noise levels. The emission is even more crucial in the systems where recyclables are collected separately, which requires a greater number of trips to be performed. This study addresses MSWM’s strategic aspect by minimizing the total cost of replacing waste collection vehicles while meeting emission constraints. The Fleet Transition Problem (FTP) was formulated and solved using a MARKAL-based approach. The objective of the FTP and a mixed integer linear program used to solve it is minimizing the overall cost of fleet modernization throughout a multi-phase planning horizon so that the sustainable transition of the fleet can be assured. Computational experiments affirmed the model’s effectiveness in strategizing fleet transition. This research outlines a multi-period model for transitioning to a zero-emission fleet and demonstrates the FTP’s potential for strategic decision-making. Notably, the study observes a consistent reduction in permissible emissions across the planning horizon.

In this study, we considered the structural stability, electronic properties, and phonon dispersion of the cubic (c-ZrO₂), tetragonal (t-ZrO₂), and monoclinic (m-ZrO₂) phases of ZrO₂. We found that the monoclinic phase of zirconium dioxide is the most stable among the three phases in terms of total energy, lowest enthalpy, highest entropy, and other thermodynamic properties. The smallest negative modes were found for m-ZrO₂. Our analysis of the electronic properties showed that during the m–t phase transformation of ZrO₂, the Fermi level first shifts by 0.125 eV toward higher energies and then decreases by 0.08 eV in the t–c cross-section. The band gaps for c-ZrO₂, t-ZrO₂, and m-ZrO₂ are 5.140 eV, 5.898 eV, and 5.288 eV, respectively. Calculations based on the analysis of the influence of doping 3.23, 6.67, 10.35, and 16.15 mol. %Y₂O₃ onto the m-ZrO₂ structure showed that the enthalpy of m-YSZ decreases linearly, which accompanies further stabilization of monoclinic ZrO₂ and an increase in its defectiveness. A doping-induced and concentration-dependent phase transition in ZrO₂ under the influence of Y₂O₃ was discovered, due to which the position of the Fermi level changes and the energy gap decreases. It has been established that, not only for pure systems but including those doped with Y₂O₃, the main contribution to the formation of the conduction band is made by the p-states of electrons. The t-ZrO₂ (101) and t-YSZ (101) surface models were selected as optimal surfaces for water adsorption based on a comparison of their surface energies. An analysis of the mechanism of water adsorption on the surface of t-ZrO₂ (101) and t-YSZ (101) showed that H₂O on unstabilized t-ZrO₂ (101) is adsorbed dissociatively with an energy of -1.22 eV, as well as by the method of molecular chemisorption with an energy of - 0.69 eV and the formation of a hydrogen bond with a bond length of 1.01 Å. In the case of t-YSZ (101), water is molecularly adsorbed onto the surface with an energy of -1.84 eV. Dissociative adsorption of water occurs at an energy of -1.23 eV, near the yttrium atom. The results show that ab initio approaches are able to describe the mechanism of doping-induced phase transitions in (ZrO₂+Y₂O₃)-like systems, based on which it can be assumed that DFT calculations can also flawlessly evaluate other physical and chemical properties of YSZ, which have not yet been studied quantum chemical research. The obtained results complement the database of research works carried out in the field of the application of biocompatible zirconium dioxide crystals and ceramics in green energy generation and can be used in designing humidity-to-electricity converters and creating solid oxide fuel cells based on ZrO₂.

Abstract: The internationally accepted goals of eliminating climate gas emissions implies substantial investments in renewable energy (RE) facilities. This will inevitably lead to major impacts on landscapes. Landscape concerns linked to RE facilities are already leading to controversies in many local communities. In this article, we focus on the question of landscape democracy related to the establishment of RE facilities. Based on recommendations from the European Landscape Convention, an analytical framework is presented identifying three main dimensions of landscape democracy, followed by an overview of arrangements, procedures and methods that are or may be used to encourage democracy. The procedures and methods are analysed based on examples from Denmark and Norway. This is followed by an analysis of decision levels with a special focus on the principle of subsidiarity. Finally, recommendations are presented to strengthen landscape democracy in relation to the installation of RE-facilities.

This article presents a description of a new method for solving the factorization problem, based on the gradient descent algorithm. This approach demonstrates significant improvements in efficiency compared to traditional methods proposed in previous research. This article describes a new method for solving the factorization problem, based on the gradient descent algorithm, and demonstrates the transition from algebraic methods to approaches based on functional analysis. The proposed approach not only improves the efficiency of solving the problem but also allows the application of computational algorithms of functional analysis, opening new possibilities for research and optimization.

Aurora Kinase A being overexpressed in majority of cancers, appear to be an attractive therapeutic target. However, a Phase III clinical trial of Alisertib, a selective AURKA inhibitor, resulted in no better response compared to the comparator arm of chemotherapeutic regimen raising question regarding ability of the same to target the undetectable stem cell functions. In silico analysis indicated regulation of AURKA by the stemness factors Oct4 and Sox2. TCGA data indicated positive correlation of each of the factors with AURKA which were eventually validated in cell lines, patient tissues and blood by flow cytometry along with Oct4 binding on AURKA promoter being detected by ChIP assay. However, indirect immunofluorescence and cell cycle analyses indicated proliferation-independent AURKA functions during asymmetric cell division, a characteristic feature of stem cells. Thorough screening of the AURKA positive cells in patient samples denoted epithelial to mesenchymal transition and significant upregulation of Vimentin, a mesenchymal marker and ABCG2, a drug resistance marker under Oct4 or Sox2 influence. Overall, our study demonstrated combinatorial selection Oct4, Sox2, AURKA, Vimentin and ABCG2 for diagnostics and intervention of circulating breast cancer stem cells as a blood-based, cost-effective and simple approach which will be beneficial in reducing relapse.

Polymers in highly confined geometries can display complex morphologies including ordered phases. A basic component of a theoretical analysis of their phase behavior in confined geometries is the knowledge of the number of possible single-chain conformations compatible with the geometrical restrictions and the established crystalline morphology. While the statistical properties of unrestricted self-avoiding random walks (SAWs) both on and off-lattice are very well known, the same is not true for SAWs in confined geometries. The purpose of this contribution is a) to enumerate the number of SAWs on the simple cubic (SC) and face-centered cubic (FCC) lattices under confinement for moderate SAW lengths, and b) to obtain an approximate expression for their behavior as a function of chain length, type of lattice, and degree of confinement. This information is an essential requirement for the understanding and prediction of entropy-driven phase transitions of model polymer chains under confinement. In addition, a simple geometric argument is presented that explains, to first order, the dependence of the number of restricted SAWs on the type of SAW origin.

High-quality and large-size single crystals of lead-free Na0.5Bi0.5TiO3 were grown using the Czo-chralski technique. The crystals had pure perovskite structure with rhombohedral symmetry and were translucent in the visible and near infrared spectral ranges recorded in the interval 350-1050 nm. The energy gaps determined from the X-ray photoelectron spectroscopy (XPS) and optical measurements were approximately 2.92 eV. The current-voltage characteristics, depolarization current, dc (σdc) and ac (σac) electrical conductivity, and Seebeck coefficient of the crystals were investigated. The frequency/temperature-dependent electrical properties were also measured and analyzed through complex impedance spectroscopy. An overlapping reversible insulator-metal transition (resistive switching) on nanoscales, caused by the electric field, was detected. This was the first time that most of these investigations were performed for this material. The following conductivity mechanisms of NBT single crystals were identified: (i) quasi-free electron and hole conduction and hopping-charges mechanism at low temperatures, (ii) small polaron conductivity in the middle temperature range, and (iii) a significant contribution of the oxygen vacancies to conductivity in the high temperature range. The activation energy values determined from the conductivity data, the imaginary part of the electric impedance and the modulus indicate that the relaxation process in the high-temperature range is attributable to both single and double ionized oxygen vacancies, in combination with the hopping of electrons between Ti4+ and Ti3+. P-type electrical conductivity was also found. These discoveries create new possibilities of reducing the electrical conductivity of NBT and improving the process of effectively poling this material. The density of the electronic states was investigated using an ab initio method. The energy gap cal-culated for NBT (R3c) was 2.8 eV, and is well comparable to those determined from XPS and optical measurements. Our results indicate the possibility of tuning material properties by inten-tionally creating non-stoichiometry/structural defects (oxygen vacancies, cation excess and cation deficiency).

This research was devoted to study the effect of the tacticity of PMMA on the surface physicochemical properties such as the London dispersive component of the surface energy of the polymer, the polar and dispersive free energies, the Lewis’s acid-base surface parameters, and the Lewis acid and base surface energies of atactic, isotactic and syndiotactic PMMAs as a function of the temperature. Inverse gas chromatography (IGC) at infinite dilution was used to determine the surface thermodynamic properties of PMMA at different tacticities. The experimental values of the net retention time and volume of model organic molecules adsorbed on the atactic, isotactic and syndiotactic PMMAs, were obtained by IGC technique at infinite dilution. The London dispersion interaction energy was used for the separation of the polar and dispersive energy of the different n-alkanes and polar solvents adsorbed on the different PMMA surfaces. The London dispersive surface energy γ_s^d (T) of PMMAs was determined by applying the Hamieh thermal model that took into account the effect of the temperature on the surface area of adsorbed molecules. The obtained results showed non-linear variations of γ_s^d (T) of atactic, isotactic, and syndiotactic PMMAs with three maxima characterizing the three transition temperatures of PMMAs, T_g, T_g and T_(liq-liq) with a shift of these temperatures with the isotactic and syndiotactic PMMAs. It was showed that the polar interaction free energy ∆G_a^p (T) also showed the presence of the three above transition temperatures of the polymers. The study showed an important non-linearity variation of the different acid-base parameters in the various polymer surfaces proving the highest effect of the temperature and the tacticity on these parameters. The determination of the enthalpic and entropic Lewis’s acid-base parameters showed an amphoteric character for the different PMMAs. The basicity of the atactic PMMA was about four times larger than its acidity outside the neighborhood of the transition temperatures of the polymer. Whereas, the isotactic PMMA was about 2 to 2.5 times more basic than acid, while the syndiotactic PMMA exhibited the highest basicity by showing a surface 5 to 8 times more basic than acid. However, the Lewis acid-base parameters strongly depended on the temperature and sudden variations of these surface parameters were observed around the transition temperatures largely depending on the PMMA tacticity. The determination of the polar acid and base surface energies of the three PMMAs led to the same previous transition temperatures with an important effect of the tacticity of PMMA on the values of these acid-base surface energies.

The poor solvent crystallization of carbapenem CS-023 has been performed at 25 °C. The following results have been obtained: 1) A solvate crystal Form A (5/2 Ethanol·1/2 H2O) is recovered from 80 v/v% ethanol solution, 2) Form A transforms to Form H (4H2O) by the solid-phase transition through the solvate-free polymorph, Form A-2, and Form A also transformed to Form C (1Ethanol·3H2O) by the solvent-mediated transformation. In the present study, we found that Form C also transforms to Form H by the solid-phase transition through the solvate-free polymorph, Form C-2. The three polymorphs, Form A, H, and C, were composed of the helical-chain structures, respectively. However, there was an incomprehensible affair in the solid phase transition among the three polymorphs. Namely, Form A comprised a left-handed helix.On the other hand, Form C and Form H’s helix chains were in a left- and right-handed helix complex. The solid-phase transition of Form A into Form H suggested the switch of helicity in the solid. We attempted to explain the helicity change in the solid phase transition. As a result, it was suggested that the over-absorption of water of Form A-2 at high humidity plays a vital role in the helicity change.

There were designed and synthesized two new sulfone 2-aminobenzimidazole derivatives. Coordination compounds were obtained with nickel(II), copper(II), zinc(II), cadmium(II) and mercury(II) and these novel ligands. There were fully characterized by spectroscopic and analytical techniques. Single crystal X-ray structural analysis was performed on order to study the relevant intra and inter non-covalent interactions, mainly H...π, lone pair·...π, π...π, highlighting the difference between the ethyl and phenyl groups in such interactions. Dimeric and trimeric supramolecular syntons were found for some of these compounds. Their biological activity was investigated, being the copper(II) compounds with the sulfone phenyl derivative the most active.

Energy transition is a major structural change in the whole social system, and the energy system must be changed globally to replace fossil fuels. Hydropower is one of the largest renewable energy in the world. However the involuntary resettlees due to the construction of hydropower projects are suffering from being far away from their native land, losing the land cultivated for generations and the houses they live in, and losing the social relationship network based on geography and blood ties. Based on the system evaluation theory of reservoir resettlement and referring to relevant research findings, this paper constructs a comprehensive evaluation index framework for assessing the implementation effect of the PostRelocation Support (PReS) policy. The research region is located in Zhijin County, Bijie City, Guizhou Province, China. Accordingly, a combined method of a structural equation model and a fuzzy comprehensive evaluationary model is used in this paper to analyze the implementation of the PReS policy. The results show that the total score of implementing effects of the PReS policy is 4.4, with dramatic significance. The subindex scores of the resettlers’ family income, living conditions, and production conditions; the local economy; and social stability are 4.3, 4.6, 4.4, 4.6, and 4.3, respectively, with dramatic significance. This paper has analyzed and summarized the successful practices of implementing the PReS policy for reservoir resettlers in three dimensions: poverty alleviation, beautiful home construction and accelerating rural revitalization. Research shows that China's rural reservoir resettlers' PReS policy has been more effective in restoring the livelihoods of reservoir resettlers.

We present the results on photothermal (PT) and heat conductive properties of nanogranular silicon (Si) films synthesized by evaporation of colloidal droplets (drop-casting) of 100 ± 50 nm sized crystalline Si nanoparticles (NP) deposited on glass substrates. Finite difference time domain (FDTD) and finite element mesh (FEM) modeling of absorbed light intensity and photo-induced spatial temperature distribution across the Si NP films were well correlated with the local temperatures measured by micro-Raman spectroscopy and used for determination of heat conductivities in the films of various thicknesses. Cubic-to-hexagonal phase transition in these films caused by laser heating was found to be heavily influenced by the film thickness and heat conductive properties of glass substrate, on which the films were deposited. Heat conductivities across the drop-casted Si nanogranular films were found to be in the range of lowest heat conductivities of other types of nanostructurely voided Si films due to enhanced phonon scattering across inherently voided topology, weak NP-NP and NP-substrate interface bonding within nanogranular Si films.

Below T_CO=157 K the quasi-one-dimensional charge-transfer salt (TMTTF)_2SbF_6 undergoes a pronounced phase transition to a charge-ordered ground state. We have explored the non-linear and photoconductive behavior as a function of applied voltage, laser pulse energy and temperature. Besides a decay of the photoconductive signal in a double exponential fashion in the millisecond range, we discover current oscillations in the kHz range induced by the application of short laser pulses. While the resonance frequencies do not depend on voltage or laser intensity and vary only slightly with temperature, the amplitude changes linearly with the laser intensity and voltage. The findings are discussed and compared to comparable phenomena in other low-dimensional electron systems.

According to many research groups, high glucose induces over production of superoxide anions, and reactive oxygen species (ROS) in general is the link between high glucose levels and the toxicities seen at cellular levels. Respiratory complex anomalies could lead to the production of ROS. Calcium [Ca2+], at physiological levels serves as a second messenger in many physiological functions. Accordingly, mitochondrial calcium [Ca2+]m overload leads to ROS production which could be lethal to the mitochondria through various mechanisms. The F1F0-ATPase (ATP syn-thase or complex V) is the enzyme that is responsible for catalyzing the final step of oxidative phosphorylation. It does so by coupling the translocation of protons in the mitochondrial in-termembrane space and shuttling them to the mitochondrial matrix for ATP synthesis to take place. Mitochondrial complex V T8993G mutation specifically blocks the translocation of protons across the intermembrane space thereby blocking ATP synthesis leading to Neuropathy, Ataxia and Retinitis Pigmentosa Syndromes (NARP). This study seeks to explore the possibility of [Ca2+]m overload mediating the pathological roles of high glucose in defective respiratory chain mediated mitochondrial stress. The NARP cybrids are the in vitro experimental models for the cells with F1FO-ATPase defects, these cells harbor 98% of mtDNA T8993G mutation. Their coun-terparts 143B osteosarcoma cell lines are the parental cell lines used for comparisons. We uncov-ered that, NARP cells mediated and enhanced the death of the cells (apoptosis) when incubated with hydrogen peroxide (H2O2) and high glucose respectively as depicted by the MTT assay of cell viability. Furthermore, using the fluorescence probe-coupled laser scanning confocal imag-ing microscopy, NARP cells significantly enabled mitochondrial reactive oxygen species (mROS) formation and enhanced the depolarization of the mitochondrial membrane potential (ΔΨm). Elucidating the mechanisms of sugar enhanced toxicity on mitochondria would help in the fu-ture to alleviate the symptoms of patients associated with (NARP) syndromes.

Vaginal ecosystem is a unique environment where, in physiological conditions, lactobacilli dominate. However, also pathogenic microbial species, responsible of vaginitis and vaginosis, can harbor vaginal microbiota. To extend the data published by De Seta and Larsen in Pathogens (2021), here we analyzed both the anti-Candida and anti-inflammatory properties of the vaginal gel formulation, Respecta® Balance Gel (RBG), commercialized as an adjuvant to treat vaginitis and vaginosis. We evaluated its activity by an in vitro model where a monolayer of A-431 vaginal epithelial cells was infected by Candida albicans in the presence of RBG or the placebo formulation (pRBG). Specifically, we tested the RBG capacity to counteract C. albicans virulence factors as well as their anti-inflammatory properties. Our results show that, unlike the placebo, RBG reduces ,reduces, C. albicans adhesion, its capacity to form hyphae and C. albicans-induced vaginal cell damage. Interestingly, both RBG and pRBG reduce LPS-induced IL-8 secretion (being RBG the most effective) demonstrating that also the placebo retains anti-inflammatory properties. By our experimental approach we highlight the possible role of farnesol on such effects, but we would like to point out that lactic acid, polydextrose and glycogen too must be relevant in the actual application. Taken together, our results show that RBG impairs C. albicans virulence and is able to reduce the inflammation in the vaginal environment, ultimately allowing the establishment of a balanced vaginal ecosystem.

This review is a first attempt at bringing together various concepts from research on wall- and magnetically-bounded turbulent flows. Brief reviews of both fields are provided: The main similarities identified are coherent (turbulent) structures, flow generation and transport barriers. Examples are provided and discussed.

Carbon supported nanoparticles of monometallic Ni catalyst and binary Ni-Transition Metal (Ni-TM/C) electrocatalytic composites were synthesized via chemical reduction method, where TM stands for the doping elements Fe, Co, and Cu. The chemical composition, structure and morphology of the Ni-TM/C materials were characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffractometry (XRD), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM) and energy-dispersive X-ray spectroscopy (EDS). The electrochemical properties towards hydrogen oxidation reaction in alkaline medium were studied using the rotating disc electrode and cycling voltammetry methods. A significant role of the TM dopant in the promotion of the hydrogen electrooxidation kinetics of the binary Ni-TM/C materials were revealed. A record-high in exchange current density value of 0.060 mA cm²_Ni was measured for Ni₃Fe₁/C, whereas the monometallic Ni/C counterpart has only shown 0.039 mA cm²_Ni. In order to predict the feasibility of the electrocatalysts for hydrogen chemisorption, density functional theory was applied to calculate the hydrogen binding energy and hydroxide binding energy values for bare Ni and Ni₃TM₁.

The emergence of acquired resistance to EGFR-TKIs is almost inevitable even after a remarkable clinical response. Secondary mutations such as T790M and C797S are responsible for the resistance to 1st/2nd generation (1/2G) TKIs and 3G TKIs, respectively. To overcome both the T790M and C797S mutations, novel 4G EGFR-TKIs are now under early clinical development. In this study, we evaluated the efficacy of a 4G EGFR-TKI in the treatment of lung cancer with EGFR mutation as well as explored resistance mechanisms to a 4G TKI. First, we compared the efficacies of seven TKIs including a 4G TKI, BI4020, against Ba/F3 cell models that simulate resistant tumors after frontline osimertinib treatment failure because of a secondary mutation. We also established acquired re-sistant cells to BI4020 by chronic drug exposure. Ba/F3 cells with an osimertinib-resistant secondary mutation were refractory to all 3G TKIs tested (alflutinib, lazertinib, rezivertinib, almonertinib, and befotertinib). BI4020 inhibited the growth of C797S-positive cells; however it was not effective against L718Q-positive cells. Erlotinib was active against all Ba/F3 cells tested. In the analysis of resistance mechanisms of BI4020 resistant (BIR) cells, none harbored secondary EGFR mutations. HCC827BIR cells had MET gene amplification and were sensitive to a combination of capmatinib (MET-TKI) and BI4020. HCC4006BIR and H1975BIR cells exhibited epithelial to mesenchymal transition. This study suggests that erlotinib may be more suitable than 4G TKIs to overcome sec-ondary mutations after front-line osimertinib. We found that off-target mechanisms that cause re-sistance to earlier generation TKIs will also cause resistance to 4G TKIs.

We present results on the spontaneous crystallization of freely-jointed polymers of hard spheres obtained in an unprecedentedly long Monte Carlo (MC) simulation on a system of 54 chains of 1000 monomers. Starting from a purely amorphous configuration and after a transitory dominance of the hexagonal closed packed (HCP) polymorph, the system crystallizes in a final, stable, face centered cubic (FCC) crystal of very high perfection. Through refined metrics we gauge the degree of ordering and identify the regions of the phase transition and the corresponding morphologies. An analysis of chain conformational characteristics, of the spatial distribution of monomers and of the volume accessible to them shows that the phase transition is caused by an increase in translational entropy that is larger than the loss of conformational entropy of the chains in the crystal compared to the amorphous state. Polymer chains in the crystal adopt ideal random walk statistics as their great length renders local conformational details, imposed by the geometry of the FCC crystal, irrelevant.

To date, theoretical analyses have provided several useful methods/algorithms for studying transition states and non-covalent interactions. Potential Energy Scan (PES) is one such method that has found wide application in the physicochemical community. Analyzing the PES profiles of the catalytic system of FeBr3 in Electrophilic Aromatic Substitution (EAS) with molecular halogens, one can notice an obvious difference from the modern textbook mechanisms proposed in this area of study. Moreover, the newly presented Graphic Methodology (GM) allows a simple and reliable transition state determination even for very weakly bound charge transfer complexes using second-order derivatives as an efficient tool in the graphical analysis. Relative errors that can be reduced to a few parts per thousand in transition state estimation make this method a potentially very useful tool in further graphical studies of non-covalent interactions. Studies performed using high-precision semiempirical methods suggest that the process of halonium ion quenching proceeds along a completely different pathway, suggesting a possible novel transition metal-nonmetal catalytic system involved in the EAS electrophilic quenching step. The results presented here strongly suggest a future GM application that is widely used and the introduction of pseudo and pre-transition states as new terms in the description of non-covalent interactions.

The poly lactic acid (PLA) is one of the most used bio-derived thermoplastic polymers in 3D and 4D printing applications. The determination of PLA surface properties is of capital importance in 3D/4D printing technology. (1) Background: The surface thermodynamic properties of PLA polymer were determined by using the inverse gas chromatography (IGC) technique at infinite dilution. The determination of the retention volume of polar and non-polar molecules adsorbed on the PLA particles filling the column allowed us to obtain the dispersive, polar, and Lewis’s acid-base surface properties at different temperatures from 40 °C to 100 °C. (2) Methods: the applied surface method was based on our recent model that used the London dispersion equation and the new chromatographic parameter function of the deformation polarizability and the harmonic mean of the ionization energies of the PLA polymer and organic molecules. (3) Results: The application of this new method led to the determination of the dispersive and polar free surface energy of adsorption of molecules on the polymeric material, as well as the glass transition and the Lewis acid-base constants. (4) Conclusions: four interval temperatures were distinguished showing four zones of the variations of the surface properties of PLA as a function of the temperature before and after the glass transition.

The rapid advancements and the merging of hybrid quantum-classical computing, artificial intelligence (AI), machine learning (ML), and deep learning (DL) pose a potentially unseen and significant threat to encryption that may impact Post-Quantum Cryptography (PQC) transition timelines. There is a direct hybrid quantum-classical computing threat on cryptography, and there is also a direct threat AI/ML on cryptography. However, the synergistic combination of these technologies presents known and unknown threats that need attention, focus action, and research. This paper reviews Grover's Adaptive Search (GAS), which combines Grover's Algorithm with adaptive techniques to optimize search further, potentially making it even more efficient for attacking encryption. This work also examines the quantum-accelerated Harrow-Hassidim-Lloyd (HHL) Algorithm, designed to solve systems of linear equations exponentially faster than classical algorithms in certain conditions. The HHL algorithm can solve some lattice-based problems, which have implications for lattice-based encryption. This technological confluence and its potential impact on cryptography and encryption necessitate a proactive and coordinated approach to developing and implementing quantum-resistant AI/ML cryptographic solutions. This paper reviews the technological confluence and its potential implications for classical cryptography and PQC transition timelines and calls for further research.

Energy conversion and distribution (heat and electricity) is characterized by long planning horizons, investment periods and depreciation times, and it is thus difficult to plan and tell the technology that optimally fits for decades. Uncertainties include future energy prices, applicable subsidies, regulation, and even the evolution of market designs. To achieve higher adaptability to arbitrary transition paths, a technical concept based on integrated energy systems is envisioned and described. The problem of intermediate steps of evolution is tackled by introducing a novel paradigm in urban infrastructure design.It builds on standardization, modularization and economies of scale for underlying conversion units. Building on conceptual arguments for such a platform, it is then argued how actors like (among others) municipalities and district heating system operators can use this as a practical starting point for a manageable and smooth transition towards more environmental friendly supply technologies, and to commit to their own pace of transition (bearable investment/risk). environmental friendly supply technologies. Merits are not only supported by technical arguments but also by strategical and societal prospects like technology neutrality and availability of real options.

Determination of indoor location based on fine time measurement (FTM) of the round trip time (RTT) of a signal between an initiator (smartphone) and a responder (Wi-Fi access point) enables a number of applications. However, the accuracy currently attainable — standard deviations of 1–2 meter in distance measurement under favorable circumstances — limits the range of possible application. A first responder, for example, may not be able to unequivocally determine on which floor someone in need of help is in a multi-story building. The error in location depends on several factors, including the bandwidth of the RF signal, delay of the signal due to the high relative permittivity of construction materials, and the geometry-dependent “noise gain” of location determination. Errors in distance measurements have unusual properties that are exposed here for the first time. Improvements in accuracy depend on understanding all of these error sources. This paper introduces “frequency diversity,” a method for doubling the accuracy of indoor location determination using weighted averages of measurements with uncorrelated errors obtained in different channels. The properties of this method are verified experimentally with a range of responders. Finally, different ways of using the distance measurements to determine indoor location are discussed and the Bayesian grid update method shown to be more useful than others, given the non- Gaussian nature of the measurement errors.

It is shown that the 5D geodetic equations and 5D Ricci identities give us a way to create a new viewpoint on some problems of Modern Physics, Astrophysics, and Cosmology. Specifically, the application of the 5D geodetic equations in (4+1) and (3+1+1) splintered forms obtained with the help of the monad and dyad methods made it possible to introduce a new, effective generalized concept of the rest mass of the elementary particle. The latter leads one to novel connections between the General Relativity and quantum field theories, as well as all of that, including the (4+1) splitting of the 5D Ricci identities, brings about a better understanding of the magnetic monopole problem and the vital difference in the origins of the Maxwell equations and gives rise to surprising connections between them. The obtained results also provide new insight into the mechanism of the 4D Universe’s expansion and its following acceleration.

This year marks the 20th anniversary of the discovery that proteins with various cellular functions can be temporarily immobilized in the nucleolus, a process known as nucleolar sequestration. This review reflects on the progress made to understand the physiological roles of nucleolar sequestration and the mechanisms involved in protein immobilization. We discuss how nucleolar sequestration consists of a highly choreographed amyloidogenic liquid-to-solid phase transition that converts the nucleolus into Amyloid bodies (A-bodies). The study of solid condensates A-bodies will offer unique perspectives on cellular assembly of membrane-less compartments and provide alternative insights on pathological amyloidogenesis involved in neurological disorders.

The local and global order in dense packings of linear, semi-flexible polymers of tangent hard spheres are studied by employing extensive Monte Carlo simulations at increasing volume fractions. Chain stiffness is controlled by a tunable harmonic potential for the bending angle whose intensity dictates the rigidity of the polymer backbone as a function of the bending constant and equilibrium angle. The studied angles range from acute to obtuse ones, reaching the limit of rod-like polymers. We analyze how packing density and chain stiffness affect the ability of chains to self-organize at the local and global levels. The former corresponds to crystallinity as quantified by the Characteristic Crystallographic Element (CCE) norm descriptor, while the latter is computed through the scalar orientational order parameter. In all cases, we identify the critical volume fraction for the phase transition and gauge the established crystal morphologies, developing a complete phase diagram as a function of packing density and equilibrium bending angle. A plethora of structures is obtained, ranging from random hexagonal closed packed morphologies of mixed character and almost perfect face centered cubic (FCC) and hexagonal close-packed (HCP) crystals at the level of monomers, to nematic mesophases, with prolate and oblate mesogens at the level of chains. For rod-like chains, hysteresis is observed between the establishment of long-range nematic order and crystallization, while for right-angle chains both transitions are synchronized. A comparison is also provided against the analogous packings of monomeric and fully flexible chains of hard spheres.