Ferrocenium (Fc+) inherits a number of molecular/electronic properties from the neutral counterparts’ ferrocene (Fc) including the high symmetry. Both Fc+ and Fc prefer the eclipsed structure (D5h) over the staggered structure (D5d) by an energy of 0.36 kcal·mol-1. The present study using the recently developed excess orbital energy spectrum (EOES) shows that the open shell Fc+ cation exhibits similar conformer dependent configurational changes to the neutral Fc conformer pair. A further energy decomposition analysis (EDA) discloses that the reasons for the preferred structures are different between Fc+ and Fc. The dominant differentiating energy between the Fc+ conformers is the electrostatic energy (EEstat), whereas in neutral Fc, it is the quantum mechanical Pauli repulsive energy (EPauli). Within the D5h conformer of Fc+, the EOES reveals that the -electrons of Fc+ experience more substantial conformer dependent energy changes than the -electrons (assumed the hole is in a β orbital).

A new type of gold nanoparticles was synthesized by using benzoyl pyrazolone as a capping agent. The synthesized AuNPs exhibited a spherical shape and a monodisperse and fluorescence emission characteristic peak at 650 nm. The AuNPs –BMPBP was demonstrated as sensitive and selective fluorescent chemosensor for detection of Al ³⁺ ion. In the presence of Al ³⁺ ion, the fluorescent emission of BMPBP-AuNPs at 650 nm, increased with an increasing concentration of Al ³⁺ ion with a low detection limit (2 µM), the proposed method provided to apply determination of Al ³⁺ ion of tap water with satisfactory results.

Considering the safety issues of Li ion batteries, all-solid-state polymer electrolyte has been one of the promising solutions. In this point, achieving a Li ion conductivity in the solid state electrolytes comparable to liquid electrolytes (>1 mS/cm) is particularly challenging. Employment of polyethylene oxide (PEO) solid electrolyte has not been not enough in this point due to high crystallinity. In this study, hybrid solid electrolyte (HSE) systems are designed with Li_1.3Al_0.3Ti_0.7(PO₄)₃(LATP), PEO and Lithium hexafluorophosphate (LiPF₆) or Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). Hybrid solid cathode (HSC) is also designed using LATP, PEO and lithium cobalt oxide (LiCoO₂, LCO)—lithium manganese oxide (LiMn₂O₄, LMO). The designed HSE system displays 3.0 × 10⁻⁴ S/cm (55 ℃) and 1.8 × 10⁻³ S/cm (23 ℃) with an electrochemical stability as of 6.0 V without any separation layer introduction. Li metal (anode)/HSE/HSC cell in this study displays initial charge capacity as of 123.4/102.7 mAh/g (55 ℃) and 73/57 mAh/g (25 °C). To these systems, Succinonitrile (SN) has been incorporated as a plasticizer for practical secondary Li ion battery system development to enhance ionic conductivity. The incorporated SN effectively increases the ionic conductivity without any leakage and short-circuits even under broken cell condition. The developed system also overcomes the typical disadvantages of internal resistance induced by Ti ion reduction. In this study, optimized ionic conductivity and low internal resistance inside the Li ion battery cell have been obtained, which suggests a new possibility in the secondary Li ion battery development.

Master Valentim’s fountain became an important historical patrimony for Brazil, being portrayed by famous artists among them Jean-Baptiste Debret. In 1938, it was registered as cultural heritage by the Brazilian National Historical and Artistic Heritage Institute (IPHAN), and in 1990 it was subjected to excavation and restoration works. The fountain was built in Gneiss and Lioz limestone, with metallic plates and mortar connecting the Gneiss blocks. Currently, deteriorations in the fountain stones can be observed such as light stains and some aesthetic modifications caused by inadequate restorations. Petrography, XRF, XRD, Physical Properties, Colorimetry, Electrical Conductivity, ICP-OES, SEM-EDX, and TGA were performed in order to characterize the Gneiss blocks, the metallic plates, the stones used in previous restorations, as well as light stains observed on the Gneiss blocks. The petrography and XRD analyses inferred that light stains may have been caused by the formation of an insoluble salt as a result of the association of the lead from the plates with other elements. The XRD analysis on the light staining area indicated presence of cerussite (PbCO₃), and anglesite (PbSO₄), which are the probable cause of the light stains. The SEM-EDX results suggested that sulfur is the main element associated to lead.

We herein provide an overview of the most recent multidisciplinary process advances that have occurred in the food industry as a result of changes in consumer lifestyle and expectations. The demand for fresher and more natural foods is driving the development of new technologies that may efficiently operate at room temperature. Moreover, the huge amount of material discarded by the agro-food production chain lays down a significant challenge for emerging technologies that can provide new opportunities by recovering valuable by-products and creating new applications. Aiming to design industrial processes, there is a need of pilot scale plants such as the “green technologies development platform” that was established by the authors. The platform is made up of a series of multifunctional laboratories that are equipped with non-conventional pilot reactors developed in direct collaboration with partner companies in order to bridge the enormous gap between academia and industry via the large-scale exploitation of relevant research achievements. Selected key, enabling technologies for process intensification make this scale-up feasible. We make use of two selected examples, the grape and olive production chains, to show how cavitational reactors, which are based on high-intensity ultrasound and rotational hydrodynamic units, can assist food processing and the sustainable recovery of waste to produce valuable nutraceuticals as well as colouring and food-beverage additives.

In this paper, a new anode environmentally friendly for hydrogen production was developed based on 430 stainless steel with an electrodeposited cobalt layer. The novelty of this work is the cobalt source once the electrodeposition bath was obtained from recycling of spent Li-ion batteries cathode with composition LiCoO₂. The electrodeposited cobalt behaves as supercapacitor in KOH 1M. In the linear voltammetry in KOH 1M, when the overpotential reaches 370 mV, the anodic density current for 430 SS/Co is 19 mA cm⁻². Thus, the anode developed in this paper achieves the double of density current with half of production cost if compared with 316SS. Moreover the anode construction described in this paper is an excellent option for Li- ion battery recycling.

In this paper the application of recycled Li-ion batteries spent cathode (LIB-SC) combined with NaHCO₃/H₂O₂ system is presented for the first time in the literature as an alternative for degradation of potentially toxic organic molecules. The model pollutant choice was methylene blue molecule. The spent cathode composition corresponds to LiCoO₂, which was proved by the XRD and EDX. Regarding the decolorization of methylene blue solution, the addition of NaHCO₃ in comparison with only H₂O₂ reduces the complete decolorization time in 96%. This reduction occurs because the radical CO₃ is more stable than OH. In this way, the application the system proposed in this article is aimed at solving two major global problems: the disposal of cell phone batteries and the pollution of liquid effluents.

Selective hydrogenation of nitrobenzene was carried out under solvent-free conditions using supported AuPd nanoparticles catalyst, prepared by modified impregnation method (MIm), as efficient catalyst. >99% yield of aniline (AN) was obtained after 15 hours at 90 °C, 3 bar H2 that can be used without any further purification or separation, therefore reducing cost and energy input. Supported AuPd nanoparticles catalyst, prepared by MIm, was found to be active and stable even after 4 recycle experiments whereas the same catalyst prepared by SIm deactivated during the recycle experiments. The most effective catalyst was tested for the chemoselective hydrogenation of 4-chloronitrobenzene (CNB) to 4-chloroaniline (CAN). The activation energy of CNB to CAN was found to be 25 kJ mol-1, while that of CNB to AN was found to be 31 kJ mol-1. Based on this, the yield of CAN was maximized (92%) by lowering the reaction temperature to 25 °C.

There are many welded structures in the world such as bridges and viaducts that are subject to fatigue. These structures, generally made of non-alloy or low-alloy steels, have been put into operation some of them with many years ago and have accumulated a large number of variable load cycles over the time. For this reason the occurrence of fatigue phenomenon is inevitable and consists in the occurrence of failures at stresses applied to the structure, below the yield limit of the material. These stresses under the static loads would not cause the failures to appear..This paper will investigate whether two reconditioning techniques “weld toe grinding” and “WIG remelting weld toe”, influences favorably the behavior of welded structures made from HSLA steel, in static and variable loads and therefore if the application of these techniques is justified in both cases. In the paper will be presented the chemical composition and mechanical properties of the base and filler materials, micro and macrostructures, graphics with the variation of microhardness, static and fatigue tensile tests will be performed, and it will be rised durability curve in case of fatigue tests.

Carbon fiber reinforced polymer (CFRP) has been used widely in strengthening of steel structures. Steel/CFRP systems subjected to elevated temperatures is realistic in a summer climate event in many countries where the temperature in steel may approach 50 °C or even higher, which will lead to the degradation of the bond performance between CFRP and steel. Therefore, predicting the bond behavior of the CFRP/steel system under elevated temperature is critical. This paper investigated the mechanical performance of CFRP/steel adhesively-bonded double strap joints at elevated temperatures. Thirty CFRP-steel double strap joints were tested to failure under temperatures between 10 °C and 90 °C. It was found that the joint failure mode changed from adherend failure to debonding failure as the temperature approached T_g. In addition, the ultimate load and joint stiffness decreased significantly at temperatures near to and greater than T_g. Based on the experimental results, a model is proposed to predict the bond stress of the CFRP/steel at different temperatures.

The exploitation of lipid membranes in biosensors has provided the ability to reconstitute a considerable part of their functionality to detect trace of food toxicants and environmental pollutants. Nanotechnology enabled sensor miniaturization and extended the range of biological moieties that could be immobilized within a lipid bilayer device. This chapter reviews recent progress in biosensor technologies based on lipid membranes suitable for environmental applications and food quality monitoring. Numerous biosensing applications are presented, putting emphasis on novel systems, new sensing techniques and nanotechnology-based transduction schemes. The range of analytes that can be currently detected include, insecticides, pesticides, herbicides, metals, toxins, antibiotics, microorganisms, hormones, dioxins, etc. Technology limitations and future prospects are discussed, focused on the evaluation/ validation and eventually commercialization of the proposed sensors.

This review considers the generation of relatively simple biomolecules, e.g., primary amino acids, resulting from the rapid collapse of bubbles in aqueous solutions containing various, low molar mass, gases. Some of the possible primary reactions occurring to produce the biomolecules are introduced and discussed. A brief discussion is included on the possible involvement of hydrodynamic cavitation, at the primordial seashore, as the initiating processes for the formation of the first organic molecules on prebiotic earth and the origins of life on Earth some 4 billion years ago.

The search for graphene or few layer graphene production methods that are simple, allow mass production and yield good quality material continues to provoke intense investigation. The present work contributes through the study of the aqueous exfoliation of four types of graphene sources, namely graphite and graphite nanoflakes with different morphologies and geographical origin. The exfoliation was achieved in an aqueous solution of a soluble pyrene derivative that was synthesized to achieve maximum interaction with the graphene surface at low concentration (5 x 10-5 M). The yield of bilayer and few layer graphene obtained was quantified by Raman spectroscopic analysis and the adsorption of the pyrene derivative on the graphene surface was studied by thermogravimetric analysis and X-ray diffraction. The whole procedure was rationalized with the help of molecular modeling.

Herein, we report about the monometallic Ni and bimetallic Pd-Ni catalysts supported on CeO2-Al2O3 binary oxide, which were investigated in oxy-steam reforming of methanol (OSRM). Monometallic and bimetallic supported catalysts were prepared by wet aqueous impregnation and subsequent impregnation method, respectively. The physicochemical properties of the catalytic systems were investigated using various methods such as: BET, XRD, TPR-H2, TPD-NH3, XPS and SEM-EDS techniques. It has been proven that the addition of palladium to the nickel catalyst facilitates its reduction. The activity tests performed for all catalysts confirmed the promotion effect of palladium on catalytic activity of nickel catalyst and selectivity towards hydrogen production. Both nickel and bimetallic palladium-nickel supported catalysts showed excellent stability during the reaction. Such catalytic systems are valuable for the advance of the field of fuel cell technology.

Crystalline β-cobalt hydroxide (β-Co(OH)₂) of different morphologies have been successfully synthesized with the addition of sodium hydroxide to cobalt nitrate solution and aging in the mother liquor. The rate of NaOH addition, ranging from 0.1 mL/min to 10 mL/min, influences the surface morphology with the obtained storage capability of the respective electrode. Characterization of the β-Co(OH)₂ was fully developed, including X-ray diffraction, scanning and transmission electron microscopy, and BET analyses. At a lower rate of NaOH addition, particles are like platelets, while for a higher rate (≥2 mL/min) grains are fused together forming a larger crystallite size. This result is supported by the X-ray diffraction structural analysis, where the phase evolution of (002) plane becomes distinct for the higher rate of NaOH addition. Lithium cobalt oxide (LiCoO₂) was synthesized through oxidation from the as-prepared β-Co(OH)₂ and LiOH. The electrochemical performance of as obtained LiCoO₂ is investigated using charge-discharge and cyclic voltammetric studies. The precursor β-Co(OH)₂ prepared at a lower rate of 0.1 mL/min in LiCoO₂ demonstrated the best electrochemical performance of 155 mAh/g. After 50 cycles, the capacity retention rate was 67% compared with the first cycle. Finally, we have attempted to correlate the amount of the available OH^- ions with the formation of platelets and the discharge capacity. This work has developed a methodology for the synthesis of LiCoO₂ using β-Co(OH)₂ in a facile chemical solution process.

Tea and coffee are the most commonly used beverages throughout the world. Both decoctions are rich in small organic molecules such as phenolics/polyphenolics, purine alkaloids, many methylxanthines, substituted benzoic and cinnamic acids. Many of these molecules are physiologically chemopreventive and chemoprotective agents against many severe conditions such as cancer, Alzheimer, Parkinsonism, inflammation, sleep apnea, cardiovascular disorders, bradycardia, fatigue, muscular relaxation, and oxidative stress. Caffeine, a purine alkaloid, is a common metabolite of both tea and coffee aqueous decoctions and its concentration in tea/coffee depends on the fermentation process, preparation of the water extract and quality of tea leaves/coffee beans. A 250 ml of a coffee cup contains 100-150 mg caffeine while the same volume of strong tea contains 25-40 mg caffeine. The present paper presents the potential of caffeine as a potent chemopreventive agent that can be used for numerous physiological disorders.

True contact between solids with randomly rough surfaces tends to occur at a large number of microscopic contact patches. So far, two scaling regimes have been identified for the number density n(A) of contact-patch sizes A in elastic, non-adhesive, self-affine contacts. At small A, n(A) is approximately constant, while n(A) decreases as a power law at large A. Using Green’s function molecular dynamics, we identify a characteristic (maximum) contact area Ac above which a superexponential decay of n(A) becomes apparent if the contact pressure is below the pressure p_cp at which contact percolates. We also find that A_c increases with load relatively slowly far away from contact percolation. Results for A_c can be estimated from the stress autocorrelation function G_σσ (r) with the following argument: the radius of characteristic contact patches, r_c, cannot be so large that G_σσ (r_c) is much less than p_c². Our findings provide a possible mechanism for the breakdown of the proportionality between friction and wear with load at large contact pressures and/or for surfaces with a large roll-off wavelength.

Hydrogen peroxide is an important chemical of increasing demand in today’s world. Currently, the anthraquinone autoxidation process dominates the industrial production of hydrogen peroxide. Herein, hydrogen and oxygen are reacted indirectly in the presence of quinones to yield hydrogen peroxide. Owing to the complexity and multi-step nature of the process, it is advantageous to replace the process with an easier and straightforward one. The direct synthesis of hydrogen peroxide from its constituent reagents is an effective and clean route to achieve this goal. Factors such as water formation due to thermodynamics, explosion risk, and the stability of the hydrogen peroxide produced hinder the applicability of this process at an industrial level. Currently, the catalysis for the direct synthesis reaction is palladium based and the research into finding an effective and active catalyst has been ongoing for more than a century now. Palladium in its pure form, or alloyed with certain metals are some of the new generation of catalysts that are extensively researched. Additionally, to prevent the decomposition of hydrogen peroxide to water, the process is stabilised by adding certain promoters such as mineral acids and halides. A major part of today’s research in this field focusses on the reactor and the mode of operation required for synthesising hydrogen peroxide. The emergence of microreactor technology has helped in setting up this synthesis in a continuous mode, which could possibly replace the anthraquinone process in the near future. This review will focus on the recent findings of the scientific community in terms of reaction engineering, catalyst and reactor design in the direct synthesis of hydrogen peroxide.

In order to improve the strength of PVA/xylan composite films and endow them with ultraviolet (UV) shielding ability, TiO2-KH550 nanoparticle was synthesized and added into the PVA/xylan matrix. The TiO2-KH550 nanoparticle dispersed well in the 0.04% sodium hexametaphosphate (SHMP) solution under ultrasonic and stirring treatments. Investigations on the properties of films showed that TiO2-KH550 had the positive impact on improving the strength, moisture and oxygen barrier properties of the composite films. The maximum tensile strength (27.3 MPa), the minimum water vapor permeability (2.75×10-11 g•m-1•s-1•Pa-1) and oxygen permeability (4.013 cm3•m-2•24h-1•0.1MPa-1) were obtained under the addition of 1.5% TiO2-KH550. The tensile strength of TiO2-KH550 reinforced composite film was increased by 70% than that of the pure PVA/xylan composite film, and the water vapor and oxygen permeability were decreased by 31% and 41%, respectively. Moreover, the UV transmittance of film at the wavelength of 400 nm was almost zero when adding 1.5~2.5% of TiO2-KH550, which indicated the PVA/xylan composite films were endowed with excellent UV light shielding ability.

Versatile hybrid organic polymers are prepared using two active intermediates such as cynuric chloride and chitosan derivatives. The prepared chalcones are characterized by using FT-IR, UV, and proton NMR, thermal analysis and Minimum inhibitory Concentration. Thermal stability of the synthesized hybrid polymer is found using TGA and the hybrid chitosan derivative chalcone is thermally stable up to 270 °C. The antimicrobial activity of the prepared chitosan containing chalcone moiety are find out using Minimum Inhibitory Concentration (MIC) method. The synthesized versatile chalcone shows excellent antimicrobial activity against gram-negative bacteria such as Pseudomonas aeruginosa; and Gram-positive bacteria Chalcone containing halogen moiety shows high activity (MIC 7.8 µg/mL) than the hydroxyl containing chalcone. Cytotoxicity activity of the synthesized composites shows high activity.

Controlling the concentration of free radicals in polymerization systems is advantageous for preparing cationic polyacrylamide (CPAM) with high molecular weight and acceptable dissolvability. In this study, a novel ultraviolet (UV)-initiated system characterized with adjustable light intensity and redox-azo complex initiator was used to synthesize a CPAM flocculant named NP. Comparatively, another CPAM flocculant named SP with stable UV light intensity and single initiator was prepared. The chemical structure, morphology, and thermal stability were analyzed through instrumental analysis. Proton nuclear magnetic resonance indicated that NP was successfully prepared, and a small fraction of cationic homopolymer was mixed in the product. Polymerization conditions were optimized, and polymerization mechanism was determined by investigating the effects of various parameters on intrinsic viscosity, conversion, and dissolvability. Results showed that the best performance was obtained at indexes of 0.45 wt‰ redox initiator concentration, 0.2 wt‰ azo initiator concentration, 40.0 wt% of cationic monomer, first- and second-stage light intensities of 8.5 and 13 mW/cm², respectively, and 3 wt% urea. Sludge conditioning performances of NP and SP were comparatively evaluated, and the mechanism was determined by investigating the sedimentation behavior and floc size distribution. High intrinsic viscosity, porous morphology structure, and the mixed cationic homopolymer of NP resulted in better sludge conditioning performance.

An efficient, eco-compatible and very cheap method for the construction of triazoles via eliminative azide–olefin cycloaddition (EAOC) reaction has been developed by a catalytic system IL/FeCl3, offering an highly regioselective approach to structurally diverse 1,5-disubstituted 1,2,3-triazoles in up to 95% yield. This strategy features the reuse of catalytic system through simple operations. Mechanistic studies indicated that an asynchronous concerted dipolar cycloaddition-elimination process might be involved.

Transparent electrodes (TEs) made of metallic nanowires, such as Ag, Au, Cu, and Ni, have attracted rising attention for several reasons: 1) they can act as a substitute for tin oxide-based TEs such as indium-tin oxide (ITO) and fluorine-doped tin oxide (FTO); 2) various methods exist for fabricating such TEs such as filtration, spraying and meyer bar coating; 3) greater compatibility with different substrates can be achieved due to the variety of fabrication methods; and 4) extra functions in addition to serving as electrodes, such as catalytic abilities, can be obtained due to the metals that compose the TEs. There are a large number of applications for TEs, ranging from electronics and sensors to biomedical devices. This short review is a summary of recent progress, mainly during the past five years, on silver nanowire-based TEs. The focus of the review will be on theory development, mechanical, chemical and thermal stability and optical properties. The many applications of TEs are outside the scope of this review.

3D bioprinting holds great promise in the field of regenerative medicine as it can create complex structures in a layer-by-layer manner using cell-laden bioinks, making it possible to imitate native tissues. Current bioinks lack both the high printability and the biocompatibility required in this respect. Hence, the development of bioinks that are capable of both properties is needed. In our previous study, a furfuryl-gelatin based bioink, crosslinkable by visible light, was used for creating mouse mesenchymal stem cell-laden structures with high fidelity. In this study, lattice mesh geometries were printed in a comparative study to test against the properties of a traditional rectangular-sheet. After 3D printing and crosslinking, both structures were analysed for swelling and rheological properties, and their porosity estimated using scanning electron microscopy. Results showed that the lattice structure was relatively more porous but sturdy and exhibited a lower degradation rate compared to the rectangular-sheet. Further, the lattice allowed encapsulation of a greater number of cells, allowing them to proliferate to a greater extent compared to the rectangular-sheet that retained a lesser number of cells initially. All of these results collectively affirmed that the lattice poses as a superior scaffold design for tissue engineering applications.

Protein-DNA interactions are critical for the successful functioning of all natural systems. The key role in these interactions is played by processes of protein search for specific sites on DNA. Although it has been studied for many years, only recently microscopic aspects of these processes became more clear. In this work, we present a review on current theoretical understanding of the molecular mechanisms of the protein target search. A comprehensive discrete-state stochastic method to explain the dynamics of the protein search phenomena is introduced and explained. Our theoretical approach utilizes a first-passage analysis and it takes into account the most relevant physical-chemical processes. It is able to describe many fascinating features of the protein search, including unusually high effective association rates, high selectivity and specificity, and the robustness in the presence of crowders and sequence heterogeneity.

Water quality monitoring was an important objective in the surroundings. In this study, we investigated the sensing characteristics of the arrayed flexible chloride sensor with XBee wireless sensing system. The sensitivity and linearity of the wireless chloride sensing devices were 91.6 mV/pCl and 0.988, respectively. The hysteresis voltages were 50.14 mV and 36.71 mV during the cycles of 1 M → 10⁻¹ M → 1 M → 10⁻³ M → 1 M and 1 M → 10⁻³ M → 1 M → 10⁻¹ M → 1 M, respectively. The selectivity coefficients of the ClO⁻ ion, ClO₄⁻ ion, NO₃⁻ ion and I⁻ ion for Cl⁻ ion were 5.0 × 10⁻², 1.0 × 10⁻¹, 5.9 × 10⁻³ and 5.6×10⁻¹, respectively. The sensing characteristics of real time measurement were investigated for dynamic microfluidic. The arrayed flexible chloride sensor was integrated with the microfluidic device, syringe pump and wireless sensing system. The sensitivity and linearity were 273.1 mV/pCl and 0.978 at 35 μL/min, respectively.

A study has been carried out on Ta and Nb recovery by liquid-liquid extraction process using 4-methylacetophenone (4-MAcPh) as organic phase. The 4-MAcPh was compared to methylisobutylketone (MIBK) with respect to extraction efficiencies (kD values) at different concentrations of H2SO4 in the aqueous phase. The results showed a similar extraction of Nb for both solvents. However, for Ta extraction efficiency is increased by a factor of 1.3 for 4-MAcPh. In addition, the MIBK solubilized completely after 6 mol L-1 of H2SO4 against only a loss of 0.14 to 4% for 4-MAcPh between 6 and 9 mol L-1 of H2SO4. The potential of 4-MAcPh has also been studied to selectively recover Ta from a model capacitor waste solution. The results showed a selectivity for Ta in the presence of impurities such as Fe, Ni, Mn. The 4-MAcPh also presents the advantage of having physicochemical properties adapted to its use in liquid-liquid extraction technologies such as mixer-settlers.

Abstract: We have filled a 24 mm diameter glass sphere with a transparent polymer-gel that is radio-fluorogenic, i.e. it becomes (permanently) fluorescent when irradiated, with an intensity proportional to the local dose deposited. The gel consists of >99.9% tertiary-butyl acrylate (TBA) pre-polymerized to ~15% conversion, and ~100 ppm maleimido-pyrene (MPy). Its dimensions and physical properties are close to those of the vitreous body of the human eye. We have irradiated the gel with a 3 mm diameter, 200 kVp X-ray beam with a dose rate of ~1 Gy/min. A 3D (video) view of the beam within the gel has been constructed from tomographic images obtained by scanning the sample through a thin sheet of UV light. To minimize optical artifacts, the cell was immersed in a square tank containing a refractive-index-matching medium. The 20%-80% penumbra of the beam was determined to be ~0.4 mm. The research was a preparatory investigation of the possibility of using the method to monitor the millimetre diameter proton pencil beams used in ocular radiotherapy.

The degradation and detachment of the polyamide (PA) layer in thin-film composite (TFC) membranes due to chlorine based chemical cleaning and material difference of PA layer and substrate are two major bottlenecks of forward osmosis (FO) technology. In this study, a new type of FO membranes were prepared by controlling self-polymerization of dopamine (DA) in the aqueous phase and the reaction with trimesoyl chloride (TMC) during interfacial polymerization (IP) process. These membranes were characterized by attenuated total reflection Fourier transform infrared (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), field-emission scanning electron microscopy (FESEM) and water contact angle measurements. The influence of synthesis parameters such as pH of the aqueous phase, reaction time, temperature, and monomer concentrations were systematically investigated. The optimized membrane showed enhanced structure stability in ethanol (7.1 times higher) and chlorine resistance (72.3 times higher) than the conventional Piperazine(PIP)/TMC membrane due to（poly-dopamine）PDA bio-adhesion and polyester groups in the membrane structure. In general, DA/TMC membranes could be an effective strategy to fabricate high-performance FO membranes with excellent structural stability and chlorine resistance.

A novel gas-phase electrocatalytic system based on a low-temperature proton exchange membrane (Sterion) was developed for the gas phase electrocatalytic conversion of CO2 to liquid fuels. This system achieved gas-phase electrocatalytic reduction of CO2 at low temperatures (below 90 ºC) over a Cu cathode by using water electrolysis-derived protons generated in-situ on an IrO2 anode. Three Cu-based cathodes with varying metal particle sizes were prepared by supporting this metal on an activated carbon at three loadings (50, 20, and 10 wt%; 50%Cu-AC, 20%Cu-AC, and 10%Cu-AC, respectively). The cathodes were characterized by N2 adsorption–desorption, temperature-programmed reduction (TPR), and X-ray diffraction (XRD) whereas their performance towards the electrocatalytic conversion of CO2 was subsequently studied. The membrane electrode assembly (MEA) containing the cathode with the largest Cu particle size (50%Cu-AC, 40 nm) showed the highest CO2 electrocatalytic activity per mole of Cu, with methyl formate being the main product. This higher electrocatalytic activity was attributed to the lower Cu–CO bonding strength over large Cu particles. Different product distributions were obtained over 20%Cu-AC and 10%Cu-AC, with acetaldehyde and methanol being the main reaction products, respectively. The CO2 consumption rate increased with the applied current and the reaction temperature.

In this work, we report the fabrication of the new heterojunction of two 2D hybrid layered semiconductors, ZnO(stearic acid)/V₂O₅(hexadecylamine), and its behavior in the degradation of aqueous methylene blue under visible light irradiation. The optimal photocatalyst efficiency, reached at a ZnO(stearic acid)/ V₂O₅(hexadecylamine) ratio of 1:0.25, results to be about six times higher than that of pristine zinc oxide. Reusability test shows that after three photocatalysis cycles no significant changes in neither the dye degradation efficiency loss nor photocatalyst structure occur. Visible light photocatalytic performance observed indicates there is synergetic effect between both 2D nanocomposites used in the heterojunction. The visible light absorption enhancement promoted by the narrower bandgap V₂O₅ based components; an increased photo generated charge separation favored by extensive interface area; and abundance of hydrophobic sites for dye adsorption appear as probable causes of the improved photocatalytic efficiency in this hybrid semiconductors heterojunction. Estimated band-edge positions for both conduction and valence band of semiconductors together with experiments using specific radical scavengers allow a plausible photodegradation mechanism.

Fabrication of a nanocrystal zinc oxide (ZnO)/nitrogen-doped (N-doped) graphene composite using a novel and facile in situ sol-gel technique is demonstrated. Two-dimensional nanostructure morphology with uniform ZnO nanoparticles (average diameter of 10.25 nm) anchored on N-doped graphene nanosheets was observed via electron microscopy. Because of the polar heteroatoms on the graphene sheets, an abundance sites for polysulfide absorption were provided. More importantly, the strong chemical interaction between ZnO and polysulfides efficiently hindered the transport of polysulfides. Consequently, the lithium/sulfur (Li/S) battery with the ZnO/N-doped graphene composite-coated separator delivered enhanced performance in terms of discharge capacity and cycling stability when compared to the cell with a normal separator. With the modified separator, the battery achieved a discharge capacity as high as 942 mAh g^-1 for the first cycle and remained at 90.02 mAh g^-1 after the 100th charge/discharge test at 0.1 C. Results indicate that impeding the shuttling of polysulfides contributes to efficiently improving the behavior of the Li/S battery.

Bamboo plastic composites have become a hot research topic and a key focus of research. However, the many strong, polar, hydrophilic hydroxyl groups in bamboo flour (BF) results in poor interfacial compatibility between BF and hydrophobic polymers. Maleic anhydride-esterified (MAH-e-BF) and lactic acid-esterified bamboo flour (LA-e-BF) were prepared using an in situ solid-phase esterification method with BF as the raw material and maleic anhydride or lactic acid as the esterifying agent. Fourier transform infrared spectroscopy results confirmed that BF esterification with maleic anhydride and lactic acid was successful, with the esterification degrees of MAH-e-BF and LA-e-BF at 21.04 and 14.36%%, respectively. Esterified BF was characterized by scanning electron microscopy, contact angle testing, X-ray diffractometry, and thermogravimetric analysis. The results demonstrated that esterified BF surfaces were covered with graft polymer and the surface roughness and bonding degree of MAH-e-BF clearly larger than those of LA-e-BF. The hydrophobicity of esterified BF was significantly higher than BF and the hydrophobicity of MAH-e-BF better than LA-e-BF. The crystalline structure of esterified BF showed some damage, with MAH-e-BF exhibiting a greater decrease in crystallinity than LA-e-BF. Overall, the esterification reaction improved BF thermoplasticity, with the thermoplasticity of MAH-e-BF appearing better than LA-e-BF.

In this paper a novel type of a highly sensitive gas sensor device based on the surface photovoltage effect is described. The developed surface photovoltage gas sensor is based on a reverse Kelvin probe approach. As the active gas sensing electrode the porous ZnO nanostructured thin films are used deposited by the direct current (DC) reactive magnetron sputtering method exhibiting the nanocoral surface morphology combined with an evident surface nonstoichiometry related to the unintentional surface carbon and water vapor contaminations. Among others, the demonstrated SPV gas sensor device exhibits a high sensitivity of 1 ppm to NO₂ with a signal to noise ratio of about 50 and a fast response time of several seconds under the room temperature conditions.

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.

Gas chromatography-olfactometry/mass spectrometry coupled with headspace-solid phase microextraction (HS-SPME/GC-O/MS) was applied for the characterization of volatile compounds in Tom Yum soup and its individual ingredients. Using HS-SPME with a 50/30 µm DVB/CAR/PDMS fiber and an extraction temperature of 40 °C for 50 min along with an HP-5MS capillary column, 101 peaks in the HS-SPME/GC-MS chromatogram of Tom Yum soup were detected, and 96 compounds were identified including alcohols, aldehydes, esters, ethers, and terpenes. These findings are based on the comparison of MS spectra with the NIST library as well as experimental and literature retention index data. In comparison with the compound profiles of each individual ingredient of Tom Yum soup (both before and after cooking), five extra volatile compounds in Tom Yum soup were found after the cooking process. Furthermore, odor descriptions of the eighteen aroma compounds in Tom Yum soup, along with the odor ingredient sources, were also obtained.

Malignant melanoma is a highly aggressive type of cancer that requires radical treatment strategies to inhibit the cancer cell progression and metastasis. In recent years, preclinical research and clinical trials on melanoma treatment are considerably focused on the adjuvant-based immunotherapy for enhancing the immune response of innate immune cells against cancer cells. However, the clinical outcome of these adjuvant-based treatments are inadequate due to improper delivery system for these immune activators to reach the target site. Hence, we developed a vaccine formulation containing tumor lysate protein (TL) and poly I:C (PIC) complexed with positively charged poly (sorbitol-co- polyethylenimine (PEI)(PSPEI). The resulting ionic PSPEI-polyplexed antigen/adjuvant (PAA) (PSPEI-PAA) nanocomplexes were stable at the physiological condition, non-toxic and enhanced intracellular uptake in immature dendritic cells. In murine B16F10 tumor xenograft model, PSPEI-PAA nanocomplexes significantly suppressed tumor growth and did not exhibit any noticeable sign of toxicity. Additionally, the cytotoxic T lymphocytes (CTLs) assay involving co-culturing of splenocytes isolated from the PSPEI-PAA-treated mice with that of B16F10 cells significantly revealed enhanced cancer killing by the TL-reactivated CTLs compared to untreated control mice bearing tumor. Therefore, we strongly believe that PSPEI-PAA nanocomplexes could be an efficient antigen/adjuvant delivery system and also enhance the antitumor immune response against melanoma tumor in the future clinical trials.

Na-magadiite exchanged with cetyl-trimethylammonium cations provided organophilic silicate materials that allowed the effective removal of the acidic dye "eosin". The organic cations were intercalated into the interlayer spacing of the layered silicate via an exchange reaction between the organic cations from their bromide salt and the solid Na-magadiite at room temperature. Different techniques were used to characterize the effect of the initial concentration of the surfactant on the structure of the organo-magadiites. The C, H, N analysis indicated that a maximum of organic cations of 1.03 mmol/g was achieved at initial concentrations higher than 0.25 mmol/g and was accompanied by an expansion of the basal spacing of 3.15 nm, with a tilted angle of 64.5° to the silicate layers. The conformation of the organic surfactants was probed using solid-state ¹³C, finding mainly the trans conformation similar to that of the starting cetyl trimethylammonium bromide salt (C16TMABr). Thermal gravimetric analysis was carried out to study the thermal stability of the resulting organo-magadiites. The intercalated surfactants started to decompose at 200 °C, with a mass loss percentage of 8 % to 25 %, depending on the initial loading of the surfactant, and was accompanied by a decrease of the basal spacing from 3.20 nm to 2.51 nm, as deduced from the in situ X-ray diffraction studies. At temperatures below 220 °C, an expansion of the basal spacing from 3.15 to 3.35 nm occurred. These materials were used as a removal agent for the anionic dye "eosin". The maximum amount of the dye removed was related to the organic cation content and to the initial concentration of eosin, with an improvement from 2.5 mg/g to 98 mg/g. This value decreased when the organo-magadiite was preheated at temperatures above 200 °C. The regeneration tests indicated that an 85 % removal efficiency was maintained after 6 cycles of use for the organo-magadiites.

Veratrum californicum is a rich source of steroidal alkaloids such as cyclopamine, a known inhibitor of the Hedgehog (Hh) signaling pathway. Here we provide a detailed analysis of the alkaloid composition of V. californicum by plant part through quantitative analysis of cyclopamine, veratramine, muldamine and isorubijervine in the leaf, stem and root/rhizome of the plant. To determine if additional alkaloids in the extracts contribute to Hh signaling inhibition, we replicated the concentrations of these alkaloids observed in extracts using commercially available standards and compared the inhibitory potential of the extracts to alkaloid standard mixtures using Shh-Light II cells. Alkaloid combinations enhanced Hh signaling pathway antagonism compared to cyclopamine alone, and significant differences were observed in the Hh pathway inhibition between the stem and root/rhizome extracts and their corresponding alkaloid standard mixtures, indicating that additional alkaloids present in these extracts contribute to Hh signaling inhibition.

Mercury (Hg) fish and seafood contamination is a global concern and needs worldwide sea investigations in order to protect consumers. The aim of this study was to investigate the Hg concentration by means of a rapid and simple analytical technique with direct Mercury Analyzer (DMA-80) in pelagic fish species, Tetrapturus belone (spearfish), Thunnus thynnus (tuna) and Xiphias gladius (swordfish) caught in the Mediterranean Sea. Hg contents were evaluated also in Salmo salar (salmon) as pelagic fish not belonging to the Mediterranean area. The results obtained were variable ranging between 0,015-2,562 mg kg-1 for T. thynnus specie, 0,477-3,182 mg kg-1 for X. gladius, 0,434-1,730 mg kg-1 for T. belone and 0,004-0,019 mg kg-1 for S. salar, respectively. The total Hg tolerable weekly intake (TWI) and % tolerable weekly intake (TWI%) values according to the European Food Safety Authority (EFSA) were calculated. The results highlighted that the pelagic species caught in the Mediterranean Sea should be constantly monitored due to their high Hg contents as well as their TWI and TWI% with respect to S. salar samples.

The organic extract of the Caribbean sponge Smenospongia aurea has been shown to contain an array of novel chlorinated secondary metabolites derived from a mixed PKS-NRPS biogenetic route, such as the smenamides. Here we report the presence of a biogenetically different compound, smenopyrone (1), a polypropionate containing two -pyrone rings. The structure of smenopyrone, including its relative and absolute stereochemistry, was determined by spectroscopic analysis (NMR, MS, ECD) supported by comparison with model compounds from the literature. Pyrone polypropionates are unprecedented in marine sponges, but are commonly found in marine mollusks, where their biosynthesis by symbiotic bacteria has been hypothesized and at least in one case demonstrated. As pyrones have recently been recognized as bacterial signaling molecules, we speculate that smenopyrone could mediate inter-kingdom chemical communication between S. aurea and its symbiotic bacteria.

The surface chemistry and the morphology of SnO2 nanowires, deposited by Vapour Phase Deposition (VPD) method on Au-covered silicon substrate, were studied before and after subsequent air exposure. For this purpose, surface-sensitive methods including X-ray Photoelectron Spectroscopy (XPS), Thermal Desorption Spectroscopy (TDS) and the Scanning Electron Microscopy (SEM) were applied. The studies presented within this paper allowed to determine the surface non-stoichiometry combined with the presence of carbon contaminations, in a good correlation with the surface morphology. The relative concentrations of the main components [O]/[Sn]; [C]/[Sn]; [Au]/[Sn] together with the O – Sn; O – Si bondings were analyzed. The results of TDS remained in a good agreement with the observations from XPS. Moreover, conclusions obtained for SnO2 nanostructures deposited with the use of Au catalyst were compared to the previous obtained for Ag-assisted tin dioxide nanowires. The information obtained within this studies are of great importance for the potential application of SnO2 nanowires deposited on Au covered Si substrate in the field of novel chemical nanosensor devices, since the results can provide an interpretation of how aging effects influence gas sensor dynamic characteristics.

Ferulic acid esters have been suggested as a group of natural chemicals with sunscreen function. The study aimed to utilize an environment-friendly enzymatic method to produce octyl ferulate by esterification of ferulic acid with octanol. The Box-Behnken design with response surface methodology (RSM) was adopted to evaluate the effects of synthesis variables, including reaction temperature (70–90 °C), enzyme amount (1000–2000 PLU) and stir speed (50–150 rpm), on the molar conversion of octyl ferulate. According to the joint test, both the reaction temperature and enzyme amount had great impacts on the molar conversion. RSM-developed second-order polynomial equation further showed great ability on data-fitting. Based on ridge max analysis, the optimum parameters for the biocatalyzed reaction were: 72 h reaction time, 92.2 °C reaction temperature, 1831 PLU enzyme amount and 92.4 rpm stir speed, respectively. Finally, the molar conversion of octyl ferulate under optimum condition was verified to be 93.2 ± 1.5%. In conclusion, high yield of octyl ferulate synthesized by commercial immobilized lipase under elevated temperature conditions has been suggested, which our findings could broaden the utilization of the lipase and provide a biocatalytic approach, instead of the chemical method, for ferulic acid ester synthesis.

Degussa P25 is a benchmark form of TiO₂ used worldwide in photocatalysis studies. Currently no such benchmark exists for co-catalysts, which are essential for many photocatalytic reactions. Here, we present the preparation of Pt nanocluster co-catalysts on TiO₂ using an unmodified commercial source and equipment that is commonly available. Transmission electron microscopy reveals that the procedure produces TiO₂ decorated with Pt atom and nanoclusters (1-5 atoms). Optical reflectance and X-ray diffraction measurements show that the procedure does not affect the TiO₂ polymorph or UV-Vis absorbance. Gas phase photocatalytic splitting of heavy water (D₂O) shows that the Pt nanocluster decorated TiO₂ outperforms Pt nanoparticle (produced by photodeposition) decorated TiO₂ in D₂ production. Pt nanoclusters, produced directly from a commercial source, with high co-catalyst activity are prime candidates to be used in benchmark photocatalytic reactions.

Tantalum doped ZnO structures (ZnO:Ta) were synthesized and some of their characteristics were studied. ZnO material was deposited on silicon substrates by using a hot filament chemical vapor deposition (HFCVD) reactor. The raw materials were a pill made of a mixture of ZnO and Ta₂O₅ powders, and molecular hydrogen was used as a reactant gas. Percentage of tantalum was varied from 0 to 500 mg by varying the percentage of tantalum oxide in the mixture of the pill source, by holding a fixed amount of 500 mg of ZnO in all experiments. X-ray diffractograms confirmed the presence of zinc oxide in the wurtzite phase and metallic zinc with a hexagonal structure, and no other phase was detected. Displacements to lower angles of reflection peaks, compared with those from samples without contamination, were interpreted as the inclusion of the Ta atoms in the matrix of the ZnO. This fact was confirmed by EDS and XRD measurements. From SEM images from undoped samples exhibited mostly micro sized semi-spherical structures while doped samples displayed a trend to grown as nanocrystalline rods. The presence of tantalum during the synthesis affects the way of the growth. Green photoluminescence at naked eye was observed when Ta doped samples were illuminated by ultraviolet radiation and confirmed by PL spectra. PL intensity on Ta doped ZnO varied from those undoped samples up to 8 times.

The processing of alkanes (the main components of natural gas) for obtaining of industrially important chemical products is one of the most urgent environmental problems, because the major share of raw materials are burned in torches. Therefore, the main goal of the work is the development of catalysts and conditions for obtaining of important petrochemical products from light alkanes. For the preparation of catalysts, Mo, Cr and Ga oxide catalysts as well as catalysts based on heteropoly compounds, supported on natural materials were used. The catalysts were prepared by the capillary impregnation method and used in oxidative conversion in a flowing unit while varying the process conditions. It has been determined that 5 and 10% MoCrGa catalysts are optimal for obtaining of liquid and gaseous products, and 1% catalyst is more favorable for the synthesis of gaseous products. Supported catalysts from heteropoly acid Н₃PW₁₂O₄₀ are highly active in oxidative dehydrogenation and cracking processes, which are concurrent. High activity is caused by dispersity of catalysts, formation of crystal hydrates and amorphous phase of heteropoly acid in a condition of interaction with carrier. Maximum yield of C₂H₄ - 35.2% at 973 K, C₃H₆ – 20.0% and C₄H₈ – 14.3% at 773 К were observed.

In the present study, the performance of a 70 L photobioreactor, operating outdoors, was investigated using a purple bacterial strain as Rhodopseudomonas sp. S16-VOGS3 for producing poly-3-hydroxybutyrate (PHB). The novel photobioreactor was equipped with 5L-shaped rows; the bottom of every row was placed in a stainless-steel tank containing water with controlled temperature. The photofermentation trials were carried out under fed-batch mode and under a semi-continuous regimen using lactic acid as carbon source. The effect of the irradiance and the C/N ratio on the PHB accumulation was investigated, in order to evaluate the optimal bacterial growth. The results showed the feasibility of the prototype photobioreactor for the production of PHB by Rhodopseudomonas sp. S16-VOGS3 under the natural light/dark cycle. During the fed-batch growth (144 h long), the cumulative PHB increased quickly reaching the maximum value of 377 mg/L and decreased to 255 mg/L during the semi-continuous regimen (336 h long).

In this paper, the modification of two synthetic steps to obtain EMICORON, with respect to the usual protocol, is reported. EMICORON is a benzo[ghi]perylen-diimmide which was synthesized the first time in our laboratory in 2012 and showed to have in-vivo antitumor activities interfering with tumor growth and development by a multi-target mechanism of action. The provided modifications regarded the reaction times and the reaction conditions as well as the work-up procedures and allowed to increase the global yield of the process from 28% to about 40%. Thus, this new procedure may be more suitable in order to get larger amounts of EMICORON for further preclinical studies.

Joining of aluminium alloys to steels has been extensively studied, especially in the automotive sector. However, aluminium alloys are known to be difficult to join with steels when methods involving fusion welding are used because of hot cracking problem. Hence, a high strength joint between these dissimilar metals would be of benefit especially in reducing the weight of products. In this work the torch brazing method was applied to join AR500 steel with AA7075 aluminium alloy using Al-Si-Zn base filler metal at various flame times. The effect of the brazing work on the intermetallic phase formation and the mechanical strength of the joints were investigated. In this work, the maximum shear load obtained was 6460 N and the presence of the intermetallic phases had reduced the shear strength of the brazed joints. However, the torch brazing process using Al-Si-Zn filler metal had successfully facilitated the joining of these dissimilar metals.

A nanostructured electrochemical bi-sensor system for analysis of milks has been developed using the Layer by Layer technique. The non-enzymatic sensor [CHI+IL/CuPcS]2, is a layered material containing a negative film of the anionic sulfonated copper phthalocyanine (CuPcS) acting as electrocatalytic material, and a cationic layer containing a mixture of an ionic liquid (IL) (1-butyl-3-methylimidazolium tetrafluoroborate) that enhances the conductivity and chitosan (CHI) that facilitates the enzyme immobilization. The biosensor ([CHI+IL/CuPcS]2-GAO) results from the immobilization of galactose oxidase on the top of the LbL layers. FTIR, UV-vis and AFM have confirmed the proposed structure and cyclic voltammetry has demonstrated the amplification caused by the combination of materials in the film. Sensors have been combined to form an electronic tongue for milk analysis. Principal Component Analysis has revealed the ability of the sensor system to discriminate between milk samples with different lactose content. Using PLS-1 calibration models, correlations have been found between the voltammetric signals and chemical parameters measured by classical methods. PLS-1 models provide excellent correlations with lactose content. Additional information about other components such as fats, proteins and acidity can also be obtained. The method developed is simple and the short response time permits its use in assaying milk samples on-line.

The aim of the present study is to provide new insights into the CO2 and CH4 adsorption using a set of biomass-based activated carbons obtained by physical and chemical activation of olive-stones. The adsorption behavior is analyzed by means of pure gas adsorption isotherms up to 3.2 MPa at two temperatures (303.15 and 323.15 K).The influence of the activation method on the adsorption uptake is studied in terms of both textural properties and surface chemistry. For three activated carbons the CO2 adsorption was more important than that of CH4. The chemically activation resulted in higher BET surface area and micropore volume that lead to higher adsorption for both CO2 and CH4. For methane the presence of mesopores seems to facilitate the access of the gas molecules into the micropores while for carbon dioxide, the presence of oxygen groups enhanced the adsorption capacity.

It is important for researchers in material domain to reconstruct and visualize the microstructure of alloy, which helps discover morphologies and properties that can only be found in three dimensional and microscopic space. However, because of the limitation of state-of-the-art sensors, the internal microstructure of the material is not easy to obtain. In this paper, a novel automatic 3D reconstruction method is proposed using diffraction contrast tomography technology to capture the 3D microstructure of Al-La alloy. The pipeline of the proposed method starts from the imaging of Al-La alloy with the LabDCT technique from Carl Zeiss AG, which produces a sequence of 2D microstructure sections. Then, a segmentation algorithm based on superpixel and lifted multicut is proposed to extract the 2D microstructure in an image section. Finally, 2D segmentations are joined together to reconstruct and visulize the 3D microstructure. As a result, a novel morphology of Al-La alloy is recovered with both dendrite and lamellar morphologies. The proposed method has the advantage of the ability to losslessly recover the internal microstructure.

In this work, numerical simulations for the absorption and scattering efficiencies of spheroid core–shell nanoparticles (CSNs) were conducted and studied using the discrete-dipole approximation method. The characteristics of surface plasmon resonances (SPR) depend upon shell thickness, the compositions of the core and shell materials, and the aspect ratio of the constructed CSNs. We used different core@shell compositions, specifically Au@SiO₂, Ag@SiO₂, Au@TiO₂, Ag@TiO₂, Au@Ag, and Ag@Au, for extinction spectra analysis. We also investigated coupled resonance mode wavelengths by adjusting the composition’s layer thickness and aspect ratio. In this study, we show that the extinction efficiency of the Ag@TiO₂ core–shell nanoparticles (CSNPs) was higher than that of the others, and we examined the impact of TiO₂ shell thickness and Ag core radius on SPR peak positions. From the extinction spectra we found that the Ag@TiO₂ nanoparticle had better refractive index sensitivity and figure of merit when the aspect ratio was set to 0.3. All of the experimental results proved that the tunability of these plasmonic resonances was highly dependent on the material used, the layer thickness, and the aspect ratio of the core@shell CSNPs.

The proper hydrogenation of Hyper-coal (HPC) using 1, 2, 3, 4-tetrahydroquinoline (THQ) was able to decrease the oxygen content and adjust the molecular structure of HPC for preparing the spinnable pitch with high softening point (SP). The spinnable pitch prepared from the THQ-soluble (QS) fraction of HPC as a precursor consisted more naphthenic carbon groups than that prepared from the 1-methylnaphthalene (1-MN) soluble (MNS) fraction of HPC. The HPC-QS derived pitch showed excellent spinnability even the SP of 260°C, and the tensile strength of the resultant carbon fiber was up to 1350 MPa with a diameter around 8 µm by only heat treatment at 800°C for 5 min.

Fabrication of a nanocrystal zinc oxide (ZnO)/nitrogen-doped (N-doped) graphene composite using a novel and facile in situ sol-gel technique is demonstrated. Two-dimensional nanostructure morphology with uniform ZnO nanoparticles (average diameter of 10.25 nm) anchored on N-doped graphene nanosheets was observed via electron microscopy. Because of the polar heteroatoms on the graphene sheets, an abundance sites for polysulfide absorption were provided. More importantly, the strong chemical interaction between ZnO and polysulfides efficiently hindered the transport of polysulfides. Consequently, the lithium/sulfur (Li/S) battery with the ZnO/N-doped graphene composite-coated separator delivered enhanced performance in terms of discharge capacity and cycling stability when compared to the cell with a normal separator. With the modified separator, the battery achieved a discharge capacity as high as 942 mAh g^-1 for the first cycle and remained at 90.02 mAh g^-1 after the 100th charge/discharge test at 0.1 C. Results indicate that impeding the shuttling of polysulfides contributes to efficiently improving the behavior of the Li/S battery.

Arthrospira platensis is the widely available source of spirulina and contains distinctive natural pigments including carotenoids and C-phycocyanin (C-PC). In this study, the major carotenoid and C-PC contents were determined in seven commercially available spirulina powder products and laboratory-prepared A. platensis trichomes (AP-1) by an LC-DAD method and a UV-Visible spectrometry, respectively. The correlation of these two pigment content levels with Hunter color coordinates and antioxidant activity was also evaluated. The L* value failed to show a significant correlation with pigment content, but a positive correlation was observed between a* values and the contents of total carotenoid and C-PC. As b* values decreased, the total carotenoid and C-PC contents increased. AP-1 exhibited the highest content of total carotenoids, chlorophyll a and C-PC, and antioxidant activities among the samples. This observation could be related to degradation of these pigments during the mass production process. The carotenoid profiles suggested that the commercial spirulina powders originated from two different sources, A. platensis and A. maxima. Total carotenoid and C-PC content exhibited positive significant correlations with antioxidant activities measured by DPPH and ABTS assays. These results provide a strong scientific foundation for the establishment of standards for the commercial distribution of quality spirulina products.

In this work, we propose an easy and a low cost method for the synthesis of Nitrogen-Doped Graphene NDG and its silver nanowires NW functionalization NWGN. The synthesis was performed using the improved graphene oxide method, chemical reduction of graphene oxide in the presence of caffeine as green nitrogen source and the subsequently the silver nanowires growth in the surface, by the chemical reductions salts in the presence of NG. Achieving a homogeneous growing (coating) of graphene sheets. The samples were analyzed using conventional characterization techniques: SEM-EDX, XRD, FT-IR, RAMAN, TEM, HRTEM, STEM and XPS.

Novel collector lead(II)-benzohydroxamic acid (Pb(II)-BHA) complexes in aqueous solution were characterized by using experimental approaches, including Ultraviolet-visible (UV-Vis) spectroscopy and electrospray ionization–mass spectrometry (ESI-MS), as well as first-principle density functional theory (DFT) calculations with consideration for solvation effects. The Job plot delineated that a single coordinated Pb(BHA)⁺ should be formed first, and the higher coordination number complexes can be formed subsequently. Moreover, the Pb(II)-BHA species can aggregate with each other to form complicated structures, such as Pb(BHA)₂ or highly complicated complexes. ESI-MS results validated the existence of Pb-(BHA)_n=1,2 under different solution pH values. Further, the first-principles calculations suggested that Pb(BHA)⁺ should be the most stable structure, and the Pb atom in Pb(BHA)⁺ will act as an active site to attack nucleophiles. These findings are meaningful to further illustrate the adsorption mechanism of Pb(II)-BHA complexes in mineral processing.

1) Background: The objective was to evaluate the corrosion resistance of different commercially pure ultrafine-grained (UFG) titanium and its alloys with acid etched surface processed by equal-channel angular pressing (ECAP); 2) Methods: Coarse-grained and UFG titanium samples were investigated using polarization resistance technique. Surface characteristics of the native oxidized layer were evaluated by TEM and XRD. Electrochemical tests were under physiological electrolyte at a rate of 1 and 10 mV/s. Weight loss tests were performed after immersion into HCl solution for up to 3 years; 3) Results: UFG titanium was less susceptible to corrosion which was identified under lower rates and at higher polarization resistance than its coarse grain counterparts. Titanium Grade 2 and Grade 4 demonstrated similar corrosion susceptibility. Titanium Grade 5 revealed a thin and tightly adhered native oxide layer with adequate corrosion resistance; 4) Conclusions: ECAP process imposed a more compact and adhered oxidized layer. Surface etching techniques delivered a thicker native TiO₂ layer, being both grain refinement and surface etching techniques responsible for the improved corrosion resistance of Titanium samples under physiological environment after 3 years of observation.

The aim of this study was to develop a novel nanostructured lipid carriers (NLCs) with hepatocytes targeting as carriers for the magnetic resonance imaging (MRI) contrast agent (i.e., magnetic nanostructured lipid carriers, MNLCs), and to evaluate the targeting ability of the MNLCs with T2-weighted MRI both in vitro and in vivo. Here, the galactose-octadecylamine (Gal-ODA) conjugates were synthesized by chemical coupling reaction between lactose acid (LA) and octadecylamine (ODA). Then the superparamagnetic iron oxide (SPIO) loaded nanostructured lipid carrier (conjugated by Gal-ODA, Gal-NLC-SPIO) was prepared by emulsification-ultrasonic method using monoglyceride as lipid materials. The Gal-NLC-SPIO with a diameter of about 50 nm could specifically internalize into LO2 (human hepatic cell line) cells. In vitro MRI results also proved the specific targeting ability of Gal-NLC-SPIO to LO2 cells. The in vivo MR imaging experiments using an orthotopic intrahepatic xenograft tumor model further validated the hepatocytes targeted effect of Gal-NLC-SPIO. The results of this study suggested that Gal-NLC-SPIO can be used as a contrast agent to aid in the diagnosis of hepatic diseases.

Bitumen aging is the major factor which contributes to the deterioration of the road pavement. Oxidation and volatilization are generally considered as the most important phenomena affecting aging in asphalt paving mixtures. The present study was carried to investigate whether various antioxidants provided by natural resources such as phospholipids, ascorbic acid as well as lignin from rice husk, could be used to reduce age hardening in asphalt binders. A selected bituminous material was modified by adding 2 % w/w of the anti-aging natural additives and subjected to accelerated oxidative aging regimes according to the Rolling Thin Film Oven Test (RTFOT) method. The effects of aging were evaluated based on changes in sol-gel transition temperature of modified bitumens measured through Dynamic Shear Rheology (DSR). Moreover, changes of Electron Paramagnetic Resonance (EPR) spectra were monitored on the bituminous fractions asphaltene and maltene separated by solvent extraction upon oxidative aging. The phospholipids-treated binder exhibited the highest resistance to oxidation and the lowest age-hardening effect compared to the other tested anti-oxidants. The combination of EPR and DSR techniques represents a promising method for elucidating the changes in associated complex properties of bitumen fractions promoted by addition of free radical scavengers borrowed by green resources.

The capacity of 3D printing (3DP) technologies to initiate speedy polymerization of solvent free resins accounts for their utility in the manufacturing of medical devices. Nonetheless, independent biological evaluation of 3D printed materials is recommended due to the unique parameters of the manufacturing process, which can influence their physical, chemical, and biological properties. In this study, E-Shell 450 material indicated for 3DP of hearing aid shells and inner ear devices was examined for biological safety using zebrafish bioassays adapted to OECD fish embryo test. In addition, the proprietary material was characterized for composition using headspace gas-chromatography mass spectrometry (GC-MS). To initiate test, newly fertilized zebrafish eggs were cultured on non-treated and ethanol-treated materials in glass petri dishes with ultrapure water, incubated at 28.5°C and assessed for developmental endpoints of toxicity at 24h interval until 96h. Data confirmed non-treated material was extremely toxic in bioassays within 24h whereas ethanol-treated material showed a relative lower toxicity possibly due to ethanoic-aqueous interactions as observed by GC-MS. With the current influx of 3D printing materials, users are urged to exercise caution. Operators must also take cognizance of the potential toxicity of the chemicals used in 3DP and implement safety measures to limit their exposure.

Cold gas-dynamic spray (cold spray) is an evolving coating deposition and restoration technology in which particles are deposited above the sonic speed. This paper presents the non-destructive three-dimensional characterization of cold sprayed stainless steel coating. The visualization of coating morphology and volumetric porosity, and the analyses of porosity size and spatial distributions confirmed that dense stainless steel coating with non-connected, micron-sized gradient porosity is successfully produced by cold spray. The suitability of X-ray tomography for characterizing cold sprayed coatings is assessed.

The dopamine D3 receptor is an important CNS target for the treatment of a variety of neurological diseases. Selective dopamine D3 receptor antagonists modulate the improvement of psychostimulant addiction and relapse. In this study, five and six featured pharmacophore models of D3R antagonists were generated and evaluated with the post-hoc score combining two survival scores of active and inactive. Among Top 10 models, APRRR215 and AHPRRR104 were chosen based on the coefficient of determination (APRRR215: R2training = 0.80; AHPRRR104: R2training = 0.82) and predictability (APRRR215: Q2test = 0.73, R2predictive = 0.82; AHPRRR104: Q2test = 0.86, R2predictive = 0.74) of their 3D-quantitative structure–activity relationship models. Pharmacophore-based virtual screening of a large compound library from eMolecules (> 3 million compounds) using two optimal models expedited the search process 100-fold speed increase compared to the docking-based screening (HTVS scoring function in Glide) and identified a series of hit compounds having promising novel scaffolds. After the screening, docking scores, as an adjuvant predictor, were added to two fitness scores (from the pharmacophore models) and predicted Ki (from PLSs of the QSAR models) to improve accuracy. Final selection of the most promising hit compounds were also evaluated for CNS-like properties as well as expected D3R antagonism.

A graphene-containing LDH was prepared by re-hydration of the oxides produced by the calcination of an organic LDH. While the memory effect is a widely recognized effect on oxides produced by inorganic LDHs, it is unprecedented from the calcination/re-hydration of organic ones. Different temperatures (400, 600 and 1100 °C) were tested, on the basis of thermogravimetric data. Water instead of a carbonate solution was used for the re-hydration, with CO₂ available from water itself and/or air to induce a slower process with an easier and better intercalation of the carbonaceous species within the layers. The samples were characterized by X-ray Powder Diffraction (XRPD), IR and Raman spectroscopy and scanning electron microscopy (SEM). XRPD indicate the presence of carbonate LDH mixed with a layered phase with a larger d-spacing. IR confirmed that the prevailing anion is carbonate, coming from the water used for the re-hydration and/or air. Raman data indicated the presence of low-ordered graphenic species moieties and SEM the absence of separated graphene of graphitic sheets, suggesting an intimate mixing of the carbonaceous phase with reconstructed LDH. Organic LDHs gave better memory effect after calcination at 400 °C. Conversely, the graphenic species are observed after rehydration of the sample calcined at 600 °C with a reduced memory effect, demonstrating the interference of the carbonaceous phase with LDH reconstruction and the bonding with LDH layers to form a graphene-LDH nanocomposite.

Hierarchical micro-/mesoporous graphitic carbon spheres (HGCS) with a uniform diameter of ~0.35 μm were synthesized by Fe-catalyzed graphitization of amorphous carbon spheres resultant from hydrothermal carbonization. The HGCS resultant from 3 h at 900 °C with 1.0 wt% Fe catalyst had high graphitization degree and surface area as high as 564 m²/g. They also exhibited high specific capacitance of 140 F/g at 0.2 A/g, good electrochemical stability with 94% capacitance retention after consecutive 2500 cycles. The graphitization degree of the HGCS contributed about 60% of their specific capacitance, and their specific capacitance per unit surface area was as high as 0.2 F/m² which was much higher than in the most cases of porous amorphous carbon materials reported before. In addition, the HGCS showed a high adsorption capacity of 182.8 mg/g for methylene blue (MB), which was 12 times as high as that in the case of carbon spheres before graphitization.

Various optically active 2-hydroxyamide derivatives are produced based on the kinetic resolution of racemic 2-hydroxyamides with a diphenylacetyl component and (R)-benzotetramisole [(R)-BTM], a chiral acyl-transfer catalyst, via asymmetric esterification and acylation. It was revealed that a tertiary amide can be used with this novel protocol to achieve high selectivity [22 examples; s-value reaching over 250]. The resulting chiral compounds could be transformed into other useful structures while maintaining their chirality.

This study evaluated the influence of the addition of increasing quantities of Hippophae rhamnoides L. leaves (HRL) on the radical scavenging activity, main oenological parameters and organoleptic characteristics of three white wines made from moschofilero and one white wine made from riesling grapes respectively. Radical Scavenging activity, reducing power, total phenol content (TPC) and color intensity increased in a linear manner in relation to HRL treatments. Indicatively the addition of 0.8 g/L of HRL increased the radical scavenging activity as determined via the inhibition of the DPPH radical from 23.2 to 58.4% in comparison to the initial values. Equally the reducing power as determined by the FRAP assay increased from 34.5 to 82.3%, TPC increased from 12.3 to 26.8% and the color intensity increased from 39-50% . The main oenological attributes examined, remained unchanged after the HRL addition. The addition of up to 0.4 g/L of HRL did not have a major impact on the organoleptic characteristics of the wines tasted whereas concentrations higher than 0.8 g/L were not considered beneficial. Results denote that the addition of Hippophae rhamnoides L. leaves to white wines contributes positively to the overall antioxidant capacity and could be used as an antioxidant agent in wines vinified in the absence of sulphur dioxide.

Mere similar grades of same excipients manufactured by two different manufacturers often differ significantly that they even have an impact on the variations in final product or dosage form. Solid lipids are one of the most available options as matrix former in sustained drug delivery. Due to their chemical and physical complexity, lipids may exhibit a complex behaviour (i.e. melting crystallization and polymorphism). The aim of this study was to evaluate the physical and chemical properties of two Glyceryl Monostearate (GMS) lipids (Geleol from Gattefosse and Capmul GMS 50K from Abitec Corp. USA) and how these properties may affect during melt granulation process for sustained release applications. Thermal processing was applied on GMS samples to understand the polymorphic nature and suitability as meltable binders. Niacin was used as model drug. A thorough evaluation of GMS samples and sustained release tablets was undertaken using analytical techniques such as differential scanning calorimetry (DSC), X-ray diffraction (XRD). Moreover, melt viscosity study assisted to apprehend the behaviour of GMS samples in hot melt extrusion processing. Surface morphology of the drug and extruded granules examined via SEM and AFM revealed high level of surface interaction and dense structure of drug inside lipid matrix. The DSC and XRD study confirmed that Geleol could not withstand the heat treatment applied during thecontinuous melt granulation processing. The shifting of stable β form to an unstable α form in Geleol was detected. In the contrary case, Capmul GMS 50K was able to withstand the heat treatment supported by the applied analytical techniques. Nonetheless,both GMS samples perform differently in final dosage form. This change in stable β form to an unstable α form affected dissolution profiles at 3 months storage in accelerated condition. This study helped to interpret the complex solid-state behaviour of solid lipid extrudates with different compositions, in order to the simply and outline a suitable formulation strategy for the development of lipid-based oral dosage forms.

The important sampling parameters of a headspace solid phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC-MS) procedure, extraction temperature, extraction time and sample volume were optimized to quantify 23 important impact odorants in reduced alcohol red and white wines. A three-factor design of Box-Behnken experiments was used to determine optimized sampling conditions for each analyte, and a global optimized condition at every ethanol concentration of interest determined using a desirability function that accounts for a low signal response for compounds. Shiraz and Chardonnay wines were dealcoholized from 13.7 and 12.2% v/v ethanol respectively, to 8 and 5% v/v, using a commercially available membrane-based technology. A sample set of the reduced alcohol wines were also reconstituted to their natural ethanol level to evaluate the effect of ethanol content reduction on volatile composition. The three-factor Box-Behnken experiment ensured an accurate determination of the headspace concentration of each compound at each ethanol concentration, allowing comparisons between wines at varying ethanol levels to be made. Overall, the results showed that the main effect of extraction temperature was considered the most critical factor when studying the equilibrium of reduced alcohol wine impact odorants. The impact of ethanol reduction upon the concentration of volatile compounds clearly resulted in losses of impact odorants from the wines. The concentration of most analytes decreased with dealcoholization compared to that of the natural samples. Significant differences were also found between the reconstituted volatile composition and 5% v/v reduced alcohol wines, revealing that the dealcoholization effect is the result of a combination between the type of dealcoholization treatment and reduction in wine ethanol content.

We discuss the electrodeposition of two-dimensional (2D) Pt-nanostructures on HOPG achieved under constant applied potential versus a Pt counter electrode (Eappl = ca. - 2.2 V vs RHE). The deposition conditions are discussed in terms of the electrochemical behavior of the electrodeposition precursor (H2PtCl6). We performed cyclic voltammetry (CV) of the electrochemical Pt deposit on HOPG and on Pt substrates to study the relevant phenomena that affect the morphology of Pt deposition. Under conditions where the Pt deposition occurs and H2 evolution is occurring at the diffusion-limited rate (- 0.3 V vs RHE), Pt forms larger structures on the surface of HOPG, and the electrodeposition of Pt is not limited by diffusion. This indicates the need for large overpotentials to direct the 2D growth of Pt. Investigation of the possible effect of Cl- showed that Cl- deposits on the surface of Pt at low overpotentials, but strips from the surface at potentials more positive than the electrodeposition potential. The CV of Pt on HOPG is a strong function of the nature of the surface. We propose that during immersion of HOPG in the electrodeposition solution (3 mM H2PtCl6, 0.5 M NaCl, pH 2.3) Pt islands are formed spontaneously, and these islands drive the growth of the 2D nanostructures.

High porosity and mass transport properties of microfiltration polymeric membranes benefits nutrients supply to cells when used as scaffolds in interstitial perfusion bioreactors for tissue engineering. High nutrients transport is assumed when pore size and porosity of the membrane are in the micrometric range. The present work demonstrates that the study of membrane fouling by proteins present in the culture medium, though not done usually, should be included in the routine testing of new polymer membranes for this intended application. Two poly(ε-caprolactone) microfiltration membranes presenting similar average pore size (~0.7µm) and porosity (>80%) but different external surface porosity and pore size have been selected as case study. The present work demonstrates that a membrane with lower surface pore abundance and smaller external pore size (~0.67 µm), combined with adequate hydrodynamics and tangential flow filtration mode is usually more convenient to guarantee high flux of nutrients. On the contrary, having large external pore size (~1.70µm) and surface porosity would incur in important internal protein fouling that could not been prevented with the operation mode and hydrodynamics of the perfusion system. Additionally, the use of glycerol in the drying protocols of the membranes might cause plasticization and a consequent reduction of mass transport properties due to membrane compaction by the pressure exerted to force perfusion. Therefore, preferentially, drying protocols that omit the use of plasticizing agents are recommended.

Novel 1,2,3-triazole compounds 3–4 were synthesised via the regioselective addition and cyclization reaction of 1,1-enediamines (EDAMs) 1 with p-methylbenzenesulfonyl azide (TsN₃) 2 in 1,4-dioxane at refluxing for 5 hours. As a result, 1,2,3-triazoles 3–4 can be easily and efficiently obtained via catalyst-free click chemistry. The reactions have some advantages such as metal-free catalyst, excellent yield, inexpensive raw materials, and convenient final treatment.

The development of a novel and simple inhibition biosensor array for detection of water pollutants based on immobilized bacteria is the main goal of this work. A series of electrochemical measurements (i.e. cyclic voltammograms) were carried out on screen-printed gold electrodes with three types of bacteria, namely Escherichia coli, Shewanella oneidensis, and Methylococcus capsulatus, immobilized via poly L-lysine. For comparison purposes, similar measurements were carried out on bacteria samples in solutions,; also optical measurements (fluorescence microscopy, optical density, and flow cytometry) were performed on the same bacteria in both liquid and immobilized forms. The study of the effect of heavy metal ions (lead), pesticides (atrazine) and petrochemicals (hexane) on DC electrochemical characteristics of immobilized bacteria revealed a possibility of pattern recognition of the above inhibition agents in aquatic environment.

Alumina dispersion-strengthened copper, Glidcop, is used widely in high-heat-load ultra-high-vacuum components for synchrotron light sources (absorbers), accelerator components (beam intercepting devices) and in nuclear power plants. Glidcop has similar thermal and electrical properties to OFE (oxygen free electrical) copper, but has superior mechanical properties, thus making it a feasible structural material; its yield and ultimate strength are equivalent to those of mild-carbon steel. The purpose of this work has been to develop a brazing technique to join Glidcop to Mo, using a commercial Cu-based alloy. The effects of the excessive diffusion of the braze along the grain boundaries on the interfacial chemistry and joint microstructure, as well as on the mechanical performance of the brazed joints, has been investigated. In order to prevent the diffusion of the braze into the Glidcop alloy, a copper barrier layer has been deposited on Glidcop by means of RF-sputtering.

Forensic detection of non-volatile nitro explosives poses a tough analytical challenge. A colorimetric sensor comprising ultrasonically prepared silica-dye microspheres was developed for sensitive gas detection of cyclohexanone, a volatile marker of explosives 1,3,5-trinitro-1,3,5-triazinane (RDX) and 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX). The silica-dye composites were synthesized from the hydrolysis of ultrasonically sprayed organosiloxanes under mildly heating conditions (150 ^oC), which yields microspherical, nanoporous structures with high surface area (~300 m²/g) for gas exposure. The sensor inks were deposited on cellulose paper and gave sensitive colorimetric responses to trace amount of cyclohexanone vapors even at sub-ppm levels, with the detection limit down to ~150 ppb. The sensor showed high chemical specificity towards cyclohexanone against humidity and other classes of common solvents, including ethanol, acetonitrile, ether, ethyl acetate, and ammonia. Paper-based colorimetric sensors with hierarchical nanostructures could represent an alternative sensing materials for practical applications in the detection of explosives.

Increase demand for palm oil production has indirectly increased waste and pollution. Empty fruit bunch (EFB), which is the major solid waste from this industry, has the potential to be further treated into valuable product. In this study, cellulose will be extracted from EFB through alkali treatment and acid hydrolysis treatment with a different approach and further modified via acetylation and silylation technique. The modified samples are to be utilized to reduce pollution due to palm oil mill effluent (POME) and carbon dioxide (CO2) emission from the industry. The characterization of the extracted and modified cellulose was carried out using attenuated total reflectance-Fourier transform infrared (ATR-FTIR), thermogravimetric analysis (TGA) and scanning electron microscope (SEM). ATR-FTIR analysis revealed that the cellulose was successfully extracted from raw EFB and the cellulose-acetyl, nanocrystalline cellulose (NCC) and cellulose-2 has been successfully modified from the cellulose. TGA analysis shows that both modified cellulose have higher thermal stability compared to raw EFB and extracted cellulose. SEM morphology of the modified cellulose shows a higher surface area due to the wrinkled formation while the wax layer and cuticle pore has been diminished clearly. The modified sample gave a significant performance where cellulose-acetyl absorbed 98.5% of oil compared to unmodified cellulose-1 sample that only absorbed 5% of oil from POME. NCC-AEAPDMS adsorbed physically and chemically 3.5 cm3/g CO2 gas compared to NCC sample, which undergoes only physical adsorption with maximum capacity up to 2.4 cm3/g. Thus, modification can enhanced the performance of cellulose for industrial applications.

Elephant dung coffee (Black Ivory Coffee) is a special Thai coffee produced from Arabica coffee cherries consumed by Asian elephants and collected from their feces. In this work, elephant dung coffee and controls were analyzed using static headspace gas chromatography hyphenated with mass spectrometry (SHS GC–MS), and chemometric approaches were applied for multivariate analysis and the selection of marker compounds that are characteristic of the coffee. Seventy-eight volatile compounds belonging to 13 chemical classes were tentatively identified, including 6 alcohols, 5 aldehydes, one carboxylic acid, 3 esters, 17 furans, one furanone, 13 ketones, 2 oxazoles, 4 phenolic compounds, 14 pyrazines, one pyridine, 8 pyrroles and 3 sulfur-containing compounds. Moreover, four potential discriminant markers of elephant dung coffee, including 3-methyl-1-butanol, 2-methyl-1-butanol, 2-furfurylfuran and 3-penten-2-one were established. The proposed method may be useful for elephant dung coffee authentication and quality control.

Vilsmeier–Haack reaction of (E)-1-(1-(3,5-difluorophenyl)ethylidene)-2-phenylhydrazine (1) using dimethyl formamide in excess of phosphorous oxychloride by conventional method, resulted in the synthesis of title compound 3-(3,5-difluorophenyl)-1-phenyl-1H-pyrazole-4- carbaldehyde (2) in good yield and high purity. Structure characterization of the novel title compound was done by IR, ¹H NMR, ¹³C NMR and mass spectral analysis.

Background: The official standard for quality control of honey is currently based on physicochemical properties. However, this method is time-consuming, cost intensive, and do not lead to information on the originality of honey. This study aims to classify raw stingless bee honeys by bee species origins as a potential classifier using NMR-LCMS-based metabolomics approach. Methods: Raw stingless bee honeys were analysed and classified by bee species origins using proton nuclear magnetic resonance (1H NMR) spectroscopy and an ultra-high performance liquid chromatography-quadrupole time of flight mass spectrometry (UHPLC-QTOF MS) in combination with chemometrics tools. Results: The honey samples were able to be classified into three different groups based on the bee species origins of Heterotrigona itama, Geniotrigona thoracica, and Tetrigona apicalis. D-Fructofuranose (H. itama honey), β-D-Glucose, D-Xylose, α-D-Glucose (G. thoracica honey), and L-Lactic acid, Acetic acid, L-Alanine (T. apicalis honey) identified via 1H NMR data and the diagnostic ions of UHPLC-QTOF MS were characterized as the discriminant metabolites or putative chemical markers. Conclusion: It could be suggested that the quality of honey in terms of originality and purity can be rapidly determined using classification technique by bee species origins via 1H NMR- and UHPLC-QTOF MS-based metabolomics approach.

Carbon nanotubes (CNTs) are effective supports for nano metals and together they represent hybrids that combine unique properties of both. A microwave induced reaction was used to deposit nano palladium on carboxylated and octadecylamine functionalized multiwall CNTs, which were used to carry out C-C coupling reactions in DMF and toluene. These hybrids showed excellent catalytic activity with yield as high as 99.8% while its enhancement with respect to commercially available Pd/C catalyst reached as high as 109%, and the reactions times were significantly lower. Polarity of the functionalized form was found to be a significant factor with the polar carboxylated CNT showing better activity in DMF while the relatively nonpolar octadecyl amine was better in toluene. The results suggest the possibility of tailor making functionalized CNT when used as catalyst supports

Optimum selectivity of enhanced oil recovery techniques would play a substantial role in the economic prosperity of petroleum industries which might be virtually eliminated unnecessary expenditures. In this paper, the simultaneous utilization of foaming agent, surfactant polymer (SP), and supercritical carbon dioxide were taken into the investigation under the miscible condition to evaluate the efficiency of each scenario on the cumulative recovery factor, water cut and pressure drop. According to the results of this experimental evaluation, SP-foam flooding had witnessed the highest blockage which is caused to have the maximum recovery factor due to the mobilization of more oil volume in the low permeable pores and cracks. Furthermore, the utilization of surfactant with supercritical carbon dioxide had experienced the least recovery factor regarding the insufficient foam generation which is led to less mobilization of oil phase in the pore throats.

3D plotting is an additive manufacturing technology enabling biofabrication, thus the integration of cells or biologically sensitive proteins or growth factors into the manufacturing process. However, most (bio-)inks developed for 3D plotting were not shown to be processed into clinical relevant geometries comprising critical overhangs and cavities, which would collapse without a sufficient support material. Herein, we have developed a support hydrogel ink based on methylcellulose (mc), which is able to act as support as long as the co-plotted main structure is not stable. Therefore, 6 w/v %, 8 w/v % and 10 w/v % mc were allowed to swell in water, resulting in viscous inks, which were characterized for their rheological and extrusion properties. The successful usage of 10 w/v % mc as support ink was proven by multichannel plotting of the support together with a plottable calcium phosphate cement (CPC) acting as main structure. CPC scaffolds displaying critical overhangs or a large central cavity could be plotted accurately with the newly developed mc support ink. The dissolution properties of mc allowed complete removal of the gel without residuals, once CPC setting was finished. Finally, we fabricated a scaphoid bone model by computed tomography data acquisition and co-extrusion of CPC and the mc support hydrogel.

The color changes corresponding to chromophore structures in lignin caused by exposure of Eucalyptus（Eucalyptus grandis and E. urophylla）to heat were investigated. Eucalyptus wood samples were heated in saturated steam atmospheres for 10 h at 110℃, 130℃, and 150℃. The lignin was isolated before and after heat treatment. The physicochemical properties of the lignin and changes in chromophore structures during heat treatment was evaluated through wet chemical analysis, FTIR, UV-Vis, GPC, XPSand 13C-NMR. The color of the wood became darker and redder with the increase in pressure and temperature. Depolymerization and dehydration reactions occurred via demethoxylation with heat treatment in saturated steam at 110℃ or 130℃. Lignin condensed to form insoluble compounds after heat treatment in saturated steam at 150℃. G units increased and S units decreased through demethylation during heat treatment, as revealed by FTIR and 13C-NMR analysis.

In this work, we firstly explored a mild, clean, and highly efficient approach for the synthesis of graphene quantum dots (GQDs). GQDs with carboxyl groups or amino groups, were prepared from one-pot environmentally friendly method assisted by hydrogen peroxide, respectively. It was proved that carboxyl groups played an important role in the fluorescence quenching. Based on these findings, we developed a novel fluorescent nanosensor by combining molecularly imprinted polymers (MIPs) with carboxyl functionalized GQDs for the determination of tetracycline (TC) in aqueous samples. The nanocomposite was prepared using a sol-gel process. GQDs-MIPs showed strong fluorescent emission at 410 nm when excited at 360 nm, which was subsequently quenched in the presence of TC. Under optimum conditions, the fluorescence intensity of GQDs-MIPs decreased in response to the increase of TC concentration with good linearity rage of 1.0-104 µg L-1. The limit of detection was determined to be 1 µg L-1. The fluorescence intensity of GQDs-MIPs was more strongly quenched by TC compared to the corresponding non-imprinted polymers, GQDs-NIPs. With the high sensitivity, the material was also successfully worked for the detection of TC in real spiked milk samples.

Electrospun nanofiber-supported thin film composite membranes are among the most promising membranes for seawater desalination via forward osmosis. In this study, a high-performance electrospun polyvinylidenefluoride (PVDF) nanofiber-supported TFC membrane was successfully fabricated after molecular layer-by-layer polyelectrolyte deposition. Negatively-charged electrospun polyacrylic acid (PAA) nanofibers were deposited on electrospun PVDF nanofibers to form a support layer consisted of PVDF and PAA nanofibers. This resulted to a more hydrophilic support compared to the plain PVDF nanofiber support. The PVDF-PAA nanofiber support then underwent a layer-by-layer deposition of polyethylenimine (PEI) and PAA to form a polyelectrolyte layer on the nanofiber surface prior to interfacial polymerization, which forms the selective polyamide layer of TFC membranes. The resultant PVDF-LbL TFC membrane exhibited enhanced hydrophilicity and porosity, without sacrificing mechanical strength. As a result, it showed high pure water permeability and low structural parameter values of 4.12 Lm⁻²h⁻¹bar⁻¹ and 221 µm, respectively, significantly better compared to commercial FO membrane. Layer-by-layer deposition of polyelectrolyte is therefore a useful and practical modification method for fabrication of high performance nanofiber-supported TFC membrane.

The conventional rolled-up model for carbon nanocones assumes that the cone is constructed from a rolled-up graphene sheet joined seamlessly, which predicts five distinct vertex angles. This model completely ignores any effects due to the changing curvature and all bond lengths and bond angles are assumed to be those for the planar graphene sheet. Clearly curvature effects will become more important closest to the cone vertex, and especially so for the cones with the smaller apex angles. Here we construct carbon nanocones which in the assembled cone are assumed to comprise bond lengths and bond angles which are, as far as possible, equal throughout the structure at the same distance from the conical apex. Predicted bond angles and bond lengths are shown to agree well with those obtained by relaxing the conventional rolled-up model using the LAMMPS software. The major objective here is not simply to model physically realisable carbon nanocones for which numerical procedures are far superior, but rather to produce an improved model that takes into account curvature effects close to the vertex, and from which we may determine an analytical formula which represents an improvement on that for the conventional rolled-up model.

Controlling functional properties of matter and combine them for engineering a functional device is nowadays a common direction of scientific community. For instance, heterogeneous magnetic nanostructures can make use of different types of geometrical and compositional modulations to achieve the control of the magnetization reversal along with the nano-entities and thus enabling the fabrication of spintronic, magnetic data storage and sensing devices, among others. In this work, diameter modulated FeNi nanowires are fabricated paying special effort to obtain sharp transition regions between two segments of different diameters (from about 450 nm to 120 nm), enabling precise control over the magnetic behavior of the sample. Micromagnetic simulations performed on single bi-segmented nanowires predict a double step magnetization reversal where the wide segment magnetization switches near 200 Oe through a vortex domain wall, while at 500 Oe the magnetization of the narrow one is reversed through a corkscrew like mechanism. Finally, these results are confirmed with magneto-optic Kerr effect measurements at the transition of isolated bi-segmented nanowires. Furthermore, macroscopic vibrating sample magnetometry is used to demonstrate that the magnetic decoupling of nanowire segments is the main phenomenon occurring over the entire fabricated nanowires.

Traditional Filuferru is an ancient spirit from Sardinia, Italy, usually obtained from the distillation of wine or grape marc. In this contribution, the results of the first chemical characterization of a wide number of craft Filuferru samples has been accomplished in terms of evaluation of the alcoholic strength, qualitative and quantitative GC-MS analysis of the volatile composition of the distillate, and its trace element composition by means a ICP-MS method. Both instrumental methods have been validated and applied on 21 craft samples of Filuferru, whereas one sample of commercial distillate has been analyzed for comparison purposes. Alcoholic strength ranged between 41.0 and 62.4% (v/v). Sixty volatile compounds were identified and ten of them have been quantified. Analogies and differences with Grappa (i.e. the Italian distilled spirit most close to Filuferru) have been highlighted in the qualitative and quantitative profile of this matrix. Often meaningful amounts of acetaldehyde, ethyl acetate, dietyl acetal and acetic acid were measured. Elemental analysis, performed on toxic, non-toxic elements and oligoelements, 18 in total, revealed a wide variability of concentrations in both analytes and samples. High concentrations of Cu are sometimes evidenced, likely caused by losses from the distillation apparatus. The principal components analysis (PCA) allowed the differentiation of the ten volatile compounds quantified in two groups: the former, described mainly by PC1, constituted by acetic acid, ethyl acetate, dietyl acetal and acetaldehyde, and the second, described by PC2, constituted by 1-propanol, 2-methyl-1-propanol, the two coeluiting isomers 2-methyl-1-butanol and 3-methyl-1-butanol,1-hexanol, 2-phenylethanol and 2,3-butanediol. Data obtained may be useful in order to establish a regulation for the production of high-quality traditional Filuferru from Sardinia.

Human mesenchymal stem cells (hMSCs) constitute of cells having potential of self-renewal and proliferation and are commonly isolated from bone marrow aspirates of large bones. The osteogenic potential of these stem cells has been extensively exploited by scientists during the last many years for the biological evaluation of synthetic scaffolds with applications in tissue engineering. Current work aimed to synthesize N-arylhydrazone derivatives of orotic acid and their evaluation as stimulators of human mesenchymal stem cells. Some of the analogs show good to moderate proliferation rate.

Flavonoids are widely recognized as natural polydrugs, given their anti-inflammatory, antioxidant, sedative and antineoplastic activities. Recently, different studies have shown that flavonoid have the potential to inhibit BET bromodomains. Previous reports suggest that flavonoids are putative inhibitors of the ZA channel due to their orientation and interactions with P86, V87, L92, L94 and N140. Herein, a comprehensive characterization of the binding mode of the biflavonoid amentoflavone and fisetin is discussed. To this end, both compounds were docked with BRD4 using four docking programs. Results were post-processed with protein-ligand interaction fingerprints. To gain further insights into the binding mode of the two natural products, docking results were further analyzed with molecular dynamics. Results showed that amentoflavone makes numerous contacts in the ZA channel, as previously described for flavonoids and kinase inhibitors. It was also found that amentoflavone can potentially make contacts with non-canonical residues for BET inhibition. Most of these contacts were not observed with fisetin. Based on these results, amentoflavone was tested for BRD4 inhibition, showing activity in the micromolar range. This work may serve as basis for scaffold optimization and further characterization of flavonoids as BET inhibitors.

Metal-Organic Frameworks (MOFs) are a subclass of porous materials that have unique properties such as varieties of structures from different metals and organic linkers, tunable porosity from a structure or framework design, etc. Moreover, modification/functionalization of the material structure could optimize the material properties and demonstrate high potential for a selected application. MOF materials exhibit exceptional properties and make these materials widely applicable including in energy storage and heat transformation applications. This review aims to give a broad overview of MOFs and their development as adsorbent materials having the potential for heat transformation applications. We summarize current investigations, developments, and possibilities of metal-organic frameworks (MOFs) especially the tuning of the porosity and hydrophobic/hydrophilic design required for this specific application. These materials applied as adsorbent are promising in the thermal driven adsorption for heat transformation using water as working fluid and related application.

Renewable resources gain increasing interest as source for environmentally benign biomaterials, such as drug encapsulation/release compounds, and scaffolds for tissue engineering in regenerative medicine. Being the second largest naturally abundant polymer, the interest in lignin valorization for biomedical utilization is rapidly growing. Depending on resource and isolation procedure, lignin shows specific antioxidant and antimicrobial activity. Today, efforts in research and industry are directed toward lignin utilization as renewable macromolecular building block for the preparation of polymeric drug encapsulation and scaffold materials. Within the last five years, remarkable progress has been made in isolation, functionalization and modification of lignin and lignin-derived compounds. However, literature so far mainly focuses lignin-derived fuels, lubricants and resins. The purpose of this review is to summarize the current state of the art and to highlight the most important results in the field of lignin-based materials for potential use in biomedicine (reported in 2014–2018). Special focus is drawn on lignin-derived nanomaterials for drug encapsulation and release as well as lignin hybrid materials used as scaffolds for guided bone regeneration in stem cell-based therapies.

Many approaches have been developed over time to counter the bioavailability limitations of poorly soluble drugs. With advances in nanotechnology in recent decades, science and industry have been approaching this issue through the formulation of drugs as nanocrystals, which consist of pure drugs and a minimum of surface active agents required for stabilization. They are carrier-free submicron colloidal drug delivery systems with a mean particle size in the nanometer range, typically between 10 and 800 nm. By reducing particle size to nanoscale, the particle surface area available for the molecule dissolution in the direction of dissolution medium is increased, and thus bioavailability is enhanced. This approach has proven successful, as demonstrated by the number of such drug products on the market. R&D and industry have offered many technological solutions to reduce the particle size to nanoscale, and also devised solutions for the handling of particle of nanodimensions, such as methods to accurately measure nanoparticle size and techniques to prevent physicochemical and stability related problems, such as aggregation. The present work provides an overview of the more recent achievements in improving the bioavailability of poorly soluble drugs according to their administration route, and describes the methods developed to overcome physicochemical and stability related problems.

Wearable sensors for human physiological monitoring have attracted tremendous interest from researchers in recent years. However, most of the research was only done in simple trials without any significant analytical algorithms. This study provides a way of recognizing human motion by combining textile stretch sensors based on single-walled carbon nanotubes (SWCNTs) and spandex fabric (PET/SP) and machine learning algorithms in a realistic applications. In the study, the performance of the system will be evaluated by identification rate and accuracy of the motion standardized. This research aims to provide a realistic motion sensing wearable products without unnecessary heavy and uncomfortable electronic devices.

Owing to their unique physicochemical properties, nanoparticles are used in a variety of ways in the field of cancer treatment, including imaging, drug delivery, and photothermal and photodynamic therapies. The fascinating properties of nanoparticles are determined by their size, morphology, and constituent elements, and various synthetic methods and post-synthetic techniques have been applied to control these factors. Herein, we present examples of shape and composition control through galvanic replacement, a technique that exploits redox potential differences between elements to induce spontaneous ion-exchange and highlight its specific contributions to cancer treatment applications. The present article identifies the recent advances in nanoparticle formation techniques and discusses the future outlook of the field.

Novel high energy density materials N14 (1,6-dihydro-1,2,3,3a,4,5,5a,6,7,8,8a,9,10,10a-tetradecazapyrene) and N18 (1,2,2a,3,4,4a,5,6,6a,7,8,8a,9,10,10a,11,12a-octadecazacoronene) were designed, and their structures, detonation performance and stabilities were calculated employing density functional theory (DFT). Calculations reveals that they have a good balance between high energy and stability. Their energy gaps between LUMO and HOMO are all lower than that of TATB, while their impact sensitivity h_50% is estimated close to that of RDX. Concerning energy, detonation performance of the N14 (P = 43.6 GPa, D = 10040 m/s, Q = 2214 cal/g) and the N18 (P = 37.4 GPa, D = 9400 m/s, Q = 2114 cal/g) are comparable to CL-20.

A good optical quality crystal of 2-aminopyridine (2AP) metal complex crystals was grown by slow evaporation technique at room temperature. The transparent and defect less bulk size of 2-aminopyridine potassium dihydrogen orthophosphate metal complex crystals have been grown by solution growth method. The molecular structure and morphology of grown crystals was drawn and planes are indexed using WINXMORPH software. A optical absorption spectrum, the UV cut-off wavelength, Band gap (Eg), Reflectance (R), Refractive Index (n), Extinction coefficient (K) and Electrical susceptibility (χc) are calculated for 2AP metal complex crystals.

The catalytic decomposition of methane (CDM) process produces hydrogen in a single stage and avoids the CO₂ emission thanks to the formation of high added value carbon nanofilaments as by-product. In this work, Ni monometallic and Ni-Co, Ni-Cu and Ni-Fe bimetallic catalysts are tested in the CDM reaction for the obtention of fishbone carbon nanofibers (CNF). Catalysts, in which Al₂O₃ is used as textural promoter in their formulation, are based on Ni as main active phase for the carbon formation and on Co, Cu or Fe as dopants in order to obtain alloys with an improved catalytic behaviour. Characterization of bimetallic catalysts showed the formation of particles of Ni alloys with a bimodal size distribution. For the doping content studied (5 mol. %), only Cu formed an alloy with a lattice constant high enough to be able to favor the carbon diffusion through the catalytic particle against surface diffusion, resulting in higher carbon formations, longer activity times and activity at 750 °C, where Ni, Ni-Co and Ni-Fe catalysts were inactive. On the other hand, Fe also improved the undoped catalyst performance presenting a higher carbon formation at 700 °C and the obtention of narrow carbon nanofilaments from active Ni₃Fe crystallites.

The problem of limited water supply in the Vhembe District (Limpopo Province, South Africa) is exacerbated by a preponderance of dissolved salts, which cause disagreeable taste and odour in the water as reported by the communities using this water for drinking. The water treatment plant that supplies the treated water to the communities in the District sources this raw water from the Nandoni Dam at the Livhuvu river catchment. However, there are no scientific studies that have been reported in the literature which focused on determining the levels of water salinity from various water sources in the municipalities of the District. Water samples from various sites across the Nandoni Dam, a primary source of domestic water supply in the region, were collected during all the seasons basis over a period of twelve months in order to ascertain the concentrations of dissolved salts in the dam. Onsite analyses of the water samples were conducted using the YSI ProDSS multimeter, while the laboratory water analyses were conducted using the spectroquant and atomic absorption spectrometers. Although salinity tests seem to indicate that the water sampled across most of the Nandoni Dam is brackish during all seasons of the year with the highest being 750 mg/L, water samples from the dam mid-outlet and the treatment plant are slightly below the WHO brackish water bracket of 500 mg/L with unfavourable taste for drinking. Results from this study indicate that the water sourced from the Nandoni Dam is not suitable for human consumption and therefore requires integrated water resource management, as well as robust and cost-effective water desalination treatment.