The combination of chemical cross-linking and mass spectrometry is currently a progressive technology for deriving structural information of proteins and protein complexes. In addition, chemical cross-linking is a powerful tool for stabilizing macromolecular complexes for single particle cryo-electron microscopy. Broad pallets of cross-linking chemistry, currently available for the majority of cross-linking experiments, still rely on the amine-reactive N-hydroxysuccinimide esters targeting mainly N-termini and lysine side chains. These cross-linkers are divided into two groups: water soluble and water insoluble; and research teams prefer one or another speculating on the benefits of their choice. However, the effect of cross-linker polarity on the outcome of cross-linking reaction has never been studied. Herein, we use both polar (bis(sulfosuccinimidyl) glutarate) and non-polar (disuccinimidyl glutarate) cross-linkers and systematically investigated the impact of cross-linker hydrophobicity on resulting distance constraints, using bovine serum albumin as a model protein.

In extant biology, biopolymers perform multiple crucial functions. The biopolymers are synthesized by enzyme-controlled biosystems that would not have been available at the earliest stages of chemical evolution and consist of correctly sequenced and/or linked monomers. Some of the abiotic “messy” polymers approximate some functions of biopolymers. Condensation polymers are an attractive search target for abiotic functional polymers since principal polymers of life are produced by condensation and since condensation allows for the accurate construction of high polymers. Herein the formation of hyperbranched polyesters that have been previously used in the construction of enzyme-like catalytic complexes is explored. The experimental setup compares between the branched polyesters prepared under mild continuous heating and the wet-dry cycle conditions. The results reveal that period wetting during which partial hydrolysis of the polyester occurs, helps control the chain growth and retards the gel transition. It is significant to the origin of life studies that environmental, prebiotically plausible conditions could achieve such control without enzymes or a skilled chemist. As expected in marginally controlled systems, the identification of each component of the heterogeneous system has proved challenging, but it is not crucial for drawing the conclusions.

In this study, the efficiency of an anaerobic treatment system for wastewater from a South African poultry slaughterhouse was evaluated using a lab-scale static granular bed reactor (SGBR). The down-flow SGBR (2 L) was operated continuously for 138 days under mesophilic conditions (35-37 ˚C), at hydraulic retention times (HRTs) ranging from 24 to 96 h and average organic loading rates (OLRs) of 0.78 to 5.74 g COD/L.day. The SGBR achieved an average chemical oxygen demand (COD) removal efficiency of 80% and the maximum COD removal achieved was 95%, at an HRT of 24 h and average OLR of 5.74 g COD/L.day. The optimization of the SGBR, with regard to a suitable HRT and OLR, was determined using response surface methodology (RSM). The optimal SGBR performance with regard to the maximum COD removal efficiency was predicted for an OLR of 12.49 g COD/L.day and a HRT of 24 h, resulting in a 95.5% COD removal efficiency. The model R2 of 0.9638 indicated that the model is a good fit and is suitable to predict the COD removal efficiency for the SGBR.

Continuous research into the availability of phosphorus (P) in forest soil is critical for sustainable management of forest ecosystems. In this study, we used sequential chemical extraction and 31P-nuclear magnetic resonance spectroscopy (31P-NMR) to evaluate the form and distribution of inorganic P (Pi) and organic P (Po) in Casuarina forest soils of a subtropical coastal sand dune at Houlong in Taiwan. The soil samples were collected from humic (+2-0 cm) and mineral layers (mineral-I: 0-10, mineral-II: 10-20 cm) at two topographic locations (upland and lowland) by elevation. Sequential chemical extraction revealed that the NaOH-Po fraction, as moderately recalcitrant P, was the dominant form in humic and mineral-I layers in both upland and lowland soils, whereas the cHCl-Pi fraction was the dominant form in the mineral-II layer. Resistant P content, including NaOH-Pi, HCl-Pi, cHCl-Pi, and cHCl-Po fractions, was higher in the upland than lowland in the corresponding layers; however, labile P content, NaHCO3-Po, showed the opposite pattern. Content of resistant Pi (NaOH-Pi, HCl-Pi, and cHCl-Pi) increased significantly with depth, but that of labile Pi (resin-Pi and NaHCO3-Pi) and recalcitrant Po (NaHCO3-Po, NaOH-Po, and cHCl-Po) decreased significantly with depth at both locations. 31P-NMR spectroscopy revealed inorganic orthophosphate and monoesters-P as the major forms in this area. The proportions of Pi and Po evaluated by sequential chemical extraction and 31P-NMR spectroscopy were basically consistent. The results indicated that the soils were in weathered conditions. Furthermore, the P distribution and forms significantly differed between the upland and lowland by variation in elevation and eolian aggradation effects in this coastal sand dune landscape.

The annual demand for fibres continues to rise worldwide. Consequently, more and more fibres must be produced to meet this demand, most of which are melt-spun polymeric man-made fibres. [1] Smooth filaments made of polymers are mainly used for technical applications in industry. For use in clothing or home textiles, for example, a texturing process is used to give the filaments a crimp and thus a feel like that of natural fibres. In this state, they can be processed together with natural fibres and used in textiles. Partially oriented yarns (POY) are of great importance in tex-turing. The yarns are mainly crimped with the help of the so-called false-twist texturing process (FTTP). [2] Since POY accounts for about 60 % of the melt-spun filament yarn produced world-wide, the FTTP is the most important texturing process in the textile industry [3]. In this paper, the main components of false-twist texturing (FTT) machines are explained along with the state of the art and research for each component and its influence on the process. Relevant patents are dis-cussed as well as process optimisation techniques, innovative polymers and yarn types recently used in FTT, followed by a conclusion and an outlook for the process.

One of the most widely available and extensively produced varieties of industrial hemp, which generates a substantial amount of consumer-increasing waste in the form of hemp cellulose. In this study, recycling with a compressed and high-speed method that combines crushing and alkali treatment effectively converts leftover hemp fiber into ultrafine powder. SEM (Scanning Electron Microscopy), AFM (Atomic Force Microscope), FTIR (Fourier-transform Infrared Spectroscopy), and XRD (X-ray Diffraction) examined the original morphology of hemp fiber treated with alkali, fiber heated to 200 ℃, and crushed powder. Particle size, crystallinity, fiber surface, and strength increased and decreased. It became apparent that fiber strength decreased and fiber roughness significantly increased after alkali treatment. Fiber increased significantly, and crystallinity decreased after crushing. It was simple and effective for converting the leftover hemp fiber into micron-sized powder. In about 3 to 5 minutes, approximately 1 kg of dry ultrafine powder with a particle size of 10.44 μm was produced. This production method will significantly enhance future industrial applications of waste hemp fiber.

The Mahuagou gold deposit is among the most important gold deposits in the core of Huangling Anticline. However, the geochemical exploration on the surface of the mining area presents challenges due to the thin overburde.This paper focuses on the overburden soil of Fengxiangshugou (FXS) – Mahuanggou (MHG) section as the research object, utilizes chemical form analysis of gold, soil halogen survey, and heat-released mercury survey to determine the key deep-penetrating geochemical methods for mining area. The results indicated that Si and Al components of samples exhibit minimal variation, suggesting that drift loads did not influence the overburden soil. Based on the systematic clustering, As, Sb, Mo, Bi, W and Hg emerge as ore-body or ore-belt front elements of hydrothermal gold deposits. In the study area, the predominant chemical form of gold in soil is the strong organic bond. Compared to the total amount, strong organic bound gold and heat-released mercury show higher anomaly contrasts, making them crucial indicators of faults, intrusions and hidden ore bodies. Consequently, chemical form analysis of gold and heat-released mercury surveys can enhance the anomaly contrast, proving beneficial for geochemical prospecting for weak anomalies in this area.

Peptide-based drugs are promising anticancer candidates due to their biocompatibility, and low toxicity. Particularly, tumor homing peptides (THPs) have the ability to bind specifically to can-cer cells receptors and tumor vasculature. Despite their potential to develop antitumor drugs, there are few available prediction tools to assist the discovery of new THPs. Two webservers based on machine learning models are currently active, the TumorHPD (https://webs.iiitd.edu.in/raghava/tumorhpd) and the THPep (http://codes.bio/thpep), and more recently the SCMTHP (SCMTHP (pmlabstack.pythonanywhere.com), based on scoring card method. Herein, a novel method based on network science and similarity searching implemented in the starPep toolbox (http://mobiosd-hub.com/starpep/) is presented for THPs discovery. The approach leverages from exploring the structural space of THPs with Chemical Space Networks (CSNs) and from applying centrality measures to identify the most relevant and non-redundant THPs sequences within the CSN. Such THPs were considered as queries (Qs) for multi-query similarity searches that applies a group fusion (MAX-SIM rule) model. The resulting multi-query similarity searching models (SSMs) were validated with three benchmarking datasets of THPs/non-THPs. Predictions achieved accuracies ranged from 92.64 to 99.18% and Matthews Correlation Coefficients between 0.894-0.98, outperforming state-of-the-art predictors. The best model was applied to repurpose AMPs from the starPep database as THPs, which were subse-quently optimized for the TH activity. Finally, 54 promising THP leads were discovered, and their sequences were analyzed to encounter novel motifs. These results demonstrate the potential of CSNs and multi-query similarity searching for a rapid and accurate identification of THPs.

The Serra da Estrela Natural Park (NPSEs) in Portugal stands out as a well-preserved region abundant in medicinal plants, particularly known for their pharmaceutical applications in diabetes prevention and treatment. This comprehensive review explores these plants' botanical diversity, traditional uses, pharmacological applications, and chemical composition. The NPSEs boast a rich diversity with 138 medicinal plants across 55 families identified as traditionally and pharmacologically used against diabetes globally. Notably, the Asteraceae and Lamiaceae families are prevalent in anti-diabetic applications. In vitro studies reveal their significant inhibition of carbohydrate-metabolizing enzymes, and certain plant co-products regulate genes involved in carbohydrate metabolism and insulin secretion. In vivo trials demonstrate anti-diabetic effects, including glycaemia regulation, insulin secretion, antioxidant activity, and lipid profile modulation. Medicinal plants in NPSE exhibit various activities beyond anti-diabetic, such as antioxidant, anti-inflammatory, antibacterial, anticancer, and more. Chemical analysis identifies over fifty compounds like phenolic acids, flavonoids, terpenoids, and polysaccharides responsible for their efficacy against diabetes. The findings underscore the potential of NPSE medicinal plants as anti-diabetic candidates, urging further research to develop effective plant-based anti-diabetic drugs, beverages, and supplements.

The basis of modern teeth whitening systems is the use of a whitening gel, usually containing hydrogen peroxide or carbamide peroxide. The purpose of our study was to evaluate the effect of chemical and modified office teeth whitening systems on the mineral metabolism of oral fluid and to determine a safer method. The study covered 81 patients aged 22 to 35 years of both sexes with teeth color A2 and darker on the Vita Classic scale. Determination of the concentration of calcium and phosphates in the oral fluid was carried out on a spectrophotometer using ready-made Human kits. Chemical tooth whitening was performed using a gel based on 40% hydrogen peroxide. After the procedure, remineralization therapy with enamel-sealing liquid was performed for 14 days. The obtained results indicate that the most pronounced changes in the content of calcium (+74.4%, p <0.001) and рhosphates (phosphorus) (-23.07%, p <0.001) were observed when using a chemical bleaching system. After the teeth whitening procedure using a modified technique, less pronounced changes in the concentrations of calcium (+29.07, p <0.001) and phosphorus (-14%, p <0.001) were observed. The use of remineralizing agents led to a faster recovery of the initial levels of calcium and phosphates in the oral fluid. Both bleaching systems caused similar changes in the chemical composition of the oral fluid.

Abstract: Agriculture uses plastic products for containers, packaging, tunnels, drip irrigation tub-ing, mulches. Large amounts of plastics are used as mulches on the soil surface for vegetable pro-duction (tomato, cucumber, watermelon, strawberry, vine) to reduce the weed competition, in-crease water and fertilizer use efficiency and enhance crop yield. Portugal uses around 4,500 t/year of polyethylene plastic to cover approximately 23,000 ha of agricultural land and only a small amount is recovered for recycling or secondary uses because of dirt with soil, vegetation, pesticide and fertilizers. Cleaning and decontaminating polyethylene mulch are costly and commercial technology is often not accessible nor economically viable in the current economic Portuguese situation. Most plastic mulch is composed of polyethylene that degrades slowly and produces a large quantity of residues in soil with negative impact in the environment. In the present study, the effects of long-term cultivation of blueberry using green 100% high density polyethylene mulch, in the south Portugal were evaluated for soil chemical and biological changes. High density green plastic mulch did not contaminate the topsoil with di(2-ethylhexyl) phthalate and heavy metals, buttotal nitrogen and organic carbon concentrations, electric conductivity and microbial activity were reduced in the planting row compared with bare soil, without mulching. Further-more, the presence of plastic mulch did not affect negatively the presence of nematodes, and the Rhabditida (bacterial feeders) increased in the planting and covered row.

The purpose of the review is to provide new insight into the potential of surface modification of carbon fibers for enhancing the application of the carbon fibers many a fold. To this end a total of 429 papers on the subject of surface modication of carbon fibers by a variety of chemical and electrochemical methods published during the period from 2010-2022 have been reviewed. Astounding results of surface funcationalization of carbon fibers by a variety of state of the art methods resulting in the unconventional applications of the resulting modified carbon fibers are summarized in a nut-shell in schemes from 1-6 towards the end of the review. Surface modifica-tion induces functionality to carbon fibers (CFs). The vitality of CF surface modification reac-tions could only be compared to the life process of respiration that sustains the multi functional-ity of living cells. Applicability of CFs can be drastically enhanced in incomprehensible ways by surface modification. Upon surface modification, inert and non-reactive CF surface becomes chemically active and functional with utility in diverse fields, namely, health, energy, environ-ment, defense, catalysis, smart materials and many others. Surface modification methods can be broadly classified into chemical, electrochemical and physical methods. By these surface modi-fication methods, the inert FC surface becomes polar. Surface properties like roughness, wetta-bility and energy are enhanced. Modification processes like sizing, oxidation, amination, si-lanization, polymerization, nanoarchitecture induces multifunctionality on CF surface. Modi-fied CFs when used as reinforcing material in carbon fiber reinforced plastics (CFRPs), im-proved bonding at the interface with resin matrices is observed with enhanced and outstanding mechanical properties (flexural strength, flexural modulus, IFSS, ILSS, hardness, elastic modulus, bending strength and compression strength).

Vertical graphene nanowalls (VGNWs) have emerged as a highly promising material in recent years due to their exceptional properties, such as a high specific surface area, excellent electrical conductivity, scalability, and compatibility with transition metal compounds. These attributes make VGNWs a compelling candidate for various applications, including energy storage, catalysis, and sensing, fostering great interest in their use in next future commercial graphene-based sensors like optoelectronic and plasmonic devices, energy storage electrodes, and catalytic systems. Among the diverse graphene synthesis methods, plasma-enhanced chemical vapor deposition (PECVD) has proven to be a robust technique for producing large-scale graphene films and creating VGNWs on diverse substrates. However, despite substantial progress in optimizing growth conditions to achieve micrometer-sized graphene nanowalls, the outcomes are often obtained through empirical approaches, and a comprehensive understanding of the underlying physicochemical mechanisms governing nanostructure formation remains elusive. In particular, a deeper exploration of atomic-level phenomena, such as nucleation, carbon precursor adsorption, and surface diffusion of adatoms, is imperative to exert precise control over the growth process. Concerning the synthesis of VGNWs, hydrogen plays a dual role in the graphene growth process, acting as both a co-catalyst and an etchant for the nanowalls. Nevertheless, a thorough comprehension of the intricate growth process is still required. To address these knowledge gaps, this review paper aims to investigate the nucleation and growth of VGNWs using PECVD, with a specific focus on exploring the temperature effect on the graphene growth ratio and nucleation density across a wide range of temperatures. By providing valuable insights into the PECVD process, our objective is to enable the optimization of growth conditions for tailoring VGNWs' properties, thereby facilitating their application in energy storage, catalysis, and sensing fields.

Ultralong carbon nanotubes (UCNTs) are highly demanded for nanocomposites applications because of their magnificent physical and chemical properties. UCNTs are synthesized by catalytic chemical vapor deposition (CCVD) method and, before using as fillers in nanocomposites, should be purified from residual catalyst and non-CNT particles without significant destruction or scissoring of UCNTs. The role of water vapor for purification of UCNTs is investigated, the importance of water assistance in this process is confirmed. It was shown that wet air treatment of products of UCNTs CCVD synthesis under mild conditions can be used to decrease sufficiently residual catalyst content without significant carbon losses in comparison with the results obtained with dry air, while the residual iron content was shown to influence heavily on the subsequent oxidation of different forms of carbons, including UCNTs. The increasing of D/G ratio of Raman spectra after wet air treatment of products of UCNTs CCVD synthesis makes it possible to conclude that iron catalyst particles transform into iron oxides and hydroxides that caused inner structural strains and destruction of carbon shells improving removal of the catalyst particles by subsequent acid treatment. UCNTs purification with water assistance can be used to develop economically and ecologically friendly methods for obtaining fillers for nanocomposites of different applications.

With heat treatments to control drywood termites (Blattodea: Kalotermitidae), the presence of heat sinks causes heat to be distributed unevenly throughout the treatment areas. Drywood termites may move to galleries in heat sink areas to avoid exposure to lethal temperatures. Our studies were conducted in Crytotermes brevis-infested condominiums in Honolulu, Hawaii to reflect real-world condominium scenarios; either a standard heat treatment performed by a heat remediation company or an improved heat treatment was used. For improved treatments, heated air was directed into the toe-kick voids of C. brevis infested cabinets to reduce heat sink effects and increase the heat penetration into these difficult-to-heat areas. Eight thermistor sensors placed inside toe-kick voids, treatment zone, embedded inside cabinets’ sidewalls, and in a wooden cube recorded target temperatures of above 46 °C or 50 °C for 120 minutes. A pretreatment and follow-up inspections were performed at 6 months posttreatment to monitor termite inactivity using visual observations and by recording the numbers of spiked peaks on a microwave technology termite detection device (Termatrac). In improved treatment condominiums, significantly higher numbers of spiked peaks were recorded at pretreatment as compared to 6 months posttreatment. Efficacious heat treatment protocols using the improved methods are proposed.

A methodology based on the concepts that arise from Density Functional Theory named Conceptual Density Functional Theory (CDFT) was chosen for the calculation of some global and local reactivity descriptors of the Discodermins A-H family of marine peptides through the consideration of the KID (Koopmans in DFT) technique that was successfully used in previous studies of this kind of molecular systems. The determination of active sites of the studied molecules for different kind of reactivities was achieved by resorting to some CDFT-based descriptors like the Fukui functions as well as the Parr functions derived from Molecular Electron Density Theory (MEDT). A few properties identified with their ability to behave as a drug and the bioactivity of the peptides considered in this examination were acquired by depending on a homology model by studying the correlation with the known bioactivity of related molecules in their interaction with various biological receptors. With the further object of analyzing their bioactivity some parameters of usefulness for future QSAR studies, their predicted biological targets and the the ADME (Absorption, Distribution, Metabolism, and Excretion) parameters related to the Discodermins A-H pharmacokinetics are also reported.

The simultaneous evaluation of heat/mass transference procures momentous significance in the polymer industry and engineering activities. Extensive utilization of such aspects includes propylene flares, heat exchangers, energy transfiguration in chilling towers, and amputation of post fortuitous heat in nuclear reactors. Owing to such prospective demands, we interpreted the Jeffrey liquid reactive flow under non-linear convection. We scrutinized the transference of heat/mass under generalized Fourier-Fick relations. Thermal conductivity depends on temperature while mass diffusivity is dependent on concentration. Besides, heat source along with first-order chemical reaction aspects are accounted for. Relevant transformations are exerted to achieve non-linear differential systems that are solved through the homotopy scheme. Influences of divers factors are exhibited via graphical benchmark.

Naturally occurring small molecules include a large variety of natural products from different sources that have confirmed activity against epigenetic targets. In this work we review chemoinformatic, molecular modeling and other computational approaches that have been used to uncover natural products as inhibitors of DNA metiltransferases, a major family of epigenetic targets with significant potential for the treatment of cancer and several other diseases. Examples of these computational approaches include docking, similarity-based virtual screening, and pharmacophore modeling. It is also commented the chemoinformatic-based exploration of the chemical space of naturally occurring compounds as epigenetic modulators which may have significant implications in epigenetic drug discovery and nutriepigenetics.

This work is devoted to consideration and analysis of the application of molecular dynamics simulation (MDS) methods to the study of nanosized polymer polyvinylidene fluoride (PVDF) thin ferroelectric films (two-dimensional ferroelectrics) and their composites with graphene layers: 1) to study and calculations of the polarization switching time depending on the electric field and PVDF film thickness; 2) to study and calculations of the polarization switching time depending changes of the PVDF on PVDF-TrFE film; 3) to study the polarization switching time in PVDF under influence of graphene layers. All calculations at each MDS step were carried out using quantum semi-empirical methods PM3. A comparison and analysis of the results of these calculations and the kinetics of polarization switching within the framework of the Landau-Ginzburg-Devonshire theory for homogeneous switching in ferroelectric polymer films is carried out. The study of the composite heterostructures of the “graphene-PVDF” type and calculations of their polarization switching times were presented too. It is shown that replacing PVDF with PVDF-TrFE significantly changes the polarization switching times in these thin polymer films, and that introducing various graphene layers into the PVDF layered structure leads to both an increase and a decrease in the polarization switching time. Here everything also depends on the position and displacement of the ferroelectric coercive field depending on the system damping parameters.

This study develops into the application of a combined MFC unit with chemical coagulation for total treatment of inert contaminants in complex substrates. Microbial Fuel Cell (MFC) technology converts chemical energy in the form of organic matter, into bioelectricity in an environmentally friendly and effi-cient manner, reducing carbon emissions and increasing bioenergy production. An evaluation of a la-boratory scale chemical coagulation using an aluminum and poly-based coagulant on how effective it can remove bulk impurities such as particulate COD and turbidity to obtain the purest and most cost-effectively treated wastewater using a jar test is being conducted in this current study. This study aims to find the most effective treatment technologies for wastewater recovery in breweries in order to achieve zero liquid effluent discharge (ZLED). The preliminary results showed that adding a modest amount of poly and a 50 % alum alone treatment improved COD, color, and turbidity reduction. The turbidity removal efficiency achieved after chemical coagulation treatment was 90.50 % and 59.36 % COD removal, demonstrating the benefits of adopting an alum/poly based technique. To determine ZLED, this study clearly advised a combined treatment technique, specifically the MFC-flocculator unit for efficient organics and inorganics removal.

Since its first isolation in 1934, hyaluronic acid (HA) has been studied across a variety of research areas. This unbranched glycosaminoglycan consisting of repeating disaccharide units of N-acetyl-D-glucosamine and D-glucuronic acid is almost ubiquitary in humans and in other vertebrates. HA is involved in many key processes -including cell signaling, wound reparation, tissue regeneration, morphogenesis, matrix organization and pathobiology-, and has unique physico-chemical properties -such as biocompatibility, biodegradability, mucoadhesivity, hygroscopicity and viscoelasticity. For these reasons, exogenous HA has been investigated as drug delivery system and treatment in cancer, ophthalmology, arthrology, pneumology, rhinology, urology, aesthetic medicine and cosmetic. To improve and customize its properties and applications, HA can be subjected to chemical modifications: conjugation and crosslinking. The present review gives an overview regarding HA, describing its history, physico-chemical, structural and hydrodynamic properties, and biology –occurrence, biosynthesis (by hyaluronan synthases), degradation (by hyaluronidases and oxidative stress), roles, mechanisms of action and receptors. Furthermore, both conventional and recently emerging methods developed for the industrial production of HA and its chemical derivatization are presented. Finally, the medical, pharmaceutical and cosmetic applications of HA and its derivatives are reviewed, reporting examples of HA-based products which currently are on the market or are undergoing further investigations.

Due to the low content, few studies are focused on the volatile compounds of Phlomoides rotata (Benth. ex Hook. f.) Mathiesen (PR, syn. Lamiophlomis rotata (Benth.) Kudô). However, such volatile compounds may have important pharmacological activities such as antioxidant, anticancer. In order to identify the chemical markers (CMs) in the essential oils (Es) and explore the potential bioactivities, we first conduct a thoroughly investigation on the volatile compounds and evaluate their anti-oxidant activities (AOAs), to the best of our knowledge. Light yellow Es with a fresh and elegant smell are obtained by hydro-distillation with an average yield of 0.11% (mL/g). After separation through cryoprecipitation, the crystals (Cs) and EOs removed crystals (RCs) were gotten, respectively. A total of 81 components are qualified and quantified in the Es, Cs and RCs, in which 44 ones are first reported from PR. As for content, the main compounds are long-chain fatty acids (LCFAs) and their esters. Among them, palmitic acid (PA), myristic acid (MA), linoleic acid (LA), oleic acid (OA) and methyl palmitate are highlighted, Besides, hexahydrofarnesyl acetone and phytol are also prominent Four kinds of C13-norisoprenoids are first reported from PR, in which, trans-β-damascenone is potent in flavour. In sum, these eight representative compounds can be chosen as the CMs. The AOAs of Es, Cs, RCs and four CMs such as PA, MA, LA and OA are evaluated by in vitro assays. In general, PA and MA present pro-oxidant activities (POAs) or weak AOAs. LA and OA show POAs or weak AOAs in lower concentration group, whereas demonstrate medium or strong AOAs in higher concentration group. Usually, the RCs demonstrate stronger AOAs and the Cs present weaker AOAs compared with those of the corresponding Es, which should be related to their different content of PA. This study can give some hints on the utilization of such Es which are abundant in LCFAs.

Homochirality is an obvious feature of life on Earth. On the other hand, extraterrestrial samples contain largely racemic compounds. The same is true for any common organic synthesis. Therefore, it has been a perplexing puzzle for decades how these racemates could have formed enantiomerically enriched fractions as a basis for the origin of homochiral life forms. Numerous hypotheses have been put forward as to how preferentially homochiral molecules could have formed and accumulated on Earth. In this article, it is shown that homochirality of the abiotic organic pool at the time of formation of the first self-replicating molecules is not necessary and not even probable. It is proposed to abandon the notion of a molecular ensemble and to focus on the level of individual molecules. Although the formation of the first self-replicating, most likely homochiral molecule is a seemingly improbable event, on a closer look, it is almost inevitable that homochiral molecules have formed simply on a statistical basis. In this case, the non-selective leap to homochirality would be one of the first steps in chemical evolution directly out of a racemic “ocean”. Moreover, most studies focus on the chirality of the primordial monomers with respect to an asymmetric carbon atom. However, any polymer with a minimal size that allows folding to a secondary structure, would spontaneously lead to asymmetric higher structures (conformations). Most of the functions of these polymers would be influenced by this inherently asymmetric folding. To summarize, simple and universal mechanisms may have led to homochiral self-replicating systems in the context of chemical evolution. A homochiral monomer pool is deemed unnecessary and probably never existed on primordial Earth.

A simple method is presented for the continuous generation of carbon nanotube forests stably anchored on stainless-steel surfaces using a reactive-roll-to-roll (RR2R) configuration. No addition of catalyst nanoparticles is required for the CNT-forest generation, the stainless-steel substrate itself being tuned to generate the catalytic growth sites. The process enables very larges surfaces covered with CNT forests having individual CNT roots anchored to the metallic ground through primary bonds. Fog water harvesting is demonstrated and tested as one potential application using long CNT-covered wires. The RR2R is performed in the gas phase, no solution processing of CNT suspensions is used contrary to usual R2R CNT-based technologies. Full or partial CNT-forest coverage provides tuning of the ratio and shape of hydrophobic and hydrophilic zones on the surface. This enables optimization of fog water harvesters for droplet capture through the hydrophobic CNT forest, and water removal from the hydrophilic SS surface. Water recovery tests using small harp-type harvesters with CNT-forest generate water capture of up to 2.2 g/cm2h under ultrasound-generated fog flow. The strong CNT root anchoring on the stainless steel surfaces provides opportunities for (i) robustness and easy transport of the composite structure, (ii) chemical functionalization and/or nanoparticle decoration of the structures, and opens the road for a series of applications on large scale surfaces, including fog harvesting.

Inflammatory diseases are common pathological processes caused by various acute and chronic factors and some of them are autoimmune diseases. Exosomes are fundamental extracellular vesicles secreted by almost all cells, which contain a series of constituents, i.e. cytoskeletal and cytosolic proteins (actin, tubulin, histones), nucleic acids (mRNA, miRNA, DNA), lipids (diacylglycerophosphates, cholesterol, sphingomyelin, ceramide), and other bioactive components (cytokines, signal transduction proteins, enzymes, antigen presentation and membrane transport/fusion molecules, adhesion molecules). This review would be a synopsis of the actual knowledge on the contribution of exosomes from different cell sources as possible therapeutic agents against inflammation, focusing on several inflammatory diseases, neurological diseases, rheumatoid arthritis and osteoarthritis, intestinal bowel disease, asthma, liver and kidney injuries. Current knowledge indicates that the role of exosomes in therapy of inflammation and in inflammatory diseases could be distinctive. Main limitations to their clinical translation are still production, isolation, and storage. Additionally, there is an urgent need to personalize the treatments in terms of selection of exosomes, their dosages and routes of administration, and a deeper knowledge about their biodistribution, type and incidence of adverse events and long-term effects of exosomes. In conclusion, exosomes can very promising next generation therapeutic option, superior to synthetic nanocarriers and cell therapy, and can represent a new strategy of effective, safe, versatile and selective delivery systems in the future.

Different aspects in applying the nucleation theorem to the description of crystallization of liquids are analyzed. It is shown that, by employing the classical Gibbs' approach in the thermodynamic description of heterogeneous systems and assuming that the basic assumptions of classical nucleation theory commonly employed in application to crystallization hold, a general form of the nucleation theorem can be formulated valid not only for one-component but generally for multi-component systems. This result is taken then as the starting point for the derivation of particular forms of this theorem for the cases that the deviation from equilibrium is caused by variations of either composition of the liquid phase, temperature, or pressure. In this procedure, recently developed by us expressions for the curvature dependence of the surface tension, respectively, the dependence of the surface tension on pressure and/or temperature are employed. It is shown that the formulation of the nucleation theorem as proposed by Kashchiev [J. Chem. Phys. 76, 5098-5102 (1982)] holds also for multi-component systems as far as mentioned above assumptions are fulfilled. In the application of classical nucleation theory to crystallization processes it is assumed as one of its basic ingredients that the bulk properties of the critical clusters are widely identical to the properties of the newly evolving crystal phase. This assumption is, however, in general, it is not true. This limitation of the theoretical description can be overcome by the application of the generalized Gibbs approach for the specification of the dependence of the properties of critical crystal clusters on the degree of metastability of the liquid phase. Applying this method, it is demonstrated that a similar formulation of the nucleation theorem as derived based on classical nucleation theory holds true also in cases when a dependence of the state parameters of the critical clusters on the degree of deviation from equilibrium is appropriately accounted for.

Ozone and fine particles (PM_2.5) are the two main air pollutants of concern in the New South Wales Greater Metropolitan Region (NSW GMR) region due to their contribution to poor air quality days in the region. This paper focuses on source contributions to ambient ozone concentrations for different parts of the NSW GMR, based on source emissions across the greater Sydney region. The observation-based Integrated Empirical Rate Model (IER) was applied to delineate the different regions within the GMR based on the photochemical smog profile of each region. Ozone source contribution is then modelled using the CCAM-CTM (Cubic Conformal Atmospheric Model-Chemical Transport Model) modelling system and the latest air emission inventory for the greater Sydney region. Source contributions to ozone varied between regions, and also varied depending on the air quality metric applied (e.g., average or maximum ozone). Biogenic volatile organic compound (VOC) emissions were found to contribute significantly to median and maximum ozone concentration in North West Sydney during summer. After commercial domestic, power station was found to be the next largest anthropogenic source of maximum ozone concentrations in North West Sydney. However, in South West Sydney, beside commercial and domestic sources, on-road vehicles were predicted to be the most significant contributor to maximum ozone levels, followed by biogenic sources and power stations. The results provide information which policy makers can devise various options to control ozone levels in different parts of the NSW Greater Metropolitan Region.

A plenty of theories on the origin of genetic codes have been proposed so far, yet all ignored the energetic driving force, its relation to the biochemical system, and most importantly, the missing “matchmaker” between proteins and nucleic acids. Here, a new hypothesis is proposed, according to which ATP is at the origin of the primordial genetic code by driving the coevolution of the genetic code with the pristine biochemical system. This hypothesis aims to show how the genetic code was produced e.g. by photochemical reactions in a protocell that derived from a lipid vesicle enclosing various life’s building blocks (e.g. nucleotides and peptides). At extant cell, ATP is the only energetic product of photosynthesis, and is at the energetic heart of the biochemical systems. ATP could energetically form and elongate chains of both polynucleotides and polypeptides, thus acting a “matchmaker” between these two bio-polymers and eventually mediating precellular biochemical innovation from energy transformation to informatization. ATP was not the only one that could drive the formation of polynucleotides and polypeptides, but favored by precellular selection. The protocell innovated a photosynthesis system to produce ATP efficiently and regularly with the aids of proteins and RNA/DNA. The completion of permanently recording the genetic information by DNA marked the dawn of cellular life operated by Darwinian evolution. The ATP hypothesis assumes or supports the photochemical origin of life, shedding light on the origins of both photosynthetic and biochemical systems, which remains largely unknown thus far. Based on ATP hypothesis, virus (like the new coronavirus) could not be the earliest life on Earth, as it has neither biochemical systems nor lipid bilayer membrane that provided relatively isolated environment for the development of protobiochemical reactions, although it owns the genetic code of a cellular life. Virus could not be a bridge between life and non-life, but is an anti-life substance, as it depletes cellular material for its own replication, and then spreads by destroying the host cells. It can be imagined that if cellular life are completely wiped out by the virus, the complete destruction of life on Earth would be inevitable.

Fatty acids (FAs) represent an important class of metabolites, impacting on membrane building blocks and cellular regulatory networks. In nature, prokaryotes are characterized with the most impressing FA structural diversity and the highest relative contents of free fatty acids (FFAs). Thereby, nitrogen-fixing bacteria (order Rhizobiales), often found in symbiosis with legumes, attract a special interest. Indeed, FAs impact on the structure of rhizobial nodulation factors, required for successful infection of plant root. Although the FA patterns can be addressed by GC- and LC-MS, these methods are time-consuming and suffer from compromised sensitivity, low stability of derivatives and artifacts. In contrast, MALDI-TOF-MS represents an excellent platform for high-efficient metabolite fingerprinting, also applicable to FFAs. Therefore, here we propose a simple and straightforward protocol for high-throughput relative quantification of FFAs in rhizobia by the combination of Langmuir technology and MALDI-TOF-MS, which is featured with high sensitivity, accuracy and precision of quantification. Here we propose a step by step procedure comprising rhizobia culturing, pre-cleaning, extraction, sample preparation, mass spectrometric analysis, data processing and post-processing. To demonstrate the analytical potential of the protocol we illustrate it by a case study – comparison the FFA metabolomes of two rhizobia species - Rhizobium leguminosarum and Sinorhizobium meliloti.

The Ramsey theory based approach to the phase transitions of the second order is suggested. The phase transitions of the second order are seen as switching of physical interactions/chemical bonds between the entities forming the primitive cell of the material. Such a switching is typical for a phase change materials. If the energy of the primitive cell is kept constant under the change in the spatial order of the chemical bonds, the phase transition of the second order takes place. The switching of interactions between the entities forming the primitive cell is accompanied by the breaking of the initial symmetry of the cell. The order parameter/the degree of ordering characterizing the ordering within the primitive cell is re-defined. The introduced degree of ordering quantifies ordering of links/interactions/chemical bonds between entities constituting the 2D lattice; whereas, the classical “Landau degree of order” quantifies the symmetry breaking under variation in spatial locations of these entities. The suggested approach is generalized easily for 3D primitive cells. Thermal capacity of the non-symmetrical phase is larger than that of the symmetrical phase. For the primitive cells built of six interacting entities, the Ramsey Theory predicts inevitable appearance of the unstable monochromatic triangles, when the links correspond to attraction or repulsion interactions. The situation becomes different for the primitive cells built of five interacting entities.

Adaptive radiations occur mostly in response to environmental variation through the evolution of key eco-morphological innovations that allow emerging species to occupy new ecological niches. However, rapid phenotypic evolution and the evolution of key novelties are likely to also occur when a couple or few species are engaged into narrow ecological interactions. To demonstrate coevolution is a difficult task; only elusive evidences confirm that coevolution is a driver of speciation and diversification. Here we propose that the adaptive radiation of the Mediterranean orchid genus Ophrys, which gave rise to ca. 350 species since the apparition of the genus is due to the particular co-evolutionary dynamics between these plants and their pollinators. We suggest that the pollination by sexual swindle used by Ophrys orchids is the main driver of this coevolution. Flowers of each Ophrys species mimic sexually receptive females of one particular insect species, mainly bees. Male bees are attracted by pseudo-pheromones emitted by Ophrys flowers that are similar to the sexual pheromones of their females. Males lured by the flower shape, color and hairiness attempt to copulate with the flower, which glues pollen on their bodies. Pollen is eventually transferred to the stigma of another flower of the same Ophrys species during similar copulation attempts. Three observations led us to propose the scenario of an asymmetric co-evolutionary relationship between Ophrys and their pollinators. Firstly, there is a strong intra-specific competition among Ophrys individuals for the attraction of their species-specific pollinators, which is due to the high learning and memorization abilities of bees that record the pheromone signatures of kin or of previously courted partner to avoid (further) copulation attempts. Mnemonic pollinators induce thus a strong selective pressure for variation in the pseudo-pheromones emitted by individual flowers, which will potentially generate shifts in pollinator species, and hence Ophrys speciation. These pollinator shifts are adaptive for new Ophrys species because they may benefit from a competitor-free space. Secondly, such shifts in pollinator species are due to the random crossing of peaks in the olfactory landscape of the pollinator guild that is syntopic to each particular Ophrys population. This selective process on individual, random variation in pseudo-pheromone bouquets is followed by directional selection on flower phenotypes that will reinforce the attraction of the new pollinator. Thirdly, pollinators use the pseudo-pheromones emitted by Ophrys to locate suitable habitats from a distance within complex landscapes. Pollinators stay fixed for a while in these habitats by the local diversity of pseudo-pheromones, which increases their probability of encounter with a receptive female and hence the reproduction probability of both sexes. Conversely, pollinators disperse out of small suitable habitats once they have memorized the local diversity of sexual pseudo-pheromone bouquet or if fecundated Ophrys flowers repel pollinators, which decreases the probability of geitonogamy (plant advantage) but limit pollinator mating with locally emergent insect females, thus limiting inbreeding and favoring gene flow (pollinator advantage). Finally, we propose several research avenues that emerged according to this scenario of adaptive radiation by assymetric coevolution between Ophrys species and their pollinators.

Restraint use in Australian residential aged care has been highlighted by the media, and investigated by researchers, government and advocacy bodies. In 2018, the Royal Commission into Aged Care selected ‘Restraint’ as a key focus of inquiry. Subsequently, Federal legislation was passed to ensure restraint is only used in residential aged care services as the ‘last resort’. To inform and develop Government educational resources, we conducted qualitative research to gain greater understanding of the experiences and attitudes of aged care stakeholders around restraint practice. Semi-structured interviews were held with 28 participants, comprising nurses, care staff, doctors, physiotherapists, pharmacists and relatives. Two focus groups were also conducted to ascertain the views of residential and community aged care senior management staff. Data were thematically analyzed using a pragmatic approach of inductive and deductive coding and theme development. Five themes were identified during the study: 1. Understanding of restraint; 2. Support for Legislation; 3. Restraint-free environments are not possible; 4. Low-level restraint, and 5. Restraint in the community is uncharted. Although most staff, health practitioners and relatives have a basic understanding of restraint, more education is needed at a conceptual level to enable them to identify and avoid restraint practice, particularly ‘low-level’ forms and chemical restraint. There was strong support for the new restraint regulations, but most interviewees admitted they were unsure what the legislation entailed. With regards to resources, stakeholders wanted recognition that there were times when restraint was necessary and advice on what to do in these situations, as opposed to unrealistic aspirations for restraint-free care. Stakeholders reported greater oversight of restraint in residential aged care but stated that community restraint use was largely unknown. Research is needed to investigate the extent and types of restraint practice in community aged care.

The electronic structure and the participation of the simplest azomethine imine (AI) in [3+2] cycloaddition (32CA) reactions have been analysed within the Molecular Electron Density Theory (MEDT) using DFT calculations at the MPWB1K/6-311G(d) level. Electron localisation function (ELF) topological analysis reveals that AI has a pseudoradical structure, while the conceptual DFT reactivity indices characterise this TAC as a moderate electrophile and a good nucleophile. The non-polar 32CA reaction of AI with ethylene takes place through a one-step mechanism with low activation energy, 5.3 kcal/mol-1. A bonding evolution theory (BET) study indicates that this reaction takes place through a non-concerted [2n+2τ] mechanism in which the C–C bond formation is clearly anticipated prior to the C–N one. On the other hand, the polar 32CA reaction of AI with dicyanoethylene takes place through a two-stage one-step mechanism. Now, the more favourable regioisomeric transition state structure (TS) is located 8.5 kcal•mol⁻¹ below the reagents, in complete agreement with the high polar character of the TS. The current MEDT study makes it possible to extend Domingo’s classification of 32CA reactions to a new pra-type of reactivity.

Cornea severe inflammation produces opacity or even perforation, scarring, and angiogenesis, resulting in blindness. The cornea can be used to study the effect of new anti-angiogenic chemopreventive agents. We researched the anti-angiogenic effect of two extracts, Methanol (Met) and Hexane (Hex), from the seed of Cucurbita argyrosperma, in the inflamed corneas. The corneas of Wistar rats were alkali-injured and treated intragastrically for seven successive days. Clinical manifestation as opacity score, corneal neovascularization (CNV) area, re-epithelialization percentage, and histological evaluation were performed. Inflammatory (COX-2, NF-κB, and IL-1β), and angiogenic (VEGF-A, VEGFR1, VEGFR2) markers were assessed by immunohistochemistry. Cox-2, Il-1β, and Vegf-a mRNA levels were also determined. After treatments, we observed slim corneal thickness with lower opacity scores and low cell infiltration compared to untreated rats. Treatment also accelerated wound healing and decreased CNV area. The staining of inflammatory and angiogenic factors was significantly decreased. These effects are related to a down-expression of Cox-2, Il-1β, and Vegf. These results suggest that intake of C. argyrosperma seed can be used to attenuate the angiogenesis secondary to inflammation in corneal chemical damage.

The results of physico-chemical studies of individual fruit parts, including crusts, partitions, juice and seeds themselves, extracted from immature (green), unripe and mature fruits of three harvest periods are presented: 20.VII, 01.IX and 15.X. The analyses were carried out in 2019-20 during the period of active growth and ripening of fruits in the varieties Spring, Iridanaly, Guleisha pink and wild pomegranate from the Geokchay region (Azerbaijan) using standard and generally accepted physico-chemical methods. The ripe fruit (130-288 g) consisted of 60-113% of the peel (peel together with partitions), 53-140% of the juice and 17-85% of the seeds themselves. The edible part of the ripened fruits (53.85-73.2 of the total weight of the fruit) consisted of 58.54-78.65% juice and 21.35 -41.46% seeds, fresh juice contained 15.7-17.7% solids, including 12.04-13.84% sugar, 0.17-0.30% protein, 0.15—0.23% pectin, 0.30-0.40% ash and 0.26-0.57% total polyphenols. The concentrations of solids, protein, ash and total polyphenols in the seeds themselves, remaining after the extraction of juice from the grains of ripe fruits, were 50.0-58.2, 4.13-5.75, 0.60-1.0 and 0.08-0.32%, respectively. There were fewer total polyphenols, flavonoids, chlorogenic acids, catechins and leucoanthocyanins in ripe fruits, and more ascorbic acid, anthocyanins and proanthocyanidins than in unripe ones. The period from the second half of July to the beginning of September is the time of a real “boom” of common polyphenols.

SARS-CoV-2 Omicron variant spike RBD epitopes in complex with spike (S) -protein D614G mutations now predominate globally and increase infectivity by assembling more functional S proteins into the virion. On average, homeopathic medicine contains less than one molecule per dose on average. Single variable SphericalHarmonicY, LaguerreL, WhittakerM, SphericalBesselJ, LegendreP, LegendreQ, LaguerreL, ChebyshevT, and Hypergeometric1F1 Functions pFqarise in connection with the power series solution of the Schrodinger equation or in the summation of perturbation expansions in quantum mechanics. A quantum interpretation of the homeopathic method is presented here through a novel algebraic topology approach to supersymmetry and symmetry breaking in quantum fields and quantum gravity theory with the aim of developing a wide range of physical-based drug design applications in a Small Molecule Quantized Water Memory Network suggesting that the Hidden Black Hole Paradox of Information Loss might be solved under suitable conditions.

This work is a physical review, with elements of additions and thinning, on the methods of theoretical studies of nonlinear electrophysical phenomena in crystals with ion-molecular chemical bonds (CIMB). Crystals of this class include ionic dielectrics (characterized by high ionic conductivity), layered crystals, a special case of which are hydrogen-bonded crystals (HBC), defined as proton semiconductors and dielectrics (PSD).A scientific review (comparative analysis and justification of various approximations) was carried out on the methods of constructing and solving a generalized quasi-classical kinetic equation describing the mechanism of nonlinear relaxation polarization and conductivity processes in dielectric materials with ion-molecular chemical bonds (a special case is hydrogen-bonded crystals (HBC)) in a wide temperature range (1-1550 K) and polarizing field strengths (0.1-1000 V/m) at alternating field frequencies of the order of 1 kHz - 1000 MHz. The most important variant of the equations of the kinetic theory of dielectric relaxation in this work is the generalized non-linear by polarizing field quasi-classical kinetic equation of ionic (in HBC, proton) relaxation, based on the particle number balance equation (conductivity ions) in potential wells and having (in these models) the meaning of the ion current continuity equation (in HBC, protons), solved by the method of successive approximations by decomposition into infinite power series by degrees of a small dimensionless comparison parameter. It was found that in the area of ​ ​ weak fields (0.1-1 MW/m) at temperatures T = 50 - 550 K, for a number of ionic dielectrics (including HBC and similar dielectric properties and lattice structure) the generalized quasi-classical kinetic equation transforms to the linearized Fokker – Planck equation and, in the region of low (50-100K) and higher temperatures (250-550 K) begin to manifest non-linear polarization effects due to respectively proton tunneling (in the case of HBC) and volume charge relaxation (in the case of the HBC and for a wider class of ionic dielectrics). At ultra-low (1-10 K) temperatures in the region of weak fields (0.1-1 MW/m) and ultra-high temperatures (550-1550 K) in the region of strong fields (10-1000 MW/m), the contribution of this kind of effects to polarization is significantly enhanced. The effect of nonlinearities on relaxation times for microscopic acts of proton transitions across a potential barrier (assumed to be parabolic) is investigated. Nonlinear effects at volume-charge polarization in the hydrogen-bonded crystals (HBC) in alternating electric field, in radio frequency range are investigated. From the solution of the system of nonlinear Fokker-Planck equations (macroscopic kinetic equation) and Poisson, with blocking electrodes, using Fourier series, a recurrent (convenient for use in any approximation of perturbation theory) expression is constructed for complex amplitudes of relaxation modes of volumetric charge. Complex dielectric permittivity (CDP) is calculated as a series decomposition over even frequency harmonics of a variable field. The effect of quantum proton transitions and polarizing field parameters (strength, frequency) on the nonlinear properties of proton semiconductors and dielectrics has been established.