The corrosion inhibition performance of pyridine derivatives (4-methylpyridine and its quaternary ammonium salts) and sulfur-containing compounds (thiourea and mercaptoethanol) with different molar ratios on carbon steel in CO2-saturated 3.5 wt.% NaCl solution was investigated by weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy and scanning electron microscopy. The synergistic corrosion inhibition mechanism of mixed inhibitors was elucidated by the theoretical calculation and simulation. The molecule of pyridine derivatives compound with larger volume has the priority to adsorb on the metal surface, while the molecules of sulfur-containing compounds with smaller volume fill in vacancies. A dense adsorption film would be formed when 4-PQ and sulfur-containing compounds are added at a proper mole ratio.

Nowadays, the imidazolium-based ionic liquids containing acetate counter-ions are attracting much attention as both highly selective absorbents of the acidic gases and CO₂ carriers in the supported ionic liquid membranes. In this regard, the investigation of the gas transport properties of such membranes may be appropriate for better understanding of various factors affecting the separation performance and the selection of the optimal operating conditions. In this work, we have tested CH₄, CO₂ and H₂S permeability across the SILM impregnated by 1-butyl-3-methylimidazolium acetate (bmim[ace]) with the following determination of the ideal selectivity in order to compare the facilitated transport membrane performance with the SILM that dissolves acidic gases physically, namely, containing 1-butyl-3-methylimidazolium tetrafluoroborate (bmim[BF₄]). Both SILMs have showed modest individual gases permeability and ideal selectivity of CO₂/CH₄ and H₂S/CH₄ separation that achieves values up to 15 and 32, respectively. The effect of the feed gas mixture composition on the permeability of acidic gases and permeselectivity of the gas pair was investigated. It turned out that the permeation behavior for the bmim[ace]-based SILM toward the binary CO₂/CH₄, H₂S/CH₄ and ternary CO₂/H₂S/CH₄ mixtures was featured with high acidic gases selectivity due to the relatively low methane penetration through the liquid phase saturated by acidic gases.

Compounds with tyrosinase inhibitory efficacy could be effective as depigmenting agents. Although a large number of natural and synthetic tyrosinase inhibitors have been reported, few of them are used as skin-whitening agents due to poor activity and safety concerns. 3-(2,4-Dihydroxyphenyl)propionic acid (DPPA), a naturally occurring compound isolated from Ficus carica, was previously discovered as a moderate tyrosinase inhibitor. In this study, the structure-activity relationship study of DPPA was conducted. Compound 3g, with the 2,4-resorcinol subunit and terminal hydrophobic di-butylamino group, was identified with low nanomolar enzymatic IC₅₀ value. Additionally, compound 3g could effectively reduce melanin levels in B16-F10 melanoma cells treated with α-melanocyte-stimulating hormone (α-MSH) without affecting cell viability and proliferation. All these results indicated that compound 3g could be considered as a promising candidate for the treatment of diseases associated with hyperpigmentation.

This work demonstrates that a plasmid can function as an efficient biocatalyst in mediating the nitroaldol (Henry) reaction at high temperatures in ultrapure water. Compared with ssDNA, the plasmid displayed a remarkable catalytic efficiency (97% yield within 20 min). Aromatic aldehydes which bear strong or moderate electron-withdrawing groups reacted satisfactorily with nitromethane, which afforded the corresponding β-nitroalcohols in good yields within 2 h (up to 98%). By contrast, aliphatic and aromatic aldehydes with electron-donating groups did not react. Moreover, the yield significantly dropped when the size of the carbanion increased, and the yield was only 10% when nitropropane was used as the donor.

We have developed IrO_x/M-SnO₂ (M = Nb, Ta, and Sb) anode catalysts, IrO_x nanoparticles uniformly dispersed on M-SnO₂ supports with fused-aggregate structures, which make it possible to evolve oxygen efficiently, even with a reduced amount of noble metal (Ir) in proton exchange membrane water electrolysis. Polarization properties of IrO_x/M-SnO₂ catalysts for the oxygen evolution reaction (OER) were examined at 80 °C in both 0.1 M HClO₄ solution (half cell) and a single cell with a Nafion^® membrane (thickness = 50 μm). While all catalysts exhibited similar OER activities in the half cell, the cell potential (E_cell) of the single cell was found to decrease with the increasing apparent conductivities (σ_{app, catalyst}) of these catalysts: an E_cell of 1.61 V (voltage efficiency of 92%) at 1 A cm^-2 was achieved in a single cell by the use of an IrO_x/Sb-SnO₂ anode (highest σ_{app, catalyst}) with a low Ir-metal loading of 0.11 mg_Ir cm^-2 and Pt supported on graphitized carbon black (Pt/GCB) as the cathode, with 0.35 mg_Pt cm⁻². In addition to the reduction of the ohmic loss in the anode catalyst layer, the increased electronic conductivity contributed to decreasing the OER overpotential due to the effective utilization of the IrO_x nanocatalysts on the M-SnO₂ supports, which is an essential factor in improving the performance with low noble metal loadings.

Food analysis demands fast methods for routine control and high throughput of samples. Chromatographic separation enables simultaneous determination of numerous compounds in complex matrices, several approaches increasing separation efficiency and speed of analysis were involved. In this work, modern types of column with monolithic rod or superficially porous particles were employed and compared for determination of eight synthetic food dyes, their chromatographic performance was evaluated. During method optimization, cyano stationary phase Chromolith Performance CN 100 × 4.6 mm and Ascentis Express ES-CN 100 × 4.6 mm, 5 µm were selected for the separation of polar colorants. The separation was performed by gradient elution of acetonitrile/methanol and 2% water solution of ammonium acetate at flow rate 2.0 ml min-1. Mobile phase composition and the gradients were optimized in order to enable efficient separation on both columns. The method using fused-core particle column provided higher separation efficiency, narrow peaks of analytes resulted in increased peak capacity and shortening of analysis time. After the validation, the method was applied for analysis of colored beers, soft drinks and candies.

A common task in the immunodetection of structurally close compounds is to analyze the selectivity of immune recognition: it is required to understand the regularities of immune recognition and to elucidate the basic structural elements which provide it. Triazines are compounds of particular interest for such a research due to their high variability and the necessity of their monitoring to provide safety of agricultural products and foodstuffs. We evaluated the binding of 20 triazines with polyclonal (pAb) and monoclonal (mAb) antibodies obtained using atrazine as the immunogenic hapten. A total of >3000 descriptors was used in QSAR analysis of binding activities (pIC50). Comparison of the two enzyme immunoassay systems showed that the system with pAb is much easier to describe using 2D QSAR methodology, while the system with mAb can be described using the 3D QSAR COMFA. Thus, for the 3D QSAR model of the polyclonal antibodies, the main statistical parameter q² (‘leave-many-out’) is equal 0.498, and for monoclonal antibodies q² is equal 0.566. Obviously, in the case of pAb, we deal with several targets, while in the case of mAb the target is one, and therefore it is easier to describe it using specific fields of molecular interactions distributed in space.

One new La (III) based coordination polymer , namely, [La(1,4-bdc)(H2O)].(H2O) (1) (tpa = terephthalic acid) has been synthesized through the solvothermal synthesis using terephthalic acid. Structural analysis reveals that compound 1 has a 3-D network with a cube topology. The solid state photolumienescence study shows that compound 1 has a strong emission peak at 680 nm upon excitation at 220 nm . The emission peak is characteristic of the red light emission in the visible region of the electromagnetic spectrum.

This study evaluated the physicochemical, mineralogical properties, mobile chemical species’ bioavailability and translocation in Brassica juncea and Spinacea oleracea L plants of a South African coal fired power utility. Coal fly ash (CFA) disposal is associated with various environmental and health risks including air, soil, surface and ground water pollution due to the leaching of toxic chemical species; these ends up in food webs affecting  human health, while repeated inhalation causes bronchitis, silicosis, hair loss and lung cancer. The morphology, chemical, and mineralogical composition of CFA were determined using Scanning Electron Microscopy (SEM), X-ray fluorescence (XRF) and X-ray Diffraction, respectively. In pot culture experiments, S. oleracea L and B. juncea plants were grown in three sets of pots containing CFA (set 1), soil (set 2) and a mixture of CFA plus soil at ratio 1:1 (50% CFA: 50% soil) (set 3), while no plants were grown in set 4 as a control for the leachate samples. SEM showed that surface morphology of CFA has a lower degree of sphericity with irregular agglomerations of many particles. The XRF results revealed that CFA contains 43.65%, 22.68% and 10.89% of SiO₂, Al₂O₃ and Fe₂O₃ respectively which indicate that the CFA is an alumino-silicate material. While XRD showed that the coal CFA contains mullite as a major phase followed by quartz mineral phases. Chemical species such as Fe, Mn, B, Ba and Zn were accumulated highly in most parts of the plant species. However, B. juncea showed higher potential to accumulate chemical species as compared to S. oleracea L. The bioconcentration and translocation factors (BF and TF) showed that B. juncea was the most effective in terms of bioconcentration and translocation of most of the chemical species. This indicates that B. juncea has potential in application for phytoremediation of CFA dumps and could contribute to remediation of CFA dumps and reduction of potential health and environmental impacts associated with CFA.

Fatty Acid Amide Hydrolase (FAAH) is one of the enzymes responsible of endocannabinoids metabolism. The inhibition of FAAH is a useful and indirect strategy to raise endogenous cannabinoid concentrations, which would be useful for the treatment of various pathological processes in which cannabinoid concentrations are lowered. In the present work, we present an extensive 3D-QSAR/CoMSIA study on a series of 90 irreversible inhibitors of FAAH of pyrimidinyl-piperazine-carboxamide structure. The final model obtained was extensively validated (q2 = 0.734; r2test = 0.966; r2m = 0.723), and based on the information derived from the contour maps we reported a series of 10 new compounds designed as powerful FAAH inhibitors (pIC50 of the best-proposed compounds = 12.196; 12.416).

Zinc is mostly extracted from zinc oxide and sulfide minerals, and this process involves flotation as a key step. While it is easier to float the sulfide mineral, its consumption and depletion has led to an increased reliance on zinc oxide minerals, including smithsonite; hence the development of efficient ways of collecting smithsonite by flotation is an important objective. Herein, we describe the use of 2-(hexadecanoylamino)acetic acid (HAA), a novel surfactant, as a collector during smithsonite flotation. The mechanism and flotation performance of HAA during smithsonite flotation were investigated by total organic carbon (TOC) content studies, zeta potential measurements, FTIR spectroscopy, and XPS analyses, combined with micro-flotation experiments. The flotation results revealed that HAA is an excellent collector in pulp over a wide pH range (9–12) and at a relatively low concentration (2 × 10^‒4 mol/L), at which a recovery of close to 90% of the smithsonite mineral was obtained. TOC-content studies reveal that the good flotation recovery is ascribable to large amounts of collector molecule adsorbed on the smithsonite surface, while zeta potential measurements show that the HAA is chemically adsorbed onto the smithsonite. FTIR and XPS analyses reveal that the HAA-collector molecules adsorb onto the smithsonite surface as zinc-HAA complexes involving carboxylate moieties and Zn sites on the smithsonite surface in alkaline solution.

Four angucycline glycosides including three new compounds landomycin N (1), galtamycin C (2) and vineomycin D (3), and a known homologue saquayamycin B (4), along with two alkaloids 1-acetyl-β-carboline (5) and indole-3-acetic acid (6), were identified from the fermentation broth of an intertidal sediments derived Streptomyces sp. Their structures were mainly established by IR, HR-ESI-MS, 1D and 2D NMR techniques. Among the isolated angucyclines, saquayamycin B displayed potent cytotoxic activity against hepatoma carcinoma cells HepG-2, SMMC-7721 and plc-prf-5, with IC50 values 0.135, 0.033 and 0.244 μM respectively, superior to positive drug doxorubicin. Saquayamycin B treatment to SMMC-7721 cells led to the typical morphological signs of apoptosis in 4',6-diamidino-2-phenylindole (DAPI) staining experiment.

Lignin has interesting functionalities to be exploited in adhesives for medicine, foods and textiles. Nanoparticles (NPs) <100 nm coated with poly(L-lysine), PL and poly(L-glutamic acid) PGA were prepared from the laccase treated lignin to coat nanocellulose fibrils (CNF) with heat. NPs ca. 300 nm were prepared, β-casein coated and cross-linked with transglutaminase (Tgase) to agglutinate chamois specimens. Size exclusion chromatography (SEC) and Fourier-transform infrared (FTIR) spectroscopy were used to characterize polymerized lignin, zetapotential and dynamic light scattering (DLS) to ensure coating of colloidal lignin particles (CLPs). Protein adsorption on lignin was studied by quartz crystal microbalance (QCM). Atomic force microscopy (AFM) was exploited to examine interactions between different polymers and to image NPs with transmission electron microscopy (TEM). Tensile testing showed, when using CLPs for the adhesion, the stress improved ca. 10 and strain ca. 6 times compared to polymeric lignin. For the β-casein NPs the values were 20 and 8, respectively, and for the β-casein coated CLPs between these two cases. When NPs were dispersed in adhesive formulation, the Young's moduli confirmed significant improvement in the elasticity of the joints over the adhesive alone. Exploitation lignin in nanoparticulate morphology is a potential method to prepare bionanomaterials for advanced applications.

Widely consumed forest fruits in Gabon, were analyzed for nutrient and bioactive compositions and their potential contributions to meeting the nutrient requirements of consumers. Edible pulps of Panda oleosa, Gambeya lacourtiana and Poga oleosa contained substantial amounts of bioactive compounds; flavonoids (13.5–22.8 mg/100g), proanthocyanins (2.4–7.6 mg/100g), polyphenols (49.6-77.3 mg/100g) and vitamin C (6.7–97.7 mg/100g). The highest content of β-carotene (76.6 µg/100g) was registered in fruits of Pseudospondias longifolia. The fruits of P. oleosa had the highest essential minerals Fe, Zn and Se. If a child aged 1 to 3 years consumed about 200g or if a non-lactating and non-pregnant woman consumed 300g of P. oleosa, A. lepidophyllus, G. lacourtiana, P. longifolia and P. oleosa, they could obtain substantial RDI ranging between 20-100% for energy, vitamins C and E, iron, magnesium, iron and zinc. Forest fruits can considerably contribute towards the human nutrient requirements. Based on the results of this study, forest foods should be considered in formulating policies governing food and nutrition security in Gabon.

Pharmaceuticals contain biologically active components that can pollute water courses as a result of the excretions from individuals and/or uncontrolled release of residues from chemical plants, and they can pose a hazard to health. Pharmaceutical residues can persist at low concentrations in the environment, and thus may be potentially harmful to aquatic animals and to humans.  Controlling and monitoring such residues are therefore a prime interest, for example, a solid-phase extraction uses solid sorbents to purify and preconcentrate the residues prior to their chemical analysis. In the present study, poly (acrylonitrile-co-divinylbenzene-80) sorbents are synthesised by varying the comonomer feed ratios under precipitation polymerisation conditions to deliver a family of porous polymer microspheres. Acrylonitrile confers polar characters onto the sorbents, and the acrylonitrile-derived nitrile groups can be chemically transformed via polymer-analogous reactions into thioamide and sulfonated residues which make the sorbents even more suitable for the capture of polar analytes, including selected pharmaceuticals. The utility of the porous thioamide-sulfonated containing sorbents is demonstrated via the dispersion-solid phase extraction of mefenamic acid from aqueous media; mefenamic acid is an anthranilic acid derivative which is a potent, non-steroidal anti-inflammatory drug which is found in environmental waters at low concentrations.

Diaminomaleonitrile (DAMN) is an electron-rich ligand which is commonly used in the synthesis of purines, amides and Schiff base ligands. In the last case lies the interest in this molecule, given its symmetry and apparent facility to form various ligands and complexes of interest in fields such as organic solar cells and catalysis among others. Nevertheless, its bisubstitution with aldehydes displays certain difficulty due to the double conjugated presence of the nitrile group (C≡N) in its structure, which significantly affect its coordination behavior by modulating the chemical reactivity of its amines. In addition to presenting a practical resume of guidelines for the preparation of different bisubstituted compounds from DAMN, this paper reviews the possibility of attaining a precise characterization by simple spectroscopic techniques. We provide an additional discussion for one of these techniques (commonly reported but often overlooked), given its potential to provide both the symmetry and E/Z configuration of the product. We hope the comprehensive evidence discussed and shown in this review will be helpful to further develop and understand the products derived of this interesting molecule in their broad applications.

This paper presents an overview of the principal structural and dynamics characteristics of reverse micelles (RMs) in order to highlight their structural flexibility and versatility, along with the possibility to modulate their parameters in a controlled-manner. The multifunctionality in a large range of different scientific fields is exemplified in two distinct directions: a theoretical model for mimicry of biological microenvironment and practical application in the field of nanotechnology and nano-based sensors. RMs represents a convenient experimental approach that limits the drawbacks of the conventionally biological studies in vitro, while the particular structure confers them the status of simplified mimics of cells by reproducing a complex supramolecular organization in an artificial system. The biological relevance of RMs is discussed in some particular cases referring to the confinement and crowding environment, molecular dynamics of water and cell membrane structure. The use of RMs in different range of applications seems to be more promising due to their structural and compositional flexibility, a high efficiency and selectivity being achieved. The advance in nanotechnology is based on developing new methods of nanomaterials synthesis and deposition. This review highlighting the advantages of using RMs in synthesis of nanoparticles with specific properties and in nano (bio)sensors design.

Ageing wine is a commonly practice used in winemaking since the quality and sensory profile increase due to the extractable compounds coming from wood by means of barrels or chips. The quantitative and qualitative compounds from wood depend on the species, its origins and the treatments applied in cooperages. Traditionally, oak wood species are most often used in cooperage, specifically Quercus alba, Known as American oak and Q. robur and Q. petraea both known as French oak. However, although this stage is very common for red wines, its use is still restricted in the case of white wines. However, this topic is particularly interesting, since due to the sensorial benefits of wood contact, the option for ageing white wines in barrels or chips is increasingly and widely chosen by winemakers. This review compiles the novel strategies applied to white wines by means of wood contact in the last years with the aim to increase wine quality and sensorial features.

Aflatoxins in feeds cause great health hazards to animals and in advance, to human. Potential of crude clays designated AC, KC, CC and MC and ashes VA and RA were evaluated for their capacity to adsorb aflatoxins B₁ (AFB₁), B₂ (AFB₂), G₁ (AFG₁) and G₂ (AFG₂) relative to a commercial binder Mycobinder^R (Evonik Industries AG) using in-vitro technique. On average, CC, VA, KC, MC, AC, RA and Mycobind^R adsorbed 39.9%, 51.3%, 61.5%, 62.0%, 72.6%, 84.7% and 98.1% of the total aflatoxins in buffered solution, respectively. The capacity of AC and RA was statistically (p<0.05) better in binding aflatoxins next to Mycobind^R. Capacity of the TBM and Mycobind^R to bind aflatoxins, seemed to follow the trend of their cation exchange capacity (CEC). The CEC (meq/100g) of CC, MC, KC, VA, AC, RA and Mycobind^R were 7.0, 15.4, 18.8, 25.4, 27.2, 27.2 and 38.9, respectively. On average 96.3%, 42.7%, 80.8% and 32.1% of AFB1, AFB2, AFG1 and AFG2 were adsorbed, respectively.  Binding capacity of the clays and ashes relative to Mycobind^R was about 100% for AC and RA, 50% for KC, MC and VA and 33.3% for CC.  The AC and RA seem to be promising resources in binding aflatoxins in solution.

In this work, silver nanoparticles (AgNPs) were synthesized rapidly and eco-friendlily using the extract of Mulberry leaves and aqueous solution of silver nitrate without any toxic chemical [1,2]. The Mulberry leaves extract acts as both reducing agent and stabilizing agent. The UV-Vis spectrum shows peak at 430 nm. The TEM image of synthesized AgNPs sample shows spherical shaped particles whose size range from 15 to 20 nm. TEM image of nano silver solution sample synthesized by microwave assisted method shows nearly spherical particles with an average particle size of 10 nm. The absorption UV-vis spectrum of silver nanoparticles synthesized by microwave assisted method (AgNPsmw) shows a sharp absorption band around 415 nm. After two month storage of AgNPsmw, the absorption spectrum of AgNPsmw was taken again. The UV-Vis spectrum shows negligible peak changes of silver nanoparticles have occurred after two months of storage. The synthesized AgNPs material could be used as an antimicrobial, used in the field of textile and in wastewater treatment.

This work is aiming to motivation on the prospect of evolving new thiazole dyes with respectable application properties, expected pharmacological activities. Curcumin Coupling with diverse diazonium salts of 2-amino thiazole derivatives as 2-aminobenzothiazole, 2- amino-5-phenylthiazole, 2 amino-5-methylthiazole and 2 amino-5-nitrothiazole to produce novel azo dyes. All synthesised dyes were completely confirmed their structures via elemental and spectroscopic techniques. The synthesised thiazole derivatives were examined for their “antimicrobial, anticancer and antioxidant” activities. All of the synthesized dyes were applied on synthetic fabrics as polyester and successively their dyeing properties, “light, washing, perspiration, rubbing and sublimation” fastness were evaluated. Prepared dyestuffs are suitable for dyeing polyester fabrics. It was initiate that all of prepared dyes own extraordinary colour hue, along with respectable fastness properties. Also the synthesised thiazole derivatives display moral pharmacology activity.

Positron emission tomography (PET) imaging of Colony Stimulating Factor 1 Receptor (CSF1R) is a new strategy for quantifying both neuroinflammation and inflammation in the periphery since CSF1R is expressed on microglia. AZ683 has high affinity for CSF1R (K_i = 8 nM; IC₅₀ = 6 nM) and >250-fold selectivity over 95 other kinases and, in this paper, we report the radiosynthesis of [¹¹C]AZ683 and initial evaluation of its use in CSF1R PET. [¹¹C]AZ683 was synthesized by ¹¹C-methylation of the desmethyl precursor with [¹¹C]MeOTf in 3.0% non-corrected activity yield (based upon [¹¹C]MeOTf), >99% radiochemical purity and high specific activity. Preliminary PET imaging with [¹¹C]AZ683 revealed no brain uptake in rodents and nonhuman primates suggesting that [¹¹C]AZ683 is a poor candidate for imaging neuroinflammation, but that it could still be useful for peripheral imaging of inflammation.

The three heat-induced coffee contaminants acrylamide, furfuryl alcohol (FA) and 5-hydroxymethylfurfural (HMF) were analyzed in a collective of commercial samples as well as in Coffea arabica seeds roasted under controlled conditions from very light Scandinavian style to very dark Neapolitan style profiles. Regarding acrylamide, average contents in commercial samples were lower than in a previous study in 2002 (196 compared to 303 µg/kg). The roasting experiment confirmed the inverse relationship between roasting degree and acrylamide content, i.e. the lighter the coffee the higher the acrylamide content. However, FA and HMF were inversely related to acrylamide and found in higher contents in darker roasts. Therefore, mitigation measures must consider all contaminants and not be focused isolatedly on acrylamide, specifically since FA and HMF are contained in much higher contents with lower margins of exposure compared to acrylamide.

As part of our ongoing silybin project, this study aims to introduce a basic nitrogen-containing group to 7-OH of 3,5,20-O-trimethyl-2,3-dehydrosilybin or 3-OH of 5,7,20-O-trimethyl-2,3-dehydrosilybin via an appropriate linker for in vitro evaluation as potential anti-prostate cancer agents. The synthetic approaches to 7-O-substituted-3,5,20-O-trimethyl- 2,3-dehydrosilybins through a five-step procedure and to 3-O-substituted-5,7,20-O-trimethyl-2,3- dehydrosilybins via a four-step transformation have been developed. Thirty-two nitrogen-containing derivatives of silybin have been achieved through these synthetic methods for the evaluation of their antiproliferative activities towards both androgen-sensitive (LNCaP) and androgen-insensitive prostate cancer cell lines (PC-3 and DU145) using WST-1 cell proliferation assay. These derivatives exhibited greater in vitro antiproliferative potency than silybin. Among them, 11, 29, 31, 37, and 40 were identified as five optimal derivatives with IC50 values in the range of 1.40–3.06 µM, a 17- to 52-fold improvement in potency as compared with silybin. All these five optimal derivatives can arrest the PC-3 cell cycle in the G0/G1 phase and promote PC-3 cell apoptosis. Derivatives 11, 37, and 40 are more effective than 29 and 31 in activating PC-3 cell apoptosis.

We describe the direct formation of mixed-phase (1T and 2H) MoS2 layers on Si as a photocathode via atomic layer deposition (ALD) for application in the photoelectrochemical (PEC) reduction of water to hydrogen. Without typical series-metal interfaces between Si and MoS2, our p-Si/SiOx/MoS2 photocathode showed efficient and stable operation in hydrogen evolution reactions (HERs). The resulting performance could be explained by spatially genuine device architectures in three dimensions (that is, laterally homo and vertically heterojunction structures). The ALD-grown MoS2 overlayer with the mixed-phase 1T and 2H homojunction passivates light absorber and surface states and functions as a monolithic structure for effective charge transport within MoS2. It is also beneficial in the operation of p-i-n heterojunctions with inhomogeneous barrier heights due to the presence of mixed-phase cocatalysts. The effective barrier heights reached up to 0.8 eV with optimized MoS2 thicknesses, leading to a 670 mV photovoltage enhancement without employing buried Si p-n junctions. The fast-transient behaviors via light illumination show that the mixed-phase layered chalcogenides can serve as efficient cocatalysts by depinning the Fermi levels at the interfaces. A long-term operation of ~ 70 h was also demonstrated in a 0.5 M H2SO4 solution.

One of the research priorities in atmospheric chemistry is to advance our understanding of heterogeneous reactions and their effect on the composition of the troposphere. Chemistry on aqueous surfaces is particularly important in this regard because of their ubiquity and expanse. They range from the surfaces of oceans (360 million km²), cloud and aerosol drops (~10 trillion km²) to the fluids lining the human lung (~200 m²). Typically, ambient air contains reactive gases that may affect human health, influence climate and participate in biogeochemical cycles. Despite their importance, reactions between gases and solutes at air-aqueous interfaces are not well understood. New, surface-specific techniques are required that detect and identify the intermediates and products of such reactions as they happen on liquids. This is a tall order because genuine interfacial reactions are faster than mass diffusion into bulk liquids, and may produce novel species at low concentrations. Herein, we review evidence that validates online pneumatic ionization mass spectrometry of liquid microjets dosed by reactive gases as a technique meeting such requirements. Next, we call attention to results obtained by this approach on reactions of ozone, nitrogen dioxide and hydroxyl radicals with various solutes on aqueous surfaces. The overarching conclusion is that the outermost layers of aqueous solutions are unique media, where equilibria shift and reactions proceed faster than, in some cases along different pathways from the bulk liquids. The fact that the rates and mechanisms of reactions at air-aqueous interfaces may not be deduced from experiments in bulk liquids opens new conceptual frameworks and lines of research, and adds an overlooked dimension to atmospheric chemistry.

Drinking water contamination of lead from various environmental sources, leaching consumer products and intrinsic water-pipe infrastructure is still today a matter of great concern. Therefore, new highly sensitive and convenient Pb²⁺ measurement schemes are necessary, especially for in-situ measurements at a low-cost. Within this work dye/ionophore/Pb²⁺ co-extraction and effective water phase de-colorization was utilized for highly sensitive lead measurements and sub-ppb naked-eye detection. A low-cost ionophore Benzo-18-Crown-6-ether was used, and a simple test-tube mix and separate procedure was developed. Instrumental detection limits were in the low ppt region (LOD=3, LOQ=10), and naked-eye detection was 500 ppt. Note, however, that this sensing scheme still has improvement potential as concentrations of fluorophore and ionophore were not optimized. Artificial tap-water samples, leached by a standardized method, demonstrated drinking water application. Implications for this method are convenient in-situ lead ion measurements.

Almost 50 papers on surface plasmon resonance biosensors, published between 2016 and mid-2018, are reviewed. Papers concerning the determination of large particles such as vesicles, exosomes, cancer cells, living cells, stem cells and microRNA are excluded, as these are covered by a very recent review. The reviewed papers are categorized into five groups, depending on the degree of maturity of the reported solution: ranging from simple marker detection to clinical application of a previously developed biosensor. Instrumental solutions and details of biosensor construction are analyzed, including the chips, receptors and linkers used, as well as calibration strategies. Biosensors with a sandwich structure containing different nanoparticles are considered separately, as are SPR applications for investigating the interactions of biomolecules. An analysis is also made of the markers determined using the biosensors. Concluding, there is shown to be a growing number of SPR applications in the solution of real clinical problems.

To obtain drop-in fuel properties from non-feed biomass, we herein report the catalytic hydrotreatment of microalgae biocrude, produced from hydrothermal liquefaction (HTL) of Spirulina. Our contribution focuses on the effect of temperature, initial H2 pressure, and residence time on the removal of heteroatoms (O and N). In contrast to common hydrotreating experimental protocols at batch scale, we devised a set of two-level factorial experiments and studied the most influential parameters affecting the removal of heteroatoms. It was found that up to 350 °C, the degree of deoxygenation (de-O) is mainly driven by temperature, whereas the degree of denitrogenation (de-N) also relies on initial H2 pressure and temperature-pressure interaction.Based on this, complete deoxygenation was obtained at mild operating conditions (350 °C), reaching a concurrent 47 % denitrogenation. Moreover, three optimized experiments are reported with 100 % removal of oxygen. In addition, the analysis by GC-MS and Sim-Dis gives insight to the fuel quality. The distribution of heteroatom N in lower (<340 °C) and higher (>340 °C) fractional cuts is studied by a fractional distillation unit following ASTM D-1160. Final results show that 63-68 % of nitrogen is concentrated in higher fractional cuts.

Now-a-days, the thrust area of materials’ research is to develop multifunctional materials, which have multiple properties in a single functional material. We are interested to develop multifunctional polysilanes having special functional properties such as optical activity and photoluminescence (PL) properties. In this investigation, poly(methyl phenyl silane) (PMPS) was integrated with a chiral unit and a photoactive unit by in situ photopolymerization of  (R)-N-(1-phenyl ethyl) methacrylamide (R-NPEMAM) and disperse red 1 methacrylate (DR1MA) monomer in the presence of PMPS. PMPS acted as a macrophotoinitiator and by UV exposure it produced macroradicals which initiated polymerization of chiral and photoactive monomers. Thus a block copolymer of PMPS-b-(R-NPEMAM-ran-DR1MA) was synthesized.The synthesized multifunctional organic inorganic hybrid polymer samples were characterized by FTIR and NMR spectroscopy. The molecular weights of the samples were measured by GPC analysis. The optical, chiroptical and photoluminescence properties were studied. The narrow band at about 1638 cm^-1 is due to C=O stretching vibration of -CONH- of the chiral unit.  A wide absorption peaks at 3444 cm^-1 is the characteristic of NH trans stretching vibration of secondary amide group. The asymmetric stretching of NO₂ group appeared at 1481 cm^-1 and the characteristic peak at 1427 cm^-1 was observed due to azo (-N=N-) group stretching of DR1MA unit. The Si-Si band of PMPS appeared at about 462 cm^-1 in FTIR spectra. The optical absorbance observed at 272 nm is due to π-π* transition of aromatic ring and at 330 nm corresponds to σ-σ* transition of Si-Si bond. The other electronic absorption observed in the visible region at 475 nm corresponds to the combined contribution of n-π* and π-π* transition of DR1MA unit. The photoluminescence properties of such polymers were studied for the variation of concentration of the polymer solution and variation with excitation energy such as 275 nm, 325 nm and 475 nm in THF solvent. Such synthesized multifunctional photoactive organic-inorganic polymers having unusual optical, chiroptical and photoluminescence property may find novel optoelectronic (friend foe identification and secretive code identification) applications.

DNA double-strand breaks (DSBs) are deleterious lesions that are generated in response to ionizing radiation or replication fork collapse that can lead to genomic instability and cancer.  Eukaryotes have evolved two major pathways, namely homologous recombination (HR) and non-homologous end joining (NHEJ) to repair DSBs.  Whereas the roles of protein-DNA interactions in HR and NHEJ have been fairly well defined, the functions of small and long non-coding RNAs and RNA-DNA hybrids in the DNA damage response is just beginning to be elucidated.  This review summarizes recent discoveries on the identification of non-coding RNAs and RNA-mediated regulation of DSB repair

New ligand platforms of the type p- or m-Ph{-CR(3,6-tBu2Flu)(Cp)}2 (para-, R = Me (2a), H (2b); meta-, R = Me (2c)) were synthesized via nucleophilic addition of the 3,6-tBu2-fluorenyl-anion onto the parent phenylene-bridged difulvenes (1a‒c). The corresponding discrete homodinuclear zirconium and hafnium bis(dichloro ansa-metallocene) complexes, Ph[{-CR(3,6-tBu2Flu)(Cp)}MCl2]2 (p-, R = Me (3a-Zr2, 3a-Hf2), R = H (3b-Zr2); m-, R = Me (3c-Zr2) were prepared by salt metathesis reactions. An attempt to generate in situ a heterodinuclear complex 3a-Zr-Hf was also undertaken. For the first time, Atmospheric Pressure PhotoIonization (APPI) mass-spectrometric data were obtained for all dinuclear compounds and found to be in excellent agreement with the simulated ones. Preliminary studies on the catalytic performances of these dinuclear complexes, upon activation with MAO, in ethylene homopolymerization and ethylene/1-hexene copolymerization revealed a few differences as compared to those of the monometallic analogues. In particular, slightly lower molecular weights and greater formation of short methyl and ethyl branches were obtained with the dinuclear systems.

The development of novel porous composite materials for organic dye degradation and removal has received increasing attention due to water contamination problem. In this paper, hydrothermal synthesized nano zeolite A have been encapsulated with porous periodic mesoporous organosilica (PMO) through a simple modified StÖber method an organosilane-directed growth-induced etching strategy, the obtained yolk-shell structured sample was further functionalized by the impregnation of copper, realizing the composite material with hierarchical porous and catalytic properties. The morphology, porosity and metal content of the zeolite Cu/A and Cu/[email protected] were fully characterized. As compared to the parent material, the composite Cu/[email protected] have an efficient adsorption and catalytic degradation performance on methylene blue (MB), the removal efficiency reached as high as 95% of 60 mg/L MB with 10min. These novel structured porous composites may have great potential for adsorption and degradation application including waste effluents.

Photoelectrochemical water splitting is a promising field for sustainable energy production using hydrogen. Development of efficient catalysts is essential for resourceful hydrogen production. The most efficient catalysts reported to date have been extremely precious rare-earth metals. One of the biggest hurdles in this research area is the difficulty of developing highly efficient catalysts comparable to the noble metal catalysts. Here, we report that non-noble metal dichalcogenide (Co₃Se₄) catalysts made using a facile one-pot electrodeposition method, showed highly efficient photoelectrochemical activity on a Si photocathode. To enhance light collection and enlarge its surface area even further, we implemented surface nano-structuring on the Si surface. The nano-structured Si photoelectrode has an effective area greater than that of planar silicon and a wider absorption spectrum. Consequently, this approach exhibits reduced overvoltage as well as increased photo-catalytic activity. Such results show the importance of controlling the optimized interface between the surface structure of the photoelectrode and the electrodeposited co-catalyst on it to improve catalytic activity. This should enable other electrochemical reactions in a variety of energy conversion systems.

(R)-1-(4-Amino-3,5-dichlorophenyl)-2-bromoethan-1-ol has been synthesised in 93% enantiomeric excess (ee) by asymmetric reduction of the corresponding ketone catalysed by a ketoreductase and NADPH as the co-factor in DMSO. (S)-N-(2,6-Dichloro-4-(1-hydroxyethyl)phenyl)acetamide has been synthesised in >98% ee by the same system. Both synthons are potential precursors for clenbuterol enantiomers. Clenbuterol is a β₂-agonist used in veterinary treatment of asthma in several countries. The drug is listed on the World Anti-doping Agency’s Prohibited list due to its effect on increased protein synthesis in the body. However, racemic clenbuterol has recently been shown to reduce the risk of Parkinson’s disease. In order to reveal which one (or both) of the enantiomers that cause this effect, the pure enantiomers need to be studied separately. Our biocatalytic approach in order to obtain enantiopure clenbuterol should be applicable to industrial scale.

NiFe alloy nanoparticles/graphene oxide hybrid (NiFe/GO) was prepared for electrochemical glucose sensing. The as-prepared NiFe/GO hybrid was characterized by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The results indicated that NiFe alloy nanoparticles can be successfully deposited on GO. The electrochemical glucose sensing performance of the as-prepared NiFe/GO was studied by cyclic voltammetry and amperometric measurement. Results showed that NiFe/GO modified glassy carbon electrode had sensitivity of 173 μA mM⁻¹cm⁻² for glucose sensing with a linear range up to 5 mM, which was superior to commonly used Ni nanoparticles. Furthermore, high selectivity for glucose detection can be achieved by NiFe/GO. All the results demonstrated that NiFe/GO hybrid was promising for using in electrochemical glucose sensing.

A supramolecular host-guest interaction and sensing between cationic pillar[5]arenes (CP5) and L-carnitine were developed by the competitive host-guest recognition for the first time. The fluorescence sensing platform was constructed by CP5 functionalized Au nanoparticles ([email protected]) as receptor and probe (rhodamine 123, R123), which shown a high sensitivity and selectivity to L-carnitine detection. Due to the property of the negative charge and molecular size of L-carnitine, it can be highly captured by the CP5 via electrostatic interactions and hydrophobic interactions. The mechanism of host-guest between PP5 and L-carnitine was studied by ¹H NMR and molecular docking, which indicated more affinity binding force of PP5 with L-carnitine. Therefore, a selective and sensitive fluorescent method was developed. It has a linear response of 0.1–2.0 and 2.0–25.0 μM and a detection limit of 0.067 μM (S/N = 3) for L-carnitine. The fluorescent sensing platform was also used to detect L-carnitine in human serum and milk samples, which provided potential applications of detection drugs of abuse, and had path for guarding a serious food safety issues.   

Membrane Inlet Mass Spectrometry (MIMS) was used to analyze monochloramine solutions (NH₂Cl) and ammonia solutions in a compact FTICR. Chemical ionization enables identification and quantification of the products present in the permeate. The responses of protonated monochloramine and ammonium increase linearly with the solution concentration. The enrichments were respectively 1.2 and 5.5. Pervaporation is dependent on pH and only the basic form of ammonia NH₃ pervaporates through the membrane. Unexpectedly, the small ammonia molecule permeated very slowly. It could be due to interactions with water molecules inside the membrane that create clusters. Moreover, NH₂Cl solutions, in addition to the NH₃Cl⁺ signal, presented a strong NH₄⁺ signal at m/z 18.034 . Ammonia presence in the low-pressure zone before ionization is probable as NH₄⁺ was detected with all the precursors used, particularly CF₃⁺ and trimethylbenzene that presents a proton affinity higher than monochloramine. Ammonia may be formed inside the membrane due to the fact that NH₂Cl is unstable and may react with the water present in the membrane. Those results highlight the need for caution when dealing with chloramines in MIMS and more generally with unstable molecules.

The use of fluoride (F^-) for decreasing the prevalence and incidence of tooth decay was the greatest worldwide preventive public health measure of the 20th century. There have been controversial reports about the benefits of the use of F^-, because in small amounts it helps prevent dental caries, but in high concentrations it can be potentially toxic and harmful to dental and systemic health. Since the mid-20th century, F^- has been studied by toxicologists, looking at its deleterious effects in human populations. During the last decade, the interest on the undesirable effects has resurfaced because of the knowledge that it interacts with the cellular system, even in low doses, with a very small safety margin. Acute ingestion of toxic amounts of fluoride can cause corrosive gastric mucosa injury. Also respiratory effects such as bleeding, pulmonary edema, tracheostomy and shortness of breath, have been observed in individuals who inhale hydrogen fluoride. Some researchers had shown that F^- is an oxidizing agent and a well-known reversible enzymatic inhibitor that interferes with the enzyme activity of at least 80 proteins, can altered the intracellular redox equilibrium, lipid peroxidation, as well as, alteration in the gene expression and apoptosis induction. The primary purpose of this review is to examine findings of the action of inorganic F^-, and an overview of hard and soft tissue disturbances, known as fluorosis. The goal of this review is to enhance understanding of the mechanisms by which F^- affects cells with an emphasis on human tissue-specific events.

Convenient labeling of proteins is important for observing its function under physiological conditions.  In tissues particularly, heptamethine cyanine dyes (Cy-7) are valuable because they absorb in near infrared (NIR) region (750 – 900 nm) where light penetration is maximal.  In this work, we found Cy-7 dyes with a meso-Cl functionality covalently binding to proteins with free Cys residues under physiological conditions (aqueous environments, at near neutral pH, and 37 °C).  It transpired that the meso-Cl of the dye was displaced by free thiols in protein, while nucleophilic side-chains from amino acids like Tyr, Lys, and Ser did not react.  This finding shows a new possibility for convenient and selective labeling of proteins with near-IR fluorescent probes.

Trans platinum complexes have been the landmark in unconventional drugs prompting the development of innovative structures that might exhibit chemical and biological profiles different to cisplatin. Iodido complexes made a new turning point in the platinum drug design field since their cytotoxicity was reevaluated and reported. In this new study, we have synthesized and evaluated diodido complexes bearing aliphatic amines and pyridines in trans configuration. X-ray diffraction support the structural characterization. Their cytotoxicity has been evaluated in tumor cell lines such as SAOS-2, A375, T-47D and HCT116. Moreover, we report their solution behavior and reactivity with biological models. UVA irradiation induces an increase in their reactivity towards model nucleobase 5´-GMP in early stages, and promotes the release of the pyridine ligand (spectator ligand) at longer reaction times. Density Functional calculations have been performed and the results are compared with our previous studies with other iodido derivatives.

Theoretical approaches to calculate pKa values for Brønsted acids is a challenging task that, most of the time, involves sophisticated and time-consuming methods. Therefore, heuristic approaches are efficient and appealing methodologies to approximate these values. Herein, by considering the electrostatic potential on acidic hydrogen atoms in a similar fashion that a σ–hole is defined, we calculated the maximum surface potential, V_S,max, and used it as a descriptor to correlate it with experimental acidity constants. These values were calculated using the CPCM implicit solvent model (water) with six different methods: five density functionals and the Møller–Plesset second order perturbation theory. Six different basis sets were combined with each method in order to benchmark a total of thirty-six levels of theory. Overall, 1080 calculations were performed and found to correlate with experimental data. The ωB97X-D/6-31+G(d,p) level of theory stands as the best one for consistently reproduce the reported pKa values.

Vitamin B2, also known as riboflavin (RF) is an essential micronutrient for human health and must be obtained from dietary sources. Plants biosynthesize riboflavin and are important dietary sources of vitamin B2 for humans. Our present study reports sensitive detection of Vitamin B2 in widely consumed for tea infusions, namely black, green, sage and rosemary tea infusions, by a capillary electrophoresis method combined with laser induced fluorescence detection. Moreover, the correlation between Vitamin B2 contents of tea plants with their total phenolics (TPs) and antioxidant capacity are evaluated in this study. Whereas green teas have the highest TPs and antioxidant capacity, the highest RF contents are in sage infusions. The RF contents range between 0.34 and 10.36 µg/g for all tea samples studied. Comparing RF contents of tea samples found in this study to the RF contents of known RF sources, tea infusions are proposed as important dietary sources of Vitamin B2.

The antioxidant, antimicrobial, antiproliferative, and enzyme inhibitory properties of five extracts from aerial parts of Salvia pachyphylla were examined to assess the prospective of this plant as a source of natural products with therapeutic potential. Those properties were analyzed performing a set of standard assays. The extract obtained with dichloromethane showed the most variety of components, as yielded promising results in all completed assays. Furthermore, the extract obtained with ethyl acetate exhibited that greatest antioxidant activity as well as the best xanthine oxidase inhibitory activity. Remarkably, both extracts obtained with n-hexane or dichloromethane revealed significant antimicrobial activity against the Gram-positive bacteria; also, they showed greater antiproliferative activity against three representative cell lines of the most common types of cancers in women worldwide, and against a cell line that exemplifies cancers that typically develop drug resistance. Despite that other extracts were less active, such as the methanolic or aqueous, their results are promising for the isolation and identification of novel bioactive molecules. 

Platinum(II) complexes have been found to be effective against cancer cells. Cisplatin curbs cell replication by interacting with the deoxyribonucleic acid (DNA), eventually leading to cell death and reducing cell proliferation. In order to investigate the ability of platinum complexes to affect cancer cells, two examples from the class of polyflurophenylorganoamidoplatinum(II) complexes were synthesised and tested on isolated DNA. The two compounds trans-[N,N’-bis(1,2,3,5,6-pentafluorophenyl)ethane-1,2-diaminato(1-)](2,3,4,5,6-pentafluorobenzoato)(pyridine)platinum(II) (PFB), and trans-[N,N’-bis(1,2,3,5,6-pentafluorophenyl)ethane-1,2-diaminato(1-)](2,4,6-trimethylbenzoato)(pyridine)platinum(II) (TMB) were compared with cisplatin through their reaction with DNA. Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR) spectroscopy was applied to analyse the interaction of the Pt^(II) complexes with DNA in the hydrated, dehydrated and rehydrated state. These were compared with control DNA in acetone/water (PFB, TMB) and isotonic saline (cisplatin) under the same conditions. Principle Component Analysis (PCA) was applied to compare the ATR-FTIR spectra of the untreated control DNA with spectra of PFB and TMB treated DNA samples. Disruptions in the conformation of DNA treated with the Pt^(II) complexes upon rehydration were mainly observed by monitoring the position of the IR-band around 1711 cm^-1 assigned to the DNA base-stacking vibration. Furthermore, other intensity changes in the phosphodiester bands of DNA at ~1234 cm^-1 and 1225 cm^-1 and shifts in the dianionic phosphodiester vibration at 966 cm^-1 were observed. The isolated double stranded DNA (dsDNA) or single stranded DNA (ssDNA) showed different structural changes when incubated with the studied compounds. PCA confirmed PFB had the most dramatic effect by denaturing both dsDNA and ssDNA. Both compounds, along with cisplatin, induced changes in DNA bands at 1711, 1088, 1051 and 966 cm^-1 indicative of DNA conformation changes. The ability to monitor conformational change with infrared spectroscopy paves the way for a sensor to screen for new anticancer therapeutic agents.

The craft beers are outlined as a distinctively flavored, brewed and distributed regionally, using top-fermenting (ale) yeast, bottom-fermenting (lager) yeast or spontaneously fermentation. Craft beers are largely consumed and produced in Brazil and presents great level of polyphenols, which would affect the consumer’s preference. In this way, we analyzed the relation between polyphenols, bitterness and composition of main different styles of craft beers and the consumer´s preference. Six different styles were analyzed according its polyphenol content, bitterness, chemical composition, sensory profile and preference. For preference, a panel with 62 non-trained assessors was used. For sensory profile, the quantitative descriptive analysis was performed, using expert assessors (n = 8). The preferred style was Classic American Pilsner and the style less preferred was Standard American Lager. The craft beer more preferred showed a decreased bitterness (9.52), polyphenol content (0.61 mg EAG/mL), total solids (6.75 ºBrix) and turbidity (7.27 NTU). This beer exhibited reduced sensory notes of malty, fruity, smoked, hoppy and phenolic, but a higher perception of floral, sweet and yeast notes. The bitter attribute has a reduced perception. This study advances understanding the sensory profile and complexity of craft beers styles from Southern Brazilian.

The possibilities of manufacturing batteries with Nafion 117 membranes in the Na⁺-form intercalated by mixtures of non-aqueous organic solvents used both as electrolyte, separator and binder were investigated. Electrochemical stability of various organic solvent mixtures based on N,N-dimethylacetamide, ethylene carbonate, propylene carbonate, tetrahydrofuran was characterized. It was shown that sodium battery based on Nafion-Na membrane intercalated by mixture of ethylene carbonate ‑ propylene carbonate with Na₃V_1.9Fe_0.1(PO₄)₃/C positive electrode is characterized by a discharge capacity of ca. 110 mAh g^-1 (C/10) at room temperature and shows the ability to cycle for a long time. Batteries with Nafion membrane electrolytes, containing N,N-dimethylacetamide were characterized by capacity fading during cycling, which is due to the interaction of N,N-dimethylacetamide and a negative sodium electrode.

The Biginelli reaction is a highly versatile reaction, which leads to dihydropyrimidinones/thiones. This scaffold is reported as being a privileged structure due to its ability to interact with biological targets. Synthesis of ethyl 4-(2-fluorophenyl)-6-methyl-2-thioxo-1-(p-tolyl)-1,2,3,4-tetrahydropyrimidine-5-carboxylate was achieved through the Biginelli reaction using a functionalized thiourea. In silico studies demonstrated that the compound title showed good potential for interacting with ecto-5’-nucleotidase, which has been considered as a target in designs for anti-cancer drugs.

As a part of our ongoing research on endophytic fungi, we have isolated a sesterterpene mycotoxin, fusaproliferin (FUS), from Fusarium solani strain associated with the plant Aglaonema hookerianum Schott. FUS showed rapid and sub-micromolar IC₅₀ against pancreatic cancer cell lines. Time dependent survival analysis and microscopy imaging showed rapid morphological changes in cancer cell lines 4 hours after incubation with FUS. This provides a new chemical scaffold that can be further developed to obtain more potent synthetic agents against pancreatic cancer.

Molecular dynamics(MD) simulations are playing an increasingly important role in structure-based drug discovery (SBDD). Here we review the use of MD for proteins in aqueous solvation, organic/aqueous mixed solvents (MDmix) and with small ligands, to the classic SBDD problems: binding mode and binding free energy predictions. The simulation of proteins in their condensed state reveals the solvent structure and preferential interaction sites (hot spots) on the protein surface. This information is largely transferable across all classes of protein ligands (from water to drugs) and can be used very effectively to understand ligand recognition and improve the predictive capability of well-established methods such as molecular docking. MD simulations for protein and drug or drug-like compounds are now being used but are still computationally expensive and can only be applied to specific cases. On the other hand, MDmix simulations can now be used in SBDD and we will describe the latest developments and implementations. We expect to see an increase in the application of these techniques to a plethora of protein targets to identify new drug candidates with the advent of new tools and faster computers.

The study compared antibacterial potential of hydrolysates of casein and alpha-lactalbumin from cow and goat milk on diarrhea-causing Escherichia coli and Staphylococcus aureus. Milk samples were aseptically obtained from lactating cows and goats. The samples were skimmed; casein was isolated using acetic acid and alpha-lactalbumin by filtrate thermoprecipitation at 75 °C. 50% of each isolate was reconstituted in a buffer and hydrolyzed with papain at 55 °C for 2 hours. The hydrolysates were heated to 75 °C to inactivate papain, cooled and their antibacterial activity determined by disc diffusion method. Results showed alpha-lactalbumins had higher degrees of hydrolysis and antibacterial activity than caseins; goat alpha-lactalbumin had the highest antibacterial activity with mean inhibition zones of 19.60 mm and 19.50 mm on E. coli and S. aureus. Cow alpha-lactalbumin inhibited E. coli more than S. aureus with inhibition zones of 16.80 mm and 12.50 mm. Cow and goat milk casein hydrolysates inhibited E. coli with mean inhibition zones of 8.00 mm and 10.90 mm and inhibited S. aureus with inhibition zones of 4.13 mm and 1.90 mm respectively. The research showed that the milk hydrolysates can be a source of antibiotics for diarrhea treatment. Research should be done to establish the peptide fractions associated with the observed bioactivity.

To circumvent the thermodynamic limitation of the synthesis of oxazolidinones starting from 2-aminoethanols and CO2 and realize incorporation CO2 under atmospheric pressure, a protic ionic liquid-facilitated three-component reaction of propargyl alcohols, CO2 and 2-aminoethanols was developed to produce 2-oxazolidinones along with equal amount of α-hydroxyl ketones. The ionic liquid structure, reaction temperature and reaction time were in detail investigated. And 15 mol% [TBDH][TFE] (1,5,7-triazabicylo[4.4.0]dec-5-ene trifluoroethanol) was found to be able to synergistically activate the substrate and CO2, thus catalyzing this cascade reaction under atmospheric CO2 pressure. By employing this task-specific ionic liquid as sustainable catalyst, 2-aminoethanols with different substituents were successfully transformed to 2-oxazolidinones with moderate to excellent yield after 12 h at 80 oC. This three-component reaction running under atmospheric pressure proves to be a clever detour to avoid the thermodynamic issue in the synthesis of 2-oxazolidinones starting from 2-aminoethanols and CO2.

In the last decade, the tremendous improvement in the sensitivity and also affordability of Liquid Chromatography-tandem Mass Spectrometry (LC-MS/MS) have revolutionized its application in pharmaceutical analysis, resulting in wide-spread of employing LC-MS/MS for determining pharmaceutical compounds including anticancer drugs in pharmaceutical research and also industries. Currently, LC-MS/MS has been widely used to quantify small molecule oncology drugs in various biological matrices to support preclinical and clinical Pharmacokinetic studies in R & D of oncology drugs. This mini-review article will describe the state-of-the art LC-MS/MS and its application in rapid quantification of small molecule anticancer drugs. In addition, efforts have also been made in this review to address several key aspects in the development of rapid LC-MS/MS methods, including sample preparation, chromatographic separation and matrix effect evaluation.

The field of controlled polymerization is growing and evolving at unprecedented rates, facilitating polymer scientists to engineer the structure and property of polymer materials for a variety of applications. However, the lack of degradability, particularly in vinyl polymers, is a general concern for not only environmental sustainability but also biomedical applications. In recent years, there has been a significant effort to develop reversible polymerization approaches in those well-established controlled polymerization systems. Reversible polymerization typically involves two steps including (i) forward polymerization which converts small monomers into macromolecules, and (ii) depolymerization capable of regenerating original monomers. Furthermore, recycled monomers can be repolymerized into new polymers. In this perspective, we highlight recent developments of reversible polymerization in those controlled polymerization systems and offer insight into the promise and utility of reversible polymerization systems. More importantly, the current challenges and future directions to solve those problems are discussed. We hope this perspective can serve as an “initiator” to promote continuing innovations in this fairly new area.

Adenine nucleotide (AN) 2^nd messengers such as 3’,5’-cyclic adenosine monophosphate (cAMP) are central elements of intracellular signaling, but many details of underlying processes remain still elusive. Like all nucleotides, cyclic nucleotide monophosphates (cNMPs) are net-negatively charged at physiologic pH which limits their applicability in cell-based settings. Thus, many cellular assays rely on sophisticated techniques like microinjection or electroporation. This setup is not feasible for medium- to high-throughput formats, and the mechanic stress that cells are exposed to raises the probability of interfering artefacts or false-positives. Here, we present a short and flexible chemical route yielding membrane-permeable, bio-reversibly masked cNMPs for which we employed the octanoyloxybenzyl (OB) group. We further show hydrolysis studies on chemical stability and enzymatic activation, and present results of real-time assays, where we used cAMP and Ca²⁺ live cell imaging to demonstrate high permeability and prompt intracellular conversion of some selected masked cNMPs. Consequently, our novel OB-masked cNMPs constitute valuable precursor-tools for non-invasive studies on intracellular signaling.

Catalyst material plays a pivotal role in the pharmaceutical industry process. Among them, Friedel-Craft acylation reaction is a well-known reaction to synthesis acetophenone derivatives. However, Friedel-Craft acylation mostly used acetyl chloride as starting material with Lewis acid as homogeneous catalyst, which is nonenvironmental friendly process. In this work, a simple and efficient Friedel-Craft acylation reaction is reported by using the palladium oxide doped on activated bentonite (PdOAB) as the heterogeneous catalyst. The PdOAB catalyst material was characterized with scanning electron microscopy-energy dispersive X-ray (SEM-EDX), nitrogen isotherm adsorption, Fourier transform infrared (FTIR), X-ray powder diffraction (XRD), and thermogravimetric-differential thermal analysis (TG-DTA). The acetophenone derivatives with R = -H, -Cl, -CH₃, -OCH₃, -OH and -NH₂ at para position were successfully synthesized from its corresponding aromatic compounds with glacial acetic acid in 86.6, 7.9, 91.7, 86.6, 82.7, and 78.9% yield, respectively. Therefore, a green method was established because the byproduct is water and the catalyst material can be recovered. Furthermore, the substituent (σ) constants were obtained by using Hammet equation, and the catalysis mechanism has been proposed.

Highly macroporous thin films of WO₃ were fabricated on transparent conductive substrates by application of a polymeric organic paste loaded with an amine/tungstate complex.  After spin-coating and annealing at 550^oC, the resulting yellow films are found to be comprised of channeled array of clustered nanoparticles.  These channels are confirmed by scanning electron microscopy to extend through the entire length of the coating.  The high porosity of the material enables the insertion of a co-catalyst into the internal structure of the film.  These internally functionalized composites demonstrate good photosensitivity and stability in neutral electrolyte.

Pounded yam eaten with any type of soup is a delicacy eaten by Nigerians.            It is manually prepared by pounding yam, cocoyam or combination with mortar and pestle. Preparation takes 30-45 mins. Researches on the improvements have taken place to reduce the heavy burden on the pounded yam preparation. One of the efforts made is the fabrication of pounding machine from the Department of Engineering, Federal College of Agriculture, Akure, Nigeria. The aim of this study is to carry out the organoleptic analysis of pounded yam produced from the fabricated machine. A ten-man panelist was used to determine the organoleptic analysis of the pounded yam in terms of the appearance, taste, colour, odour and texture. The panelists were scored with a class of quality grading: 22.6-25.0 (excellent), 20.2-22.5 (good), 18.2-20.1 (satisfactory), 16.2-18.1 (less satisfactory), and <15.2 (unsatisfactory). Also, sensory attributes were scored as 1= unsatisfactory, 2= less satisfactory, 3= satisfactory, 4=good, and 5= excellent. The results were statistically analysed. From the results it was found that the mean results of appearance, colour, odour, taste, and texture were 4.55, 4.43, 4.15, 4.32, and 4.08 respectively. Coefficients of variation (%) were 16.89, 17.80, 21.65, 15.67, and 24.40. The Skewness of the parameters was in negative, while only odour has its Kurtosis in negative form (-0.37). All the panelists rated the appearance (19-24%) of all the samples high above all other parameters. The Pearson Coefficient of Correlation and Principal Component Analysis showed elements of relationships between the parameters. In conclusion, the machine pounded yam was scored above satisfactory, which means the fabricated machine was efficient.

Development of biomarkers of analytes with interest in clinic is an important field of study. In this work, we synthesized and analyzed the new fluorescent acetate-biomarker, Iso-PG. The mechanism of detection is the acetate buffer mediated proton transfer reaction. The rate constants involved were obtained, and we measured the change in the fluorescence lifetime produced as a consequence of the presence of acetate in the medium. Finally, we checked its potential use as acetate biomarker in synthetic serum

Minerals might have played critical roles for the origin and evolution of possible life forms on Mars. The study of the interactions between “building blocks of life” and minerals relevant to Mars mineralogy under conditions mimicking the harsh Martian environment may provide key insight into possible prebiotic processes. Therefore, this contribution aims at reviewing the most important investigations carried out so far about the catalytic/protective properties of Martian minerals toward molecular biosignatures under Martian-like conditions. Overall, it turns out that the fate of molecular biosignatures on Mars depends on a delicate balance between multiple preservation and degradation mechanisms often regulated by minerals, which may take place simultaneously. Such a complexity requires more efforts in simulating realistically the Martian environment in order to better inspect plausible prebiotic pathways and shed light on the nature of the organic compounds detected both in meteorites and on the surface of Mars through in situ analysis.

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.

The seeds of cultivated peanut, Arachis hypogaea, are an agronomically important crop produced for human nutrition, oilseed and feed stock. Peanut seed is the single most expensive variable input cost and thus producers require seed with excellence performance in terms of germination efficiency. During the maturation process, triglycerides are stored in oil bodies as an energy resource during germination and seedling development. The stability of oil body membranes is essential for nutrient mobilization during germination. This study focused on evaluating the phytosterol composition in seed components including the kernel, embryo (heart), and seed coat or skin. Samples of different maturity classes were analyzed for macronutrient and phytosterol content. The three most abundant phytosterols, β-sitosterol, campesterol, and stigmasterol, comprised 82.29%, 86.39%, and 94.25% of seed hearts, kernels, and seed coats, respectively. Stigmasterol concentration was highest in the seed kernel providing an excellent source of this sterol known to have beneficial effects on human health. Peanut hearts contained the highest concentration of sterols by mass potentially providing protection and resources for the developing seedling. The amount of α-tocopherol increases in peanut hearts during the maturation process providing protection from temperature stress and stability required for seedling vigor. These results suggest that phytosterols may play a significant role in the performance of seeds and provides a possible explanation for the poor germination efficiency of immature seeds.

The high interest in N-heterocyclic platinum carbene complexes in cancer research stems from their high cytotoxicity to human cancer cells, their stability, as well as their ease of functionalization. However, the development of these new molecules as anticancer agents still faces multiple challenges, in particular solubility in aqueous media. Here, we synthesized platinum-NHC bioconjugates that combine water-solubility and cytotoxicity by using polyethyleneimine as polymer carrier. We showed that the activity of these conjugates is modulated by the size of the polymer and the overall density of metal ions onto polymer chains. They displayed an effective activity after only 45 minutes of exposure in vitro correlated with a quick uptake by the cells as shown by the use of various fluorescent-tagged derivatives.

In this study, the use of recycled diatomaceous earth as the extraction phase in a the solid phase microextraction (SPME) technique for the determination of polycyclic aromatic hydrocarbons (PAHs) in river water samples, with separation/detection performed by gas chromatography-mass spectrometry (GC-MS), is proposed. The optimized extraction conditions are extraction time 70 min at 80 ºC with no addition of salt. The limits of quantification were close to 0.5 μg L-1 with RSD values lower than 25% (n = 3). The linear working range was 0.5 μg L-1 to 25 μg L-1 for all analytes. The method was applied to samples collected from the Itajaí River (Santa Catarina, Brazil) and the RSD values for repeatability and reproducibility were lower than 15% and 17%, respectively. The efficiency of the recycled diatomaceous earth fiber was compared with that of commercial fibers and good results were obtained, confirming that this is a promising option for use as the extraction phase in SPME.

The high sensitivity of chiroptical responses to conformational changes and supramolecular interactions has prompted an increasing interest in the development of chiroptical applications. However, prediction and understanding the chiroptical responses of the necessary large systems may not be affordable for calculations at high levels of theory. In order to facilitate the development of chiroptical applications, methodologies capable of evaluating the chiroptical responses of large systems are necessary. Exciton chirality method has been extensively used for the interaction between two independent chromophores through the Davydov model. For systems presenting C2 or D2 symmetry one can get to the same results by applying the selection rules. In the present article, analysis of the selection rules for systems with symmetries Cn and Dn with n = 3 and 4 is used to uncover the origin of their chiroptical responses. We hope that the use of the chiroptical symmetry analysis (CSA) for systems presenting the symmetries explored herein as well as for systems presenting higher symmetries will serve as a useful tool for the development of chiroptical applications.

The expression "Follow the water" is used in order to recognize inside the universe, life as it exists on Earth. It is shown here that the expression "Follow the water in its high-subcritical state" can be used in order to recognize the components of life which form prior to the emergence of life. This specific state of water leaves signatures inside the minerals which are produced during high-subcritical water/rock interaction.

This review describes how resonance in amides is greatly affected upon substitution at nitrogen by two electronegative atoms.  Nitrogen becomes strongly pyramidal and resonance stabilisation, evaluated computationally, can be reduced to as little as 50% that of N,N-dimethylacetamide.  However, this occurs without significant twisting about the amide bond, which is borne out both experimentally and theoretically.  In certain configurations, reduced resonance and pronounced anomeric effects between heteroatom substituents are instrumental in driving the HERON (Heteroatom Rearrangement On Nitrogen)^† reaction, in which the more electronegative atom migrates from nitrogen to the carbonyl carbon in concert with heterolysis of the amide bond, to generate acyl derivatives and heteroatom-substituted nitrenes.  In other cases the anomeric effect facilitates S­_N1 and S_N2 reactivity at the amide nitrogen.

In this present study, we conducted untargeted metabolic profiling using Gas Chromatography-Mass Spectrometry (GC-MS) analysis of ascidian Didemnum bistratum to assess the chemical constituents by searching in NIST library with promising biological properties against anti-bacterial and Zika virus vector mosquitocidal Properties. Metabolites, steroids and fatty acids are abundant in crude compounds of ascidian D. bistratum and showed potential zone growth inhibition against bacterial strains Kluyvera ascorbate (10 mm). The active crude compounds of D. bistratum exhibited prominent larvicidal activity against the Zika vector mosquitoes of Aedes aegypti and Cluex quinquefasciatus (LC₅₀ values of 0.4436 to 2.23 mg/mL). The findings of this study provide a first evidence of the biological properties exhibited by D. bistratum extracts, thus increasing the knowledge about the Zika virus vector mosquitocidal properties of ascidian. Overall, ascidian D. bistratum are promising and biocontrol or eco-friendly tool against A. aegypti and C. quinquefasciatus with prospective toxicity against non-target organisms.

In recent years, with the increasing research and development of the LED industry which contains GaN, it is expected that there will be a large amount of related wastes in the future. Especially the gallium has extremely high value of economic, therefore, it is necessary to establish the recycling system of the GaN waste. However, GaN is a direct-gap semiconductor and with high energy gap, high hardness, and high melting point make it difficult to recycle. Therefore, this study will analyze the physical characteristics of LED wastes containing GaN and carry out various leaching method to leach the valuable metals from the waste optimally. Different acids are used to find out the best reagent for leaching the gallium. Different experimental parameters are discussed such as the effect of the different acid agents , concentration, pressure, solid-liquid mass ratio, temperature, and time which influence the leaching efficiency of the gallium. In this study, various leaching methods which effect the leaching efficiency of the gallium are compared and the advantages and disadvantages are discussed. Finally, pressurized acid leaching method is preferred to leach the GaN waste, and hydrochloric acid is used as the leaching solution because of its better leaching efficiency of gallium. Eventually, the leaching efficiency of the gallium can reach to 98%.

Lithium titanates are used in various applications, such as anode materials for lithium intercalation (Li4Ti5O12) or breeding materials in fusion reactors (Li2TiO3). Here, we report the formation of nano-crystalline lithium titanates by a mechanochemical approach and present a deeper insight into their structural characteristics by PXRD and solid-state NMR spectroscopy. The compounds were synthesized in a high energy planetary ball mill with varying milling parameters and different grinding tools. NaCl type Li2TiO3 (α-Li2TiO3) was formed by dry milling of lithium hydroxide with titania (rutile or anatase) and by a milling induced structure transformation of monoclinic β Li2TiO3 or spinel type Li4Ti5O12. Heating of mechanochemical prepared α Li2TiO3 induces a phase transformation to the monoclinic phase similar to hydrothermal reaction products, but a higher thermal stability was observed for the mechanochemical formed product. Microstructure and crystallographic structure were characterized by PXRD via Rietveld analysis. Detailed phase analysis shows the formation of the cubic phase from the various educts. A set of two lattice parameters for α Li2TiO3 was refined, depending on the presence of OH- during the milling process. An average crystallite size of less than 15 nm was observed for the mechanochemical generated products. The local Li environment detected by 6Li SPE MAS NMR revealed Li defects in the form of tetrahedral instead of octahedral site occupation. Subsequent adjustment of the structural model for Rietveld refinement leads to better fits, supporting this interpretation.

Traditional edible barbecue products use with lemon juice not only make the barbecue more delicious but also reduce the risk of PAHs in the barbecue products. One of the major economics crops in Taiwan, the waste from citrus fruits was very tremendous mass. However, the peelings of citrus fruits are rich in essential oil, especially, the limonene is the major. Whether the anti-carcinogenesis activities of terpene, such as limonene, in citrus fruits essential oil extraction. This study to demonstrate the PAHs content in fish skin increased markedly after being roasted at 210℃ for 20 minutes and greater mutagenicity risk of roasted fish skin was observed by Ame's test. The reduction of mutagenicity risk of roasted fish skin, which the antimutagenic abilities of substances in descending order were limonene > cold pressure oil > lemon >grapefruit. The antimutagenicity rate and ability of the three extracts were limonene: 18–23%; cold-pressed lemon oil: 18–22%; and steam distilled lemon essential oil: 8–16%. The obvious anti- mutagenicity effects against the PAHs mutagenicity of roasted fish skins can be found in citrus fruits essential oil extraction.

Polydopamine (PDA) deposition, obtained from the oxidation of dopamine and other catecholamines is an universal way to coat all known materials with a conformal coating which can subsequently be functionalyzed at will. The structural analogies between polydopamine and eumelanin, the black-brown pigment of the skin, incited to produce stable polydopamine nanoparticles in solution instead of amorphous precipitates obtained from the oxidation of dopamine. Herein, we demonstrate that size controlled and colloidally stable PDA based nanoparticles can be obtained in acidic conditions, where spontaneous auto-oxidation of dopamine is suppressed, using sodium periodate as the oxidant and a protein like alkaline phosphatase as a templating agent. The size of the [email protected]  nanoparticles depends on the dopamine/enzyme ratio and the obtained particles display the enzymatic activity of alkaline phosphatase with an activity extending up to two weeks after particle synthesis. The [email protected] alkaline phosphatase (Alp) nanoparticles can be engineered in polyelectrolyte multilayered films to potentially design model biosensors.

Essential oils are mixtures of compounds obtained from plants, including flowers, roots, bark, leaves, seeds,peel, fruits, wood, that have risen up in the last decades thanks to their beneficial properties as antibacterial, antifungal and anti-inflammatory agents. The aim of this study was to characterize and analyze 13 different commercial essential oils with two different techniques. The first is GC-MS, coupled with SPME, thanks to which 204 different VOCs have been identified. The results show that a total of 95 compounds was found only in one oil, while the others were found with different frequencies in many of them. The most represented class is that of terpenes, as widely reported in literature. The second technique is based on an array of chemical gas sensors. This system was used to investigate whether sensors are able to identify these products. It turned out that basil, cinnamon and carnation are the most identifiable oils with different number and typology of sensors, especially tin oxide and copper oxide nanowires, while cayeput and thyme are more mistakable samples. Thanks to this detailed study, it has been possible to reach and obtain novel insights for the future development of this type of research.

Pristimerin (PM) is a naturally occurring quinonemethide triterpenoid compound that isolated from the Celastraceae and Hippocrateaceae families. Its anticancer effects have attracted a great deal of attention, but the mechanisms of action remain obscure. In this study, we screened for the active compounds of Pristimerin using a drug-likeness approach. Potential protein targets of Pristimerin were predicted by PharmMapper and Coremine database. Candidate protein targets were then uploaded to GeneMANIA and GO pathway analysis. Finally, compound-target, target-pathway, and compound-target-pathway networks were constructed using Cytoscape 3.3. The results showed that Pristimerin had good drug ability and identified 13 putative protein targets. Network analysis revealed that these targets are associated with cancer, inflammation and other physiological processes. In summary, Pristimerin is predicted to target a variety of proteins and pathways to form a network that exerts systemic pharmacological effects.

In this work, unmodified screen-printed electrode (bare SPE) and Sb-film modified SPE (SbFSPE) sensors were employed for the analysis of trace amounts of Pb(II) in non-deaerated water solutions. The modified electrode was performed in situ in 0.5 mg/L Sb(III) and 0.01 M HCl. The methodology was validated for an accumulation potential of –1.1 V vs. Ag/AgCl and an accumulation time of 60 s. A comparative analysis of bare SPE and SbFSPE showed that the detection and quantification limits decrease for the bare SPE. The method with the bare SPE showed a linear response in the 69.8–368.4 µg/L concentration range, whereas linearity for the SbFSPE was in the 24.0–319.1 µg/L concentration range. This work also reports the reason why the multiple standard addition method instead of a linear calibration curve for Pb(II) analysis should be employed. Furthermore, the analytical method employing SbFSPE was found to be more accurate and precise compared to the use of bare SPE when sensors were employed for the first time, however this performance changed significantly when these sensors were reused in the same manner. Furthermore, electrochemical impedance spectroscopy was used for the first time to analyse the electrochemical response of sensors after being used for multiple successive analyses. Surface characterisation before and after multiple successive uses of bare SPE and SbFSPE sensors, with atomic force microscopy and field emission scanning electron microscopy, showed sensor degradation. The interference effect of Cd(II), Zn(II), As(III), Fe(II), Na(I), K(I), Ca(II), Mg(II), NO₃^– Bi(III), Cu(II), Sn(II), and Hg(II) on the Pb(II) stripping signal was also studied. Finally, the application of SbFSPE was tested on a real water sample (from a local river), which showed high precision (RSD = 8.1%, n = 5) and accurate results.

In this study we investigated the potential of two non-edible oil extracts from seeds of Colliguaya Integerrima (CIO) and Colliguaja Salicifolia (CSO) to use as a renewable source for polyols and eventually polyurethane foams or biodiesel. For this purpose, two novel polyols from the aforementioned oils were obtained in a one-single step reaction using a mixture of hydrogen peroxide and acetic acid. The polyol derivatives obtained from the two studied oils were characterized by spectral (FT-IR, ¹H NMR and ¹³C NMR), physico-chemical (e.g. chromatographic analysis, acid value, oxidizability values, iodine value, peroxide value, saponification number, kinematic viscosity, theorical molecular weights, density, hydroxyl number and hydroxyl functionality) and thermal (TGA) analyses according to standard methods. Physico-chemical results revealed that all parameters, with the exception of the iodine value, were higher for bio-polyols (CSP and CIP polyols) compared to the starting oils. The NMR, TGA and FT-IR analyses demonstrated the formation of polyols. Finally, the OH functionality values for CIP and CSP polyols were 4.50 and 5.00, respectively. This result indicated the possible used of CIP and CSP polyols as a raw material for the preparation of polyurethane rigid foams.

A typical vibrational spectrum in the ice phase has four separate bands: translation, libration, bending and stretching. Ice X, the final ice phase under high pressure, shows an exotic vibrational spectrum. Theoretically, an ideal crystal of ice X only has one peak at 998 cm-1 for Raman scattering and two peaks at 450 cm-1 and 1507 cm-1 for infrared absorption in this work. These three characteristic peaks are indicators of the phase transition between ice VII/VIII and ice X. Despite much experimental and theoretical work on ice X, only this study has clearly indicated these characteristic peaks in the region of the IR band. The phonon density of states shows quite different features than ice VIII, which could be verified by inelastic neutron scattering in the future. The dynamic processes of 15 vibrational normal modes are discussed and the typical hydrogen bonds are missing.

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

In this study, fig leaves, zeolite and alginate were used to prepare a biocomposite for the adsorption of Pb(II) ions from aqueous solutions. Effects of various parameters on the biosorption process such as pH, temperature, initial lead concentration and contact time have been investigated. Maximum uptake of Pb(II) ions (85%) has been achieved at pH 6, with 25 mg/L of initial concentration and at a temperature of 288.15 K. Among the applied models, the data correlated well with Freundlich and D-R models and it was established that the biosorption was physical in nature. The amount of adsorbed lead per gram of sorbent was found to be 150.3 mg/g. Thermodynamic parameters showed the exothermic heat of biosorption and the feasibility of the process. Results have suggested that the prepared biosorbent possesses promising biosorption potential.

Ion association is an important process in aqueous dissolution, precipitation, and~crystallization of ionic inorganic, organic, and biological materials. Polyoxometalates (POMs) are good model compounds for understanding the complex relationships between lattice energy, ion-pairing in solution, and salt solubility. Here we perform calorimetric measurements to elucidate trends in cluster stability, lattice energy, and ion-pairing behavior studies of simple hexatantalate salts in neat water, parent hydroxide solutions, and molybdate melts, extending previous studies on the isostructural hexaniobates. High temperature calorimetry of alkali salts of hexatantalate reveals that the enthalpies of formation from oxides of the K, Rb, and Cs salts are more similar to each other than they are for their niobate analogues and that the tantalate cluster is energetically less stable than hexaniobate. Aqueous dissolution calorimetry reveals that the cesium salt of hexatantalate has a similar concentration dependence on its dissolution enthalpy to that of hexaniobate. However, unlike~rubidium hexaniobate, rubidium hexatantalate also exhibits increased concentration dependence, indicating that hextantalate can undergo increased ion-pairing with alkali salts other than cesium, despite the dilute environments studied. Dissolution enthalpies of POM salts in the parent alkali hydroxides shows that protonation of clusters stabilizes lattices even more than the strongly associating heavy alkali cations do. Additionally, neither weak nor strong lattice ion associations necessarily correlates with respectively high or low aqueous solubility. These studies illuminate the importance of considering ion-pairing among the interrelated processes in the aqueous dissolution of ionic salts that can be extended to serving as a model of cation association to metal oxide surfaces.

Algaecides are chemicals that cause serious health problems. Conventional paints contain algaecides to improve the algae resistance on the paint film. Present research has suggested an environmental friendly paint formulation that focuses on developing algae resistance without having algaecides. In this research, Algae growth on newly developed paint is modeled by incorporating dirt resistance of paint and natural phenomena including humidity, temperature and time respectively. The fitted Model revealed explained variation of 59.65% in the average algae growth, of which, Dirt Resistance, Humidity and temperature and some of their interactions play significant role in this variation. Model suggests that the proposed newly developed paint without algaecides is more resilient to algae growth and significantly decreased the average algae growth rate by 0.53% as compared to conventional paints. Keeping the effect of all other factors constant, if dirt resistance of paint (D_c value) increases by one percent, average algae growth decreases by 12.98%; when temperature increases by 1^oC, average algae growth decreases by 22.4%; a positive unit change in the joint linear effect dirt resistance, temperature and humidity caused a decrease in average algae growth by 0.0031%. It was also observed that the individual effect of humidity variable was inversely related with average algae growth. However the combination of humidity and temperature, humidity and dirt resistance, humidity and time, and the quadratic effect of humidity were found to increase the average algae growth rate. The cubic effect of temperature variable by one degree centigrade resulted in decrease of average algae growth by 0.000907%.

The Vogel-Fulcher-Tammann equation is exposed as a particular example of the mean field theory. It is generalized by taking into account an arbitrary critical exponent of susceptibility, discriminating between different classes of universality. The Bell-Evans-Polanyi principle is employed to estimate the difference between the activation energies of flows in crystals and glasses, which appears to coincide with the excess Gibbs energy of the glass compared to the crystal.

In this work, the solar light-induced redox photoactivity of the ZnO semiconductor material was used to prepare at room temperature CuxO-ZnO composite catalysts with a control of the chemical state of the copper oxide phase. The preparation of Cu2(I)O-ZnO and Cu(II)O-ZnO composite catalysts was achieved by using Cu(acac)2 in THF-water and Cu(NO3)2 in water as metallic precursor, respectively. Prior to the implementation of the photo-assisted synthesis method, the most efficient photoactive ZnO material was selected among different ZnO materials prepared by the low temperature polyol method and through the precipitation method with carbonates and carbamates as precipitation agent, by taking the photocatalytic degradation of the 4-chlorophenol compound in water under simulated solar light as model reaction. The ZnO support materials were characterized by XRD, BET, TGA, SEM and TEM, and the synthesis method was strongly influencing their photoactivity in terms of 4-chlorophenol degradation and of total organic carbon removal. The most photoactive ZnO material was prepared by precipitation with carbonates and calcined at 300°C, and was taking advantage of a high specific surface area and a small mean crystallite size for achieving a complete 4-chlorophenol mineralization within 70 min of reaction, with a minimum Zn2+ released to the solution due to surface photocorrosion. Beside thermal catalysis applications, this work opened a new route for the facile synthesis of Cu2O-ZnO heterojunction photocatalysts, that could take advantage under solar light of the heterojunction built between the p-type semi-conductor Cu2O with direct visible light band gap and the ZnO semiconductor phase.

The synthesis of four samples of new polyurethanes was evaluated by changing the ratio of the diol monomers used, poly(propylene glycol) (PPG) and D-isosorbide, in the presence of aliphatic isocyanates such as the isophorone diisocyanate (IPDI) and 4,4′-methylenebis(cyclohexyl isocyanate) (HMDI). The thermal properties of the four polymers obtained were determined by DSC, exhibiting Tg values in the range 55-70 ºC, and their molecular structure characterized by FTIR, 1H and 13C NMR spectroscopies. The diffusion coefficients of these polymers in solution were measured by the Pulse Gradient Spin Echo (PGSE) NMR method, enabling the calculation of the corresponding hydrodynamic radii in diluted solution (1.62–2.65 nm). The molecular weights were determined by GPC/SEC and compared with the values determined by quantitative 13C NMR analysis. Finally, the biocompatibility of the polyurethanes was assessed using the HaCaT keratinocyte cell line by the MTT reduction assay method showing values superior to 70% cell viability.

Infrared spectroscopy is an effective method for the determination of compositions and concentrations of liquids, with advantages of fast response, no-sampling, flexible in use and is able for on-line monitoring. However, for trace substances in drinking water, such as nitrates and heavy metals, infrared spectroscopy is not sensitive enough for the quantitative and qualitative measurement. In this study, we improved the sensitivity of infrared spectroscopy for nitrite determination by developing an ion-exchange-enhanced diffuse reflectance spectroscopy, which consist of an accessory based on ion-exchange resin for enrichment and a FTIR spectrometer for measurement. Using this method, the limit of detection for nitrate is 1.7 mg/L, which is enough for drinking water sensing. We also verified the quantitative measurement ability of the method. Furthermore, the limit of detection and quantitative measuring range could be adjusted by changing the mass of resin and adsorption time. This study demonstrated the method can be used to detect trace nitrites in drinking water, can be applied in the field, and is sensitive, rapid, and inexpensive with a wide dynamic range.

Radical oxygen species formed in human tissue cells by many endogenous and exogenous pathways, cause extensive oxidative damage, which has been linked to various human diseases. This review paper provides an overview of lipid peroxidation and focuses on the free-radicals initiated processes of LDL oxidative modification and DNA oxidative damage, which are widely associated to the initiation and development of atherosclerosis and carcinogenesis, respectively. The article subsequently provides an overview of the recent human trials or even in vitro investigations on the potential of natural antioxidant compounds (such as carotenoids, vitamins C and E) to monitor LDL and DNA oxidative changes.

This study aimed to compare three different extracts of Saco sweet cherry, namely non-coloured fraction, coloured fraction and total extract concerning phenolic composition, antioxidant and antidiabetic potential, erythrocytes’ protection and effects on Caco-2 cells. A total of 22 phenolic compounds were identified by LC-DAD. Hydroxycinnamic acids were the most predominant in both non-coloured fraction and total extract, while cyanidin-3-O-rutinoside was the main anthocyanin found in the coloured fraction. The total extract was the most effective against DPPH, nitric oxide and superoxide radicals, and in the inhibition of α-glucosidase enzyme. Finally, the protective effect of the extracts to prevent oxidative damage in human erythrocytes was assessed. The coloured fraction revealed the best activity against hemoglobin oxidation and hemolysis. Regarding to Caco-2 cells, the coloured extract exhibited the most cytotoxic effects, while the total extract was the most efficient in protecting these cells against oxidative damage induced by t-BHP.

Inorganic nanoparticles based on magnetite improve the mechanical, thermal, and magnetic properties of microporous cryogel polymer composites. Here we report the synthesis of microporous cryogel based on the crosslinked sodium vinyl sulfonate (Na-VS) and 2-acrylamido-2-methylpropane sulfonic acid sodium salt (Na-AMPS). The magnetite nanoparticles were inserted into Na-VS/Na-AMPS cryogel either during its crosslinking polymerization or by in-situ technique after its crosslinking.  The morphology, particle sizes, thermal stability and magnetite contents of Na-VS/Na-AMPS cryogel and its magnetite composites were investigated. The prepared Na-VS/Na-AMPS cryogel and its magnetite composites were used as adsorbents for methylene blue (MB) cationic dye using optimum conditions. The magnetite Na-VS/Na-AMPS cryogel composite prepared by in-situ technique achieved the best adsorption MB removal capacity for 7 cycles among the other adsorbents via chemical adsorption mechanism at room temperature.

Menaquinone-7 is a member of the vitamin K family whose interest has considerably increased over the last decade due to its beneficial role in human health mainly in respect to bone and cardiovascular health leading to a growing use in different nutritional supplement. Menaquinone-7 can be produced by synthesis or fermentation and its purity profile can differ depending on methodologies and extraction procedures. Finished formulation show a large heterogeneity of purity profiles as well as frequent discrepancies in the nominal content compared to the actual title. In the present study we compared purity profiles of different raw material and we related them to stability assay in normal (12months/25°C/60%RH) and accelerated conditions (6 months/40°C/75% RH) in order to test their performance in presence of different common excipients. Results show that higher purity profile correlates with enhanced stability and this could explain title discrepancies found in finished products found on the market worldwide.

Enteric septicemia of catfish, columnaris disease, and streptococcosis, caused by Edwardsiella ictaluri, Flavobacterium columnare, and Streptococcus iniae, respectively, are the most common bacterial diseases of economic significance for the pond-raised channel catfish Ictalurus punctatus industry. Several management practices are used by catfish farmers to prevent large financial losses from these diseases such as the use of commercial antibiotics and other chemicals. In order to discover environmentally benign alternatives, using a rapid bioassay, we evaluated a crude extract from the roots of muscadine Vitis rotundifolia against these fish pathogenic bacteria and determined that the extract was most active against F. columnare. Subsequently, several isolated compounds from the root extract were further evaluated against F. columnare. Among these isolated compounds, (+)-hopeaphenol (2) and (+)-vitisin A (3) were found to be the most active against F. columnare, with 24-h 50% inhibition concentrations of 4.0±0.7 and 7.7±0.6 mg/L, respectively, and minimum inhibitory concentrations of 9.1±0 mg/L for each compound. Efficacy testing of 2 and 3 is necessary to further evaluate the potential for these compounds to be used as antibacterial agents for managing columnaris disease.

Determination of time-weighted average (TWA) concentrations of volatile organic compounds (VOCs) in air using solid-phase microextraction (SPME) is advantageous over other sampling techniques, but is often characterized by insufficient accuracies, particularly at longer sampling times. Experimental investigation of this issue and disclosing the origin of the problem is problematic and often not practically feasible due to high uncertainties. This research is aimed at developing the model of TWA extraction process and optimization of TWA air sampling by SPME using finite element analysis software (COMSOL Multiphysics). It was established that sampling by porous SPME coatings with high affinity to analytes is affected by slow diffusion of analytes inside the coating, an increase of analytes concentrations in the air near the fiber tip due to equilibration, and eventual lower sampling rate. The increase of a fiber retraction depth (Z) resulted in better recoveries. Sampling of studied VOCs using 23-ga Car/PDMS assembly at maximum possible Z (40 mm) was proven to provide more accurate results. Alternative sampling configuration based on 78.5 x 0.75 mm i.d. SPME liner was proven to provide similar accuracy at improved detection limits. Its modification with the decreased internal diameter from the sampling side should provide even better recoveries. The developed model offers new insight into optimization of air and gas sampling using SPME.

The development of a method to produce coumarins unsubstituted on the pyranic nucleus catalyzed from Wells–Dawson heteropolyacid (H₆P₂W₁₈O₆₂), phenol derivatives and ethyl 3,3-diethoxypropionate using Pechmann condensation under solvent-free conditions is described. This catalytic method was also applied successfully to synthesize various substituted coumarins, including the corresponding phenols and ethyl 3,3-diethoxypropionate. This work provides a novel, cheaper and safer way to syhthesize coumarins unsubstituted on the pyranic nucleus.

The research objectives of this study are to analyse the volatile compositions of different basil types available in Thai markets and to descriptively determine their aromatic qualities.  Essential oils were hydro-distillated from fresh leaves of 2 Holy basil (Ocimum sanctum) varieties namely, white and red and other basil species, including Tree basil (O. gratissimum), Sweet basil (O. basilicum var. thyrsiflorum) and Lemon basil (O. citriodorum).  Oil physicochemical characteristics and volatile chromatograms from Gas Chromatography-Mass Spectrometry (GC-MS) were used to qualitatively and quantitatively describe the chemical compositions.  Methyl eugenol, estragole and eugenol were among the major chemicals found in the essential oils of these basil types.  Classification by Principal Component Analysis (PCA) advised that these Ocimum spp. samples are grouped based on either the distinctive anise, citrus aroma (estragole, geranial and neral) or spice-like aroma (β-methyl eugenol, caryophyllene and α-cubebene).  The essential oil was also used for descriptive sensorial determination by five trained panelists, using the following developed terms: anisic, citrus, herb, spice, sweet and woody.  The panelists were able to differentiate essential oil of white Holy basil from red Holy basil based on the intensity of the anisic attribute, while the anise and citrus scents were detected as dominant in the Lemon basil, Tree basil and Sweet basil essential oils.  The overall benefit from this research was the elucidation of aromatic qualities from Thai common Ocimum species in order to assess their potential as the raw materials for future food research and development.

In this work, nine fruits cultivated in the northern Amazon were studied: abiu, acerola, araçá, bacupari, biribá, caçarí, fruta-do-conde, graviola and taperebá, with the objective of carrying out a bromatological and nutritional study of the pulps of fruits studied. Of all of them, are the pulps of graviola (76.83 ± 0.02 kcal 100 g^-1) bacupari (76.83 ± 0.02 kcal 100 g^-1) and fruta-do-conde (46.66 ± 0.02 kcal 100 g^-1). Among the macronutrients, the high concentration of potassium stands out, especially in the graviola (541.16 ± 0.24 mg 100 g^-1) and the biribá (468.21 ± 0.13 mg 100 g^-1). Among the micronutrients, iron concentrations are representative for araçá pulp (3.04 ± 0.02 mg 100g-1), abiu is rich in zinc (3.71 ± 0.02 mg 100 g^-1) and manganese (6.61 ± 0.11 mg 100 g^-1). The presence of cobalt at the level of traces in some of the pulps studied stands out. The Pearson correlation coefficient was evaluated, as well as the statistical treatment by multivariate analysis PCA to establish the correlation between the variables studied.

Silicon-based photoelectrochemical (PEC) conversion system has recently gained attention with its ability to provide cost-efficient and superior photoresponsive behavior in regard to other various semiconductor photoelectrodes. Carbon-based co-catalysts have always shared the spotlight for being rendered as alternative metal-free electrocatalysts intended for hydrogen evolution reaction (HER). In particular, a representative carbon-derived material, reduced Graphene Oxide (rGO) has attracted much attention as a non-metal catalyst for efficient and durable HER. Herein, we have deposited rGO on silicon nanowire (SiNW) structure which shows the highest reduction in the overpotential for HER up to date. This could be attributed to the synergistic effects of rGO and SiNW with unique anisotropic morphology, facile tuning capabilities, and scalable fabrication methods. Combined with nanostructured photocathode, rGO deposited SiNW showed better applied bias photon to current conversion efficiency of 3.16%, which is 158 times higher than that of bare planar Si system. In regard to this development we believe that rGO-SiNW photoelectrodes would pave the way for state-of-the-art highly efficient non-metal catalysts for energy conversion technologies.

Rice (Oryza sativa L.) processing yields ~60 million metric tons of bran annually. Rice genes producing bran metabolites of nutritional and human health importance were assessed across 17 diverse cultivars from seven countries using non-targeted metabolomics and resulted in 378-430 metabolites. Gambiaka cultivar had the highest number and Njavara had the lowest number of metabolites. The 71 rice bran compounds of significant variation by cultivar included 21 amino acids, seven carbohydrates, two metabolites from cofactors and vitamins, 33 lipids, six nucleotides, and two secondary metabolites. Tryptophan, -ketoglutarate, γ-tocopherol/β-tocopherol and γ-tocotrienol are example bran metabolites with extensive cultivar variation and genetic information. 34 rice bran components that varied between cultivars linked to 535 putative biosynthetic genes using to the OryzaCyc 4.0, Plant Metabolic Network database. Rice genes responsible for bran composition with animal and human health importance is available for rice breeding programs to utilize in crop improvement.

Antioxidant activity is an essential feature required for oxygen-sensitive merchandise and goods, such as food and corresponding packaging as well as materials used in cosmetics and biomedicine. For example, vanillin, one of the most prominent antioxidants, is fabricated from lignin, the second most abundant natural polymer in the world. Antioxidant potential is primarily related to the termination of oxidation propagation reactions through hydrogen transfer. The application of technical lignin as a natural antioxidant has not yet been implemented in the industrial sector, mainly due to the complex heterogeneous structure and polydispersity of lignin. Thus, current research focuses on various isolation and purification strategies to improve the compatibility of lignin material with substrates and enhancing its stabilizing effect. This contribution presents antioxidant capacity studies of various lignins depending on purification degree of the raw material. In detail, the antioxidant potential of lignin-based compounds is studied using the DPPH (2,2-diphenyl-1-picrylhydrazyl) assay. The purification procedure was monitored by thin layer chromatography (TLC) and showed that double-fold selective extraction is the most efficient purification procedure (confirmed by UV-Vis, FTIR, HSQC and 31P NMR spectroscopy, SEC and XRD analysis). Results are discussed regarding the dependency of antioxidant activity on lignin structure and biomass source. Thus, lignins obtained from industrial black liquor are compared with beech wood samples. In addition, the influence of lignin isolation (kraft versus organosolv) is discussed. Values of the antioxidant activity (DPPH inhibition) of kraft lignin fractions were 62-68% while beech and spruce/pine-mixed lignins showed values between 26, 64 and 42%, respectively. TPC values of the different isolated kraft lignin fractions varied between 26-35%, while beech, spruce/pine lignins were 34, 30 and 34%, respectively. Storage decreased the TPC values and increased the DPPH inhibition.

The present study was carried out at the north-eastern part of Bangladesh to investigate organochlorine pesticide (OCP) residues and microbiological quality of dried barb (Puntius sophore). Samples were collected from both producers and retailers from December 2016 to April 2017. A control sample was also prepared with the same raw fish used by the producers in the laboratory to compare the result. Gas Chromatography with Electron Capture Detector (GC-ECD) was used to detect and quantify OCP residues. Around 22 % (6) samples out of 27 were found contaminated with OCP residues. Among these six adulterated samples, four were from retailers and two from producers. Only Aldrin was detected in four samples and rest two samples were detected with both Aldrin + Dieldrin and Aldrin + Endrin. Aldrin was found between 0.332 to 0.967 ppm, Dieldrin 0.762 ppm, and Endrin 0.828 ppm. All these values were much higher than the Maximum Residual Limit (MRL) 0.1 ppm. Aerobic Plate Count (APC) of producer samples were ranged between log5.3 ± 0.02 to log5.4 ± 0.03, log6.2 ± 0.02 to log6.4 ± 0.02 for retailer samples and log5.0 ± 0.03 to log5.2 ± 0.04 for control samples. While fungal count was ranged between log3.2 ± 0.04 to log3.5 ± 0.04, log3.4 ± 0.04 to log3.6 ± 0.03 and log2.2 ± 0.05 to log2.5 ± 0.03 for producer, retailer and control samples respectively. All the producer and retailer samples and one-third of the control samples were found contaminated with Escherichia coli. Whereas, Salmonella sp. was detected as 13.3% in producer samples, 20% in retailer samples except for the control. In case of Vibrio sp., maximum count was found for retailer samples (13.3%), whereas, producer and control samples showed no detection. The finding of the present study revealed the presence of pesticides and poor microbiological quality of dried barb are alarming for the consumers of Bangladesh and which may cause chronic disease and potential long-term risk for human health.

Self-assembly membranes, composed of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC), were characterized at the total lipid concentration below 20 mM. The sizes of the assemblies varied depending on the molar ratio of DMPC and DHPC (q = [DMPC]/[DHPC]). The small assemblies with diameter of ca. 10 nm were formed at q ≤ 2.0 at 20 ºC (below phase transition temperature of DMPC). The physicochemical membrane properties were then studied using fluorescence probes, 1,6-diphenyl-1,3,5-hexatriene and 6-dodecanoyl-N,N-dimethyl-2-naphthylamine, upon the dilution. DHPC micelle showed a higher membrane fluidity, while the DMPC/DHPC membranes at q ≥ 0.5 showed lower membrane fluidities as well as DMPC vesicle in gel (ordered) phase. Upon dilution, the ordered membrane properties were maintained while the solution turbidities increased, implying the morphological change of the self-assembly, bicelle to the vesicle in gel phase. Based on the obtained results, a phase diagram of DMPC/DHPC binary system (at 20 ºC) is described: (i) the bicelle suspension is transparent and the membrane is in ordered state, (ii) the micelle suspension is transparent and the membrane is in disordered state, (iii) the vesicle suspension is turbid and the membrane is in ordered state.

Atoms in Molecules (AIM), Natural Bond Orbital (NBO), and normal coordinate analysis have been carried out at the global minimum structures of TH₅⁺ (T = C/Si/Ge). All these analyses lead to a consistent structure for these three protonated TH₄ molecules. The CH₅⁺ has a structure with three short and two long C-H covalent bonds and no H-H bond. Hence, the popular characterization of protonated methane as a weakly bound CH₃⁺ and H₂ is inconsistent with these results. However,  SiH₅⁺ and GeH₅⁺ are both indeed a complex formed between TH₃⁺ and H₂ stabilized by a tetrel bond, with the H₂ being the tetrel bond acceptor. The three-center-two-electron bond (3c-2e) in CH₅⁺ has an open structure, which can be characterized as a V-type 3c-2e bond and that found in SiH₅⁺ and GeH₅⁺ is a T-type 3c-2e bond. This difference could be understood based on the typical C-H, Si-H, Ge-H and H-H bond energies. Moreover, this structural difference observed in TH₅⁺ can explain the trend in proton affinity of TH₄.  Carbon is selective in forming a ‘tetrel bond’ and when it does, it might be worthwhile to highlight it as a ‘carbon bond’.