Economic and facile approach for synthesis of graphene-titanate nanocomposite for water reclamation.

Graphene and its composites with semiconductor materials have been received highly attention in many research areas because of their unique properties. Efficient application of graphene is hindered by the lack of cost-effective synthesis methods. In this work, an economic and facile route for mass production of graphene-titanate nanocomposite has been discussed. Graphene was prepared by exfoliation of graphite powder in 40% ethanol aqueous solution. Titanate nanotubes were grown on graphene sheets by hydrothermal method, where the dispersed graphene sheets were mixed with titanate solution and then placed in autoclave and placed in oven for 16 h at 160 °C. The prepared composite was characterized by transmission electron microscope (TEM), scanning electron microscope (SEM), Fourier transforms infrared spectroscopy (FTIR), thermogravimetric analysis (TGA). All the obtained results confirmed the synthesis of graphene and its composite with titanate in highly uniform and pure form. The adsorption efficiency of the prepared composite was tested using methylene blue (MB) as a model dye. The adsorption isotherm was investigated using Freundlich and Langmuir models. The adsorption capacity of MB was 270.27 mg/g. The obtained correlation coefficients (R2) by Freundlich and Langmuir model were 0.996 and 0.973, respectively. The adsorption kinetics was investigated and discussed using different models. The thermal stability of the developed composite is improved after MB adsorption.

DFT study of cyclic glycine-alanine dipeptide binding to gold nanoclusters.

In this work, we studied the interactions between cyclic glycine-alanine dipeptide c(GA) and gold nanoclusters (AunNCs, where n = 2-10) using density functional theory (DFT), atoms-in-molecules theory (AIM), and natural bond orbital analysis (NBO). This dipeptide (DP) consists of two amino acid residues (glycine and alanine); thus, the preference of both residues for binding to gold atoms was examined. The preference of alanine residue to the studied AunNCs was found to be greater than that of glycine residue. Two types of interactions were exhibited between the AunNCs and c(GA), the partially-covalent partially-electrostatic type and electrostatic interaction. Performance of two DFT functionals and different basis sets is assessed. The results benchmark the importance of the DFT functional with dispersion and long-range corrections, as well as the polarization functions in the basis sets for the gold lusters-peptide binding. The binding energy (ΔEbind) values of the c(GA)-AunNCs complexes in gas and water implicit solvent were compared with those previously published for cyclic glycine-glycine DP-AunNCs complexes. It was found that the ΔEbind values of the former complexes are greater than those of latter ones in water solvent.

Insight into structural properties of polyethylene glycol monolaurate in water and alcohols from molecular dynamics studies.

By means of molecular dynamics (MD) simulations, we explored the structural properties of polyethylene glycol monolaurate (PEGML) in water and in various aliphatic alcohols (methanol, ethanol, 2-propanol, 2-butanol, tert-butanol, and 1-pentanol). The PEGML and the alcohols were simulated using the optimized potentials for liquid simulations, all-atom (OPLS-AA) force field and water using the extended simple point charge (SPC/E) model. From the isothermal-isobaric (NPT, constant number of particles, constant pressure, and constant temperature) ensemble, we extracted the densities from the simulations and compared them with those from experimental results in order to confirm the validity of the selected force fields. The densities from MD simulations are in good agreement with the experimental values. To gain more insight into the nature of interactions between the PEGML and the solvent molecules, we analyzed the hydrogen-bonds, the electrostatic (Coulomb) interactions, and the van der Waals (Lennard-Jones) interaction energies extracted from MD simulations. The results were further strengthened by computing the solvation free energy by employing the free energy perturbation (FEP) approach. In this method, the free energy difference was computed by using the Bennet Acceptance Ratio (BAR) method. Moreover, the radial distribution functions were analyzed in order to gain more understanding of the solution behavior at the molecular level.

Effects of K+, Mg2+, Ca2+, Zn2+, La3+, Cr3+, Ce3+, Ce4+, and Mo5+ Doping on the Adsorption Performance and Optical Properties of Sodium Titanate Nanotubes.

Metal-doped titanate nanotubes (TNTs) were synthesized using a simple ion-exchange method. Cations with different valencies (Mg2+, Ca2+, Zn2+, K+, Cr3+, Ce3+, Ce4+, Mo5+, and La3+) were used to assess their effects on the adsorption performance and optical properties of the prepared nanotubes. All samples were characterized by X-ray powder diffraction (XRD), field-emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDXS), and elemental mapping, and the optical properties were analyzed using photoluminescence (PL) spectroscopy. The adsorption performance of the prepared doped titanate nanotubes was tested against methylene blue (MB) as a model cation dye. The results revealed that all samples except Ce(IV)-TNT showed high removal efficiencies but at different equilibrium times. Mg-TNT, Zn-TNT, and K-TNT showed higher MB removal percentages (97%) after 45 min, while Ca-TNT, Cr-TNT, Ce(III)-TNT, Mo-TNT, La-TNT, and Na-TNT showed removal efficiencies of 95, 84, 95, 96, 94, and 96% after 65, 1200, 120, 300, 180, and 105 min, respectively. The titanate nanotubes were recycled by photocatalytic degradation of the adsorbed dye molecules. The band gaps, valence band, and conduction band were calculated and compared for the potential photocatalytic water splitting application.

Direct Oligosaccharide Profiling Using Thin-Layer Chromatography Coupled with Ionic Liquid-Stabilized Nanomatrix-Assisted Laser Desorption-Ionization Mass Spectrometry.

The in-depth characterization of glycan structures is crucial to understanding their structure-function relationships and their effects on health and various diseases. Despite advances in rapid analysis, the utility of matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) is limited for complex mixtures of carbohydrates due to their low ionization efficiency and the difficulty in separating oligosaccharides because of their high structural similarity. In this study, we developed an ionic liquid (IL)-stabilized, nanomatrix-decorated, thin-layer chromatography (TLC)-MALDI MS method for simultaneous and rapid separation, detection, and identification of oligosaccharides to achieve efficient profiling. The IL demonstrated good dispersion and stabilization for the spin coating of dihydroxybenzoic acid-functionalized magnetic nanoparticles (DHB@MNPs) on the TLC plate with spot homogeneity, which contributed to the observed high reproducibility (<20% CV) and 12- and 28-fold signal enhancement. Although the TLC was not able to separate isomeric glycans, the DHB@MNPs generate diagnostic glycosidic and cross-ring cleavage ions, enabling on-spot structural elucidation of composition, sequence, branching, and linkage of glycans in each separated spot. Without chemical derivatization of glycan samples, glycan visualization by TLC and tandem MS, our integrated platform, allowed the identification of 25 oligosaccharides from human milk, and heatmap analysis revealed the variability in the oligosaccharide abundance in samples from individual donors at different lactation times, which may provide insight into the microbiota and immunity of infants. With the demonstrated simplicity of our sample preparation method along with the achieved separation and in-depth structural characterization, our approach can be used for the rapid screening of other oligosaccharide-rich samples.

Chitin and chitosan production from shrimp shells using ammonium-based ionic liquids.

Ammonium-based ionic liquids (ILs): diisopropylethylammonium acetate ([DIPEA][Ac]), diisopropylethylammonium propanoate ([DIPEA][P]) and dimethylbutylammonium acetate ([DMBA][Ac]) are used for the extraction of chitin from shrimp shells. The extracted chitins were characterized by FT-IR, TGA, XRD, SEM and 1H NMR. The yield of chitin, with moderate molecular weights, can be as high as 13.4% (mass of extracted chitin/mass of shrimp shells) when the extraction was operated at 110 °C for 24 h. The extracted chitin can be further converted into chitosan and the product has 93% degree of deacetylation. The experimental results reveal that the ILs play a remarkable role in the extraction of chitin from shrimp shells with high selectivity. These ammonium-based ILs can be a promising green solvent to extract chitin from wasted shrimp shells and then converted into chitosan.

Does the peptide backbone unit interact with gold nanoclusters? Insights from computational modeling.

Communicated by Ramaswamy H. Sarma.

Treatment of Coffee Husk with Ammonium-Based Ionic Liquids: Lignin Extraction, Degradation, and Characterization.

Four ammonium-based ionic liquids were synthesized for the selective extraction and degradation of lignin from coffee husk. The extracted lignin samples were characterized by Fourier transform infrared, gel permeation chromatography, gas chromatography-mass spectrometry, UV-vis, 1H and 13C NMR, heteronuclear single-quantum coherence-NMR, thermogravimetric analysis, X-ray diffraction, and field emission scanning electron microscopy analyses. The analyzed results confirmed that these ionic liquids are able to effectively extract and decompose the lignin to smaller molecules from the biomass. Experimental results show that a significantly high yield, 71.2% of the original lignin, has been achieved. This processing method is an efficient, economical, and environmentally friendly green route for producing high-added-value lignin from wasted coffee husk.

The effects of biological buffers TRIS, TAPS, TES on the stability of lysozyme.

To explore the mechanism of lysozyme stabilization in buffer system, we have investigated the interactions between lysozyme and the biological buffers (TRIS, TAPS, and TES) using spectroscopic techniques, including ultraviolet-visible (UV-Vis), fluorescence, thermal fluorescence, dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FTIR) and circular dichroism (CD) spectroscopy. From the series of spectroscopic studies, it is found that the native structure of the protein remains intact in the different concentrations (0.05, 0.1, 0.25, 0.5, and 1.0M) of the biological buffer aqueous solutions at pH7.0. Moreover, all these three investigated buffers are able to protect lysozyme against thermal denaturation, particularly in high concentration (1.0M) of the buffer aqueous solutions.

Coherent Experimental and Simulation Approach To Explore the Underlying Mechanism of Denaturation of Stem Bromelain in Osmolytes.

Characterization of a protein in the context of its environment is of crucial importance for a complete understanding of its function. Although biophysical techniques provide powerful tools for studying the stability and activity of the enzyme in the presence of various cosolvents, an approach of combining both experimental techniques and molecular dynamic (MD) simulations may lead to the mechanistic insight into the interactions governing the stability of an enzyme. The knowledge of these interactions can be further utilized for range of modifications in the wild form of an enzyme for various pharmaceutical applications. Herein, we employed florescence, UV-visible, circular dichroism (CD), dynamic light scattering (DLS) study, and MD simulations for comprehensive understanding of stem bromelain (BM) in the presence of betaine, sarcosine, arginine, and proline. The thermal stability of BM in the presence of 1 M of osmolytes is found to be in order: proline > betaine > buffer > arginine > sarcosine. BM gets more preferentially hydrated in the presence of betaine and proline than in sarcosine and arginine. Nonetheless, MD simulations suggest that betaine, sarcosine, and arginine at 1 M interact with the active site of BM through H-bonding except proline which are responsible for more disruption of active site. The distances between the catalytic site residues are 1.6, 1.9, 4.3, 5.0, and 6.2 Å for BM in proline, buffer, betaine, arginine, and sarcosine at 1 M, respectively. To the best of our knowledge, this is the first report on detailed unequivocal evidence of denaturation and deactivation of BM in the presence of methylamines and amino acids.

Creation of Electron-doping Liquid Water with Reduced Hydrogen Bonds.

The strength of hydrogen bond (HB) decides water's property and activity. Here we propose the mechanisms on creation and persistence of innovatively prepared liquid water, which is treated by Au nanoparticles (AuNPs) under resonant illumination of green-light emitting diode (LED) to create Au NP-treated (sAuNT) water, with weak HB at room temperature. Hot electron transfer on resonantly illuminated AuNPs, which is confirmed from Au LIII-edge X-ray absorption near edge structure (XANES) spectra, is responsible for the creation of negatively charged sAuNT water with the incorporated energy-reduced hot electron. This unique electronic feature makes it stable at least for one week. Compared to deionized (DI) water, the resulting sAuNT water exhibits many distinct properties at room temperature. Examples are its higher activity revealed from its higher vapor pressure and lower specific heat. Furthermore, Mpemba effect can be successfully explained by our purposed hypothesis based on sAuNT water-derived idea of water energy and HB.

Buffers more than buffering agent: introducing a new class of stabilizers for the protein BSA.

In this study, we have analyzed the influence of four biological buffers on the thermal stability of bovine serum albumin (BSA) using dynamic light scattering (DLS). The investigated buffers include 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid (HEPES), 4-(2-hydroxyethyl)-1-piperazine-propanesulfonic acid (EPPS), 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid sodium salt (HEPES-Na), and 4-morpholinepropanesulfonic acid sodium salt (MOPS-Na). These buffers behave as a potential stabilizer for the native structure of BSA against thermal denaturation. The stabilization tendency follows the order of MOPS-Na > HEPES-Na > HEPES ≫ EPPS. To obtain an insight into the role of hydration layers and peptide backbone in the stabilization of BSA by these buffers, we have also explored the phase transition of a thermoresponsive polymer, poly(N-isopropylacrylamide (PNIPAM)), a model compound for protein, in aqueous solutions of HEPES, EPPS, HEPES-Na, and MOPS-Na buffers at different concentrations. It was found that the lower critical solution temperatures (LCST) of PNIPAM in the aqueous buffer solutions substantially decrease with increase in buffer concentration. The mechanism of interactions between these buffers and protein BSA was probed by various techniques, including UV-visible, fluorescence, and FTIR. The results of this series of studies reveal that the interactions are mainly governed by the influence of the buffers on the hydration layers surrounding the protein. We have also explored the possible binding sites of BSA with these buffers using a molecular docking technique. Moreover, the activities of an industrially important enzyme α-chymotrypsin (α-CT) in 0.05 M, 0.5 M, and 1.0 M of HEPES, EPPS, HEPES-Na, and MOPS-Na buffer solutions were analyzed at pH = 8.0 and T = 25 °C. Interestingly, the activities of α-CT were found to be enhanced in the aqueous solutions of these investigated buffers. Based upon the Jones-Dole viscosity parameters, the kosmotropic or chaotropic behaviors of the investigated buffers at 25 °C have been examined.

Experimental and computational study of CO2 storage and sequestration with aqueous 2-amino-2-hydroxymethyl-1,3-propanediol (TRIS) solutions.

Experimental solubility data of CO2 in (5 and 10) mass% TRIS aqueous solutions were measured at (318.15 and 333.15) K and up to 10 MPa. The solubility data were well correlated with the modified Kent-Eisenberg model. The reaction mechanism, reaction energies, and equilibrium constants for the formation of bicarbonate and carbamate from CO2, H2O, and TRIS were studied using the quantum-chemical approach COSMO-RS (conductor-like screening model for real solvents) at the BP/TZVP level. The bicarbonate and carbamate formations were confirmed by using Fourier transform infrared (FTIR) spectroscopy. The results demonstrate that the formation of the bicarbonate anion is the main product formed by the direct reaction of CO2 with water and TRIS, and reveal that the carbamate anion was formed by a proton transfer from TRIS-CO2 zwitterion to TRIS. Density functional theory (DFT) calculations with transition-state optimization and intrinsic reaction coordinate (IRC) in water using IEF-PCM solvation model at the B3LYP/6-311++G(d,p) levels of theory were employed to support the reaction pathway for the bicarbonate and carbamate formations. The conversion of the absorption product to stable carbonate (CaCO3) was also investigated experimentally by adding various Ca(2+) sources, CaCl2·2H2O aqueous solution, and artificial seawater.

Active and stable liquid water innovatively prepared using resonantly illuminated gold nanoparticles.

The properties of confined liquid water, or liquid water in contact with hydrophobic surfaces, are significantly different from those of bulk liquid water. However, all of water's commonly described properties are related to inert "bulk liquid water" which comprises a tetrahedral hydrogen-bonded network. In this work, we report an innovative and facile method for preparing small water clusters (SWCs) with reduced affinity hydrogen bonds by letting bulk water flow through supported Au nanoparticles (NPs) under resonant illumination to give NP-treated (AuNT) water at constant temperature. Utilizing localized surface plasmon resonance on illuminated Au NPs, the strong hydrogen bonds of bulk water can be disordered when water is located at the illuminated Au/water interface. The prepared SWCs are free of Au NPs. The energy efficiency for creating SWCs is ∼17%. The resulting stable AuNT water exhibits distinct properties at room temperature, which are significantly different from the properties of untreated bulk water, examples being their ability to scavenge free hydroxyl and 2,2-diphenyl-1-picrylhydrazyl radicals and to effectively reduce NO release from lipopolysaccharide-induced inflammatory cells.

TES buffer-induced phase separation of aqueous solutions of several water-miscible organic solvents at 298.15 K: phase diagrams and molecular dynamic simulations.

Water and the organic solvents tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, 1-propanol, 2-propanol, tert-butanol, acetonitrile, or acetone are completely miscible in all proportions at room temperature. Here, we present new buffering-out phase separation systems that the above mentioned organic aqueous solutions can be induced to form two liquid phases in the presence of a biological buffer 2-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]ethanesulfonic acid (TES). The lower liquid phase is rich in water and buffer, and the upper phase is organic rich. This observation has both practical and mechanistic interests. The phase diagrams of these systems were constructed by experimental measurements at ambient conditions. Molecular dynamic (MD) simulations were performed for TES + water + THF system to understand the interactions between TES, water, and organic solvent at molecular level. Several composition-sets for this system, beyond and inside the liquid-liquid phase-splitting region, have been simulated. Interestingly, the MD simulation for compositions inside the phase separation region showed that THF molecules are forced out from the water network to start forming a new liquid phase. The hydrogen-bonds, hydrogen-bonds lifetimes, hydrogen-bond energies, radial distribution functions, coordination numbers, the electrostatic interactions, and the van der Waals interactions between the different pairs have been calculated. Additionally, MD simulations for TES + water + tert-butanol∕acetonitrile∕acetone phase separation systems were simulated. The results from MD simulations provide an explanation for the buffering-out phenomena observed in [TES + water + organic solvent] systems by a mechanism controlled by the competitive interactions of the buffer and the organic solvent with water. The molecular mechanism reported here is helpful for designing new benign separation materials.

Statistical model of short wavelength transport through cavities with coexisting chaotic and regular ray trajectories.

We study the statistical properties of the impedance matrix (related to the scattering matrix) describing the input-output properties of waves in cavities in which ray trajectories that are regular and chaotic coexist (i.e., "mixed" systems). The impedance can be written as a summation over eigenmodes where the eigenmodes can typically be classified as either regular or chaotic. By appropriate characterizations of regular and chaotic contributions, we obtain statistical predictions for the impedance. We then test these predictions by comparison with numerical calculations for a specific cavity shape, obtaining good agreement.

Biodiesel production with continuous supercritical process: non-catalytic transesterification and esterification with or without carbon dioxide.

The non-catalytic transesterification of refined sunflower oil with supercritical methanol, in the presence of carbon dioxide, was conducted in a tubular reactor at temperatures from 553.2 to 593.2K and pressures up to 25.0 MPa. The FAME yield can be achieved up to about 0.70 at 593.2 K and 10.0 MPa in 23 min with methanol:oil of 25:1 in molar ratio. The effect of adding CO2 on the FAME yield is insignificant. The kinetic behavior of the non-catalytic esterification and transesterification of oleic acid or waste cooking oil (WCO) with supercritical methanol was also investigated. By using the supercritical process, the presence of free fatty acid (FFA) in WCO gives positive contribution to FAME production. The FAME yield of 0.90 from WCO can be achieved in 13 min at 573.2K. The kinetic data of supercritical transesterification and esterifaication were correlated well with a power-law model.

Phase behavior and molecular dynamics simulation studies of new aqueous two-phase separation systems induced by HEPES buffer.

Here, for the first time, we show that with addition of a biological buffer, 4-(2-hydroxyethyl)piperazine-1-ethanesulfonic acid (HEPES), into aqueous solutions of tetrahydrofuran (THF), 1,3-dioxolane, 1,4-dioxane, 1-propanol, 2-propanol, tert-butanol, acetonitrile, or acetone, the organic solvent can be excluded from water to form a new liquid phase. The phase diagrams have been determined at ambient temperature. In order to understand why and how a zwitterion solute (HEPES) induced phase separation of the investigated systems, molecular dynamics (MD) simulation studies are performed for HEPES + water + THF system. The MD simulations were conducted for the aqueous mixtures with 12 different compositions. The reliability of the simulation results of HEPES in pure water and beyond the phase separation mixtures was justified by comparing the densities obtained from MD with the experimental values. The simulation results of HEPES in pure THF and in a composition inside the phase separation region were justified qualitatively. Interestingly, all HEPES molecules entirely aggregated in pure THF. This reveals that HEPES is insoluble in pure THF, which is consistent with the experimental results. Even more interestingly, the MD simulation for the mixture with composition inside the phase separation region showed the formation of two phases. The THF molecules are squeezed out from the water network into a new liquid phase. The hydrogen bonds (HBs), HB lifetime, HB Gibbs energy (ΔG), radial distribution functions (RDFs), coordination numbers (CNs), electrostatic interactions, and the van der Waals interactions between the different species have been analyzed. Further, MD simulations for the other phase separation systems by choosing a composition inside the two liquids region for each system were also simulated. Our findings will therefore pave the way for designing new benign separation auxiliary agents.

Theory of chaos regularization of tunneling in chaotic quantum dots.

Recent numerical experiments of Pecora et al. [Phys. Rev. E 83, 065201 (2011)] have investigated tunneling between two-dimensional symmetric double wells separated by a tunneling barrier. The wells were bounded by hard walls and by the potential barrier which was created by a step increase from the zero potential within a well to a uniform barrier potential within the barrier region, which is a situation potentially realizable in the context of quantum dots. Numerical results for the splitting of energy levels between symmetric and antisymmetric eigenstates were calculated. It was found that the splittings vary erratically from state to state, and the statistics of these variations were studied for different well shapes with the fluctuation levels being much less in chaotic wells than in comparable nonchaotic wells. Here we develop a quantitative theory for the statistics of the energy level splittings for chaotic wells. Our theory is based on the random plane wave hypothesis of Berry. While the fluctuation statistics are very different for chaotic and nonchaotic well dynamics, we show that the mean splittings of differently shaped wells, including integrable and chaotic wells, are the same if their well areas and barrier parameters are the same. We also consider the case of tunneling from a single well into a region with outgoing quantum waves.

Destruction of hydrogen bonds of poly(N-isopropylacrylamide) aqueous solution by trimethylamine N-oxide.

Trimethylamine N-oxide (TMAO) is a compatible or protective osmolyte that stabilizes the protein native structure through non-bonding mechanism between TMAO and hydration surface of protein. However, we have shown here first time the direct binding mechanism for naturally occurring osmolyte TMAO with hydration structure of poly(N-isopropylacrylamide) (PNIPAM), an isomer of polyleucine, and subsequent aggregation of PNIPAM. The influence of TMAO on lower critical solution temperature (LCST) of PNIPAM was investigated as a function of TMAO concentration at different temperatures by fluorescence spectroscopy, viscosity (η), multi angle dynamic light scattering, zeta potential, and Fourier transform infrared (FTIR) spectroscopy measurements. To address some of the basis for further analysis of FTIR spectra of PNIPAM, we have also measured FTIR spectra for the monomer of N-isopropylacrylamide (NIPAM) in deuterium oxide (D(2)O) as a function of TMAO concentration. Our experimental results purportedly elucidate that the LCST values decrease with increasing TMAO concentration, which is mainly contributing to the direct hydrogen bonding of TMAO with the water molecules that are bound to the amide (-CONH) functional groups of the PNIPAM. We believed that the present work may act as a ladder to reach the heights of understanding of molecular mechanism between TMAO and macromolecule.