Quantum-sized ZnO was prepared using sol–gel method with Zinc acetate dehydrate (Zn(CH3COO)2·2H2O) and lithium hydroxide monohydrate(LiOH·H2O) as raw material. The ZnO particles annealed at different temperature were characterized by means of X-ray diffraction (XRD), Infrared absorption spectroscopy (IR) and UV-Vis spectroscopy. The degradation rate of reactive brilliant blue X-BR in aqueous solution was used to evaluate the photocatalytic performance of the quantum-sized ZnO. The experimental results indicated that the photocatalytic property of the ZnO was excellent. The photocatalytic efficiency of quantum-sized ZnO was significantly influenced by the calcining heat. When calcined at 300oC, its size is 6.78 nm and the photocatalytic performance is the best. The degradation rate of reactive brilliant blue X-BR could exceed 90% in 15 min at 35oC, when the concentration of the quantum-sized ZnO was 0.35 mg/L.
The decay kinetics of the aminoethanol-generated CoII-substrate radical pair catalytic intermediate in ethanolamine ammonia-lyase from Salmonella typhimurium have been measured on timescales of <105 s in frozen aqueous solution from 190 to 217 K. X-band continuous-wave electron paramagnetic resonance (EPR) spectroscopy of the disordered samples has been used to continuously monitor the full radical pair EPR spectrum during progress of the decay after temperature step reaction initiation. The decay to a diamagnetic state is complete and no paramagnetic intermediate states are detected. The decay exhibits three kinetic regimes in the measured temperature range, as follows. i), Low temperature range, 190 ≤ T ≤ 207 K: the decay is biexponential with constant fast (0.57 ± 0.04) and slow (0.43 ± 0.04) phase amplitudes. ii), Transition temperature range, 207 < T < 214 K: the amplitude of the slow phase decreases to zero with a compensatory rise in the fast phase amplitude, with increasing temperature. iii), High temperature range, T ≥ 214 K: the decay is monoexponential. The observed first-order rate constants for the monoexponential (kobs,m) and the fast phase of the biexponential decay (kobs,f) adhere to the same linear relation on an lnk versus T−1 (Arrhenius) plot. Thus...
Sulfenic acids (RSOH) are among the most common sulfur-centered reactive intermediates generated in biological systems. Given the biological occurrence of sulfenic acids, it is important to explore the reactivity of these intermediates under physiological conditions. The Morin rearrangement is a synthetic process developed for the conversion of penicillin derivatives into cephalosporins that proceeds via nucleophilic attack of an alkene on a sulfenic acid intermediate. In its classic form, the Morin reaction involves initial elimination of a sulfenic acid from a cyclic sulfoxide, followed by intramolecular cyclization of the resulting alkene and sulfenic acid groups to generate an episulfonium ion intermediate that undergoes further reaction to yield ring-expanded products. On the basis of the existing literature, it is difficult to assess whether the reaction between an alkene and a sulfenic group can occur under mild conditions because the conditions required to generate the sulfenic acid from the sulfoxide precursor in the Morin reaction typically involve high temperatures and strong acid. In the work described here, β-sulfinylketone precursors were used to generate a “Morin type” sulfenic acid intermediate under mild conditions. This approach made it possible to demonstrate that the intramolecular cyclization of an alkene with a phenylsulfenic acid to generate an episulfonium ion intermediate can occur in neutral aqueous solution at room temperature.
Water-soluble gold nanoparticles with an average diameter of 5 nm were prepared with carboxylic acid terminated thiol ligands. These ligands contain zero to eight methylene moieties. CdTe nanocrystals with an average diameter of 5 nm were synthesized with aminoethanethiol capping. These nanocrystals displayed characteristic absorption and emission spectra of quantum dots. The amine terminated CdTe nanocrystals and carboxylic-acid-terminated gold nanoparticles were conjugated in aqueous solution at pH 5.0 by electrostatic interaction, and the conjugation was monitored with fluorescence spectroscopy. The CdTe nanocrystals were significantly quenched upon binding with gold nanoparticles. The quenching efficiency was affected by both the concentration of gold nanoparticles in the complex and the length of spacer between the CdTe nanocrystal and Au nanoparticle. The observed quenching was explained using Förster resonance energy transfer (FRET) mechanism, and the Förster distance was estimated to be 3.8 nm between the donor-acceptor pair.
The absolute pKa values of 24 representative amine compounds, including cocaine, nicotine, 10 neurotransmitters, and 12 anilines, in aqueous solution were calculated by performing first-principles electronic structure calculations that account for the solvent effects using four different solvation models, i.e. the surface and volume polarization for electrostatic interaction (SVPE) model, the standard polarizable continuum model (PCM), the integral equation formalism for the polarizable continuum model (IEFPCM), and the conductor-like screening solvation model (COSMO). Within the examined computational methods, the calculations using the SVPE model lead to the absolute pKa values with the smallest root-mean-square-deviation (RMSD) value (1.18). When the SVPE model was replaced by the PCM, IEFPCM, and COSMO, the RMSD value of the calculated absolute pKa values became 3.21, 2.72, and 3.08, respectively. All types of calculated pKa values linearly correlate with the experimental pKa values very well. With the empirical corrections using the linear correlation relationships, the theoretical pKa values are much closer to the corresponding experimental data and the RMSD values become 0.51 to 0.83. The smallest RMSD value (0.51) is also associated with the SVPE model. All of the results suggest that the first-principles electronic structure calculations using the SVPE model are a reliable approach to the pKa prediction for the amine compounds.
The removal of four parabens, methyl-, ethyl-, propyl-, and benzyl-paraben, by β-cyclodextrin (β-CD) polymer from aqueous solution was studied. Different β-CD polymers were prepared by using two cross-linkers, i.e., hexamethylene diisocyanate (HMDI) and toluene-2,6-diisocyanate (TDI), with various molar ratios of cross-linker. β-CD-HMDI polymer with molar ratio of 1:7 and β-CD-TDI polymer with ratio 1:4 gave the highest adsorption of parabens among the β-CD-HMDI and β-CD-TDI series, and were subsequently used for further studies. The adsorption capacity of β-CD-HMDI is 0.0305, 0.0376, 0.1854 and 0.3026 mmol/g for methyl-, ethyl-, propyl-, and benzyl-paraben, respectively. β-CD-TDI have higher adsorption capacities compared with β-CD-HMDI, the adsorption capacity are 0.1019, 0.1286, 0.2551, and 0.3699 mmol/g methyl-, ethyl-, propyl-, and benzyl-paraben respectively. The parameters studied were adsorption capacity, water retention, and reusability. Role of both cross-linker in adsorption, hydrophobicity of polymers, and adsorption capacity of different parabens were compared and discussed. All experiments were conducted in batch adsorption technique. These polymers were applied to real samples and showed positive results.
Multidimensional potentials of mean force for the interactions in aqueous solution of both anomers of D-glucopyranose with two planar aromatic molecules, indole and para-methyl-phenol, have been calculated using molecular dynamics simulations with umbrella sampling and were subsequently used to estimate binding free energies. Indole and para-methyl-phenol serve as models for the side chains of the amino acids tryptophan and tyrosine, respectively. In all cases, a weak affinity between the glucose molecules and the flat aromatic surfaces was found. The global minimum for these interactions was found to be for the case when the pseudoplanar face of β-D -glucopyranose is stacked against the planar surfaces of the aromatic residues. The calculated binding free energies are in good agreement with both experiment and previous simulations. The multidimensional free energy maps suggest a mechanism that could lend kinetic stability to the complexes formed by sugars bound to sugar-binding proteins.
A joint QM/MM and ab initio study on the decomposition
of urea in the gas phase and in aqueous solution is reported. Numerous possible
mechanisms of intramolecular decomposition and hydrolysis have been explored;
intramolecular NH3-elimination assisted by a water molecule is found
to have the lowest activation energy. The solvent effects were elucidated using
the TIP4P explicit water model with free energy perturbation (FEP) calculations
in conjunction with QM/MM Monte Carlo simulations. The explicit representation
of the solvent was found to be essential for detailed resolution of the
mechanism, identification of the rate-determining step, and evaluation of the
barrier. The assisting water molecule acts as a hydrogen shuttle for the first
step of the elimination reaction. The forming zwitterionic intermediate,
H3NCONH, participates in 8–9 hydrogen bonds with water
molecules. Its decomposition is found to be the rate-limiting step, and the
overall free energy of activation for the decomposition of urea in water is
computed to be ca. 37 kcal/mol; the barrier for hydrolysis by an
addition/elimination mechanism is found to be ca. 40 kcal/mol. The differences
in the electronic structure of the transition states of the
NH3-elimination and hydrolysis were examined via natural bond order
analysis. Destruction of urea’s resonance stabilization during
hydrolysis via an addition/elimination mechanism...
The mercury(II) complexes formed in neutral aqueous solution with glutathione (GSH, here denoted AH3 in its tri-protonated form) were studied using Hg LIII-edge extended X-ray absorption fine structure (EXAFS) and 199Hg NMR spectroscopy, complemented with electrospray ionization mass spectrometric (ESI-MS) analyses. The [Hg(AH)2]2− complex, with the Hg-S bond distances 2.325 ± 0.01 Å in linear S-Hg-S coordination and the 199Hg NMR chemical shift −984 ppm, dominates except at high excess of glutathione. In a series of solutions with CHg(II) ~17 mM and GSH/Hg(II) mole ratios rising from 2.4 to 11.8, the gradually increasing mean Hg-S bond distance corresponds to an increasing amount of the [Hg(AH)3]4− complex. ESI-MS peaks appear at −m/z values of 1208 and 1230 corresponding to the [Na4Hg(AH)2(A)]− and [Na5Hg(AH)(A)2]− species, respectively. In another series of solutions at pH = 7.0 with CHg(II) ~50 mM and GSH/Hg(II) ratios from 2.0 to 10.0, the Hg LIII-edge EXAFS and 199Hg NMR spectra show that at high excess of glutathione (~0.35 mol·dm−3) about ~ 70% of the total mercury(II) concentration is present as the [Hg(AH)3]4− complex, with the average Hg-S bond distance 2.42 ± 0.02 Å in trigonal HgS3 coordination. The proportions of HgSn species...
Methods were developed to perform precipitation photopolymerization of PEG-diacrylate. Previously, co-monomers have been added to PEG when precipitation polymerization was desired. In the present method, the LCST of the PEG itself was lowered by addition of the kosmotropic salt sodium sulfate to an aqueous solution. Typical of a precipitation polymerization, small microparticles or microspheres (1–5 micron) resulted with relatively low polydispersity. However, aggregate formation was often severe, presumably due to a lack of stabilization of the phase-separated colloids. Microparticles were also produced by copoymerization of PEG-diacrylate with acrylic acid or aminoethylmethacrylate. The co-monomers affected the zeta potential of the formed microparticles, but not the size. The carboxyl groups of acrylic acid-containing PEG microparticles were activated and scaffolds were formed by mixing with amine-containing PEG microparticles. Although the scaffolds were relatively weak, human hepatoma cells showed excellent viability when present during microparticle crosslinking.
Artificial mimicry of α-helices offers a basis for development of protein-protein interaction antagonists. Here we report a new type of unnatural peptidic backbone, containing α-, β- and γ-amino acid residues in an αγααβα repeat pattern, for this purpose. This unnatural hexad has the same number of backbone atoms as a heptad of α residues. 2D NMR data clearly establish the formation of an α-helix-like conformation in aqueous solution. The helix formed by our 12-mer α/β/γ-peptide is considerably more stable than the α-helix formed by an analogous 14-mer α-peptide, presumably because of the preorganized β and γ residues employed.
Optimization of nitroxides as probes for EPR imaging requires detailed understanding of spectral properties. Spin lattice relaxation times, spin packet line widths, nuclear hyperfine splitting, and overall lineshapes were characterized for six low molecular weight nitroxides in dilute deoxygenated aqueous solution at X-band. The nitroxides included 6-member, unsaturated 5-member, or saturated 5-member rings, most of which were isotopically labeled. The spectra are near the fast tumbling limit with T1 ~ T2 in the range of 0.50 to 1.1 μs at ambient temperature. Both spin-lattice relaxation T1 and spin-spin relaxation T2 are longer for 15N- than for 14N-nitroxides. The dominant contributions to T1 are modulation of nitrogen hyperfine anisotropy and spin rotation. Dependence of T1 on nitrogen nuclear spin state mI was observed for both 14N and 15N. Unresolved hydrogen/deuterium hyperfine couplings dominate overall line widths. Lineshapes were simulated by including all nuclear hyperfine couplings and spin packet line widths that agreed with values obtained by electron spin echo. Line widths and relaxation times are predicted to be about the same at 250 MHz as at X-band.
We report a sensitive method for visual detection of mercury ions (II) (Hg2+) in aqueous solution by using gold nanoparticles (Au-NPs) and thymine (T)-rich Hairpin DNA probes. The thiolated Hairpin DNA probe was immobilized on the Au-NP surface through a self-assembling method. Another thymine-rich, digoxin-labeled DNA probe was introduced to form DNA duplexes on the Au-NP surface with thymine-Hg2+-thymine (T-Hg2+-T) coordination in the presence of Hg2+. The Au-NPs associated with the formed duplexes were captured on the test zone of a lateral flow strip biocomponent (LFSB) by immunoreaction events between the digoxin on the duplexes and anti-digoxin antibodies on the LFSB. The accumulation of Au-NPs produced a characteristic red band on the test zone, enabling visual detection of Hg2+ without instrumentation. A detection limit of 0.1 nM was obtained under optimal experimental conditions. This method provides a simple, rapid, sensitive approach for the detection of Hg2+ and shows great promise for point-of-use and in-field detection of environmentally toxic mercury.
The reaction of 2-methoxyphenylethyl tosylate (MeO-1-Ts) is first-order in [N3−]. A carbon-13 NMR analysis of the products of the reactions of MeO-1-[α–13C]Ts shows the formation of MeO-1-[β–13C]OH and MeO-1-[β–13C]N3 from the trapping of a symmetrical 4-methoxyphenonium ion reaction intermediate 2+. An analysis of the rate and product data provides a value of kaz/ks = 83 M−1 for partitioning of 2+ between addition of azide ion and solvent. These data set a limit for the lifetime of 2+ in aqueous solution.
The aim of this work is to investigate the effects of different force fields and temperatures on the structural character of Aβ (12–28) peptide in aqueous solution. Moreover, the structural character of Aβ (12–28) peptide is compared with other amyloid peptides (such as H1 and α-syn12 peptide). The two independent temperature replica exchange molecular dynamics (T-REMD) simulations were completed by using two different models (OPLS-AA/TIP4P and GROMOS 43A1/SPC). We compared the models by analyzing the distributions of backbone dihedral angles, the secondary structure propensity, the free energy surface and the formation of β-hairpin. The results show that the mostly populated conformation state is random coil for both models. The population of β-hairpin is below 8 percent for both models. However, the peptide modeled by GROMOS 43A1 form β-hairpin with turn located at residues F19-E22, while the peptide modeled by OPLS-AA form β-hairpin with turn located at residues L17-F20.
The removal of ethylbenzene (E) from aqueous solution by multiwalled, single-walled, and hybrid carbon nanotubes (MWCNTs, SWCNTs, and HCNTs) was evaluated for a nanomaterial dose of 1 g/L, concentration of 10–100 mg/L, and pH 7. The equilibrium amount removed by SWCNTs (E: 9.98 mg/g) was higher than by MWCNTs and HCNTs. Ethylbenzene has a higher adsorption tendency on CNTs, so that more than 98% of it adsorbed in first 14 min, which is related to the low water solubility and the high molecular weight. The SWCNTs performed better for ethylbenzene sorption than the HCNTs and MWCNTs. Isotherms study indicates that the BET isotherm expression provides the best fit for ethylbenzene sorption by SWCNTs. Carbon nanotubes, specially SWCNTs, are efficient and rapid adsorbents for ethylbenzene which possess good potential applications to maintain high-quality water. Therefore, it could be used for cleaning up environmental pollution to prevent ethylbenzene borne diseases.
The complexing properties of p-sulfonatocalix[n]arenes (n = 4: S, n = 6: S, and n = 8: S) for rhodamine 800 (Rh800) and indocyanine green (ICG) were examined to develop a near-infrared (NIR) fluorescence detection method for acetylcholine (ACh). We found that Rh800 (as a cation) forms an inclusion complex with S[n], while ICG (as a twitter ion) have no binding ability for S[n]. The binding ability of Rh800 to S[n] decreased in the order of S > S >> S. By the formation of the complex between Rh800 and S, fluorescence intensity of the Rh800 was significantly decreased. From the fluorescence titration of Rh800 by S, stoichiometry of the Rh800-S complex was determined to be 1:1 with a dissociation constant of 2.2 μM in PBS. The addition of ACh to the aqueous solution of the Rh800-S complex caused a fluorescence increase of Rh800, resulting from a competitive replacement of Rh800 by ACh in the complex. From the fluorescence change by the competitive fluorophore replacement, stoichiometry of the Rh800-ACh complex was found to be 1:1 with a dissociation constant of 1.7 mM. The effects of other neurotransmitters on the fluorescence spectra of the Rh800-S complex were examined for dopamine, GABA, glycine, and l-asparatic acid. Among the neurotransmitters examined...
An ideal technique for observing nanoscale assembly would provide atomic-resolution images of both the products and the reactants in real time. Using a transmission electron microscope (TEM) we image in situ the electrochemical deposition of lead from an aqueous solution of lead(II) nitrate. Both the lead deposits and the local Pb2+ concentration can be visualized. Depending on the rate of potential change and the potential history, lead deposits on the cathode in a structurally compact layer or in dendrites. In both cases the deposits can be removed and the process repeated. Asperities that persist through many plating and stripping cycles consistently nucleate larger dendrites. Quantitative digital image analysis reveals excellent correlation between changes in the Pb2+ concentration, the rate of lead deposition, and the current passed by the electrochemical cell. Real-time electron microscopy of dendritic growth dynamics and the associated local ionic concentrations can provide new insight into the functional electrochemistry of batteries and related energy storage technologies.
In this paper, we report on the simple, reliable synthesis of polypyrrole (PPy)/graphene oxide (GO) composite nanosheets by using sacrificial-template polymerization method. Herein, MnO2 nanoslices were chosen as a sacrificial-template to deposit PPy, which served as the oxidant as well. During the polymerization of pyrrole on surface of GO nanosheets, MnO2 component was consumed incessantly. As a result, the PPy growing on the surface of GO nanosheets has the morphology just like the MnO2 nanoslices. This method can provide the fabrication of PPy nanostructures more easily than conventional route due to its independence of removing template, which usually is a complex and tedious experimental process. The as-prepared PPy/GO composite nanosheets exhibited an enhanced properties for Cr(VI) ions removal in aqueous solution based on the synergy effect. The adsorption capacity of the PPy/GO composite nanosheets is about two times as large as that of conventional PPy nanoparticles. We believe that our findings can open a new and effective avenue to improve the adsorption performance in removing heavy metal ions from waste water.
Time-dependent motions of 32 deoxyribodinucleoside and ribodinucleoside monophosphate anions in aqueous solution at 310 K were monitored during 40 ns using classical molecular dynamics (MD). In all studied molecules, spontaneous stacking/unstacking transitions occured on a time-scale of 10 ns. To facilitate the structural analysis of the sampled configurations we defined a reaction coordinate for the nucleobase stacking that considers both the angle between the planes of the two nucleobases and the distance between their mass-centers. Additionally, we proposed a physically meaningful transient point on this coordinate that separates the stacked and unstacked states. We applied this definition to calculate free energies for stacking of all pairwise combinations of adenine, thymine (uracil), cytosine and guanine moieties embedded in studied dinucleosides monophosphate anions. The stacking equilibrium constants decreased in the order 5’-AG-3’ > GA ~ GG ~ AA > GT ~ TG ~ AT ~ GC ~ AC > CG ~ TA > CA ~ TC ~ TT ~ CT ~ CC. The stacked conformations of AG occurred ten-times more frequently than its unstacked conformations. On the other hand, the last five base combinations showed a greater preference for the unstacked than the stacked state. The presence of an additional 2’-OH group in the RNA–based dinucleoside monophosphates increased the fraction of stacked complexes but decreased the compactness of the stacked state. The calculated MD trajectories were also used to reveal prevailing mutual orientation of the nucleobase dipoles in the stacked state.