Separation,preconcentration and speciation of chromium by solid phase extraction on immobilised ferron

A sensitive and simple method for determination of chromium species after separation and preconcentration by solid phase extraction (SPE) has been developed. For the determination of the total concentration of chromium in solution, Cr(VI) was efficiently reduced to Cr(III) by addition of hydroxylamine and Cr(III) was preconcentrated on a column of immobilised ferron on alumina. The adsorbed analyte was then eluted with 5?mL of hydrochloric acid and was determined by flame atomic absorption spectrometery. The speciation of chromium was affected by first passing the solution through an acidic alumina column which retained Cr(VI) and then Cr(III) was preconcentrated by immobilised ferron column and determined by FAAS. The concentration of Cr(VI) was determined from the difference of concentration of total chromium and Cr(III). The effect of pH, concentration of eluent, flow rate of sample and eluent solution, and foreign ions on the sorption of chromium (III) by immobilised ferron column was investigated. Under the optimised conditions the calibration curve was linear over the range of 2–400?µg?L^?1 for 1000?mL preconcentration volume. The detection limit was 0.32?µg?L^?1, the preconcentration factor was 400, and the relative standard deviation (%RSD) was 1.9% (at 10?µg?L^?1; n?=?7). The method was successfully applied to the determination of chromium species in water samples and total chromium in standard alloys.     

Radical-Mediated Halogenations of Anomerically N-Substituted Glucopyranosyl Derivatives

Abstract

Reactions of acetylated N-aryl-D-glucosylamines with N-bromosuccinimide-benzoyl peroxide or with sulfuryl chloride-azoisobutyronitrile gave aromatic halo derivatives. The corresponding N-acetylated compounds were mostly inert towards halogenation. Bromination of acetylated cellobiosylpiperidine resulted in the formation of acetobromocellobiose, while the acetylated 2,6,8-trichloro-9-(β-D-glucopyranosyl)-purine was transformed into its 5′-bromo derivative. In contrast, peracetylated glucopyranosyl isothiocyanate or azides, when treated by N-bromosuccinimide under free-radical conditions, essentially undergo an initial homolysis of the anomeric C-H bond which is faster for β-anomers. This initiates a new, simple and efficient free-radical transformation of such sugar azides into an unprecedented brornimino lactone (92% isolated yield).     

Application of SiO2-Pr-SO3H as an efficient catalyst in the Ritter reaction

Sulfonic-acid-functionalized silica was applied as an efficient heterogeneous acid catalyst in the Ritter reaction to prepare amides by reaction of various benzylic, allylic, and tertiary alcohols with various nitriles in good to excellent yields under solvent-free conditions. The simplicity of the reaction, recovery of catalyst without loss of reactivity, high yield of products, and short reaction time represent improvements over many existing methods.     

Luminescent Coordination Polymers Based on Self‐Assembled Cadmium Dipyrrin Complexes

A series of novel Cd^II complexes based on α,β‐unsubstituted dipyrrin ligands (dpm) has been prepared and characterised both in solution and in the solid state. These compounds are of the [Cd(dpm)₂] type, with the coordination sphere of the metal centre occupied by two dpm chelates. Interestingly, in contrast to what has been reported for the Zn^II analogues, in the presence of a pyridyl‐ or imidazolyl‐appended dpm ligand, the coordination number of the Cd^II cation can be increased to six, leading to an octahedral coordination sphere. As a consequence, the formation of 1‐, 2‐, and 3D coordination polymers by self‐assembly is observed. Photophysical investigations of the discrete complexes and self‐assembled networks have demonstrated that both types of compounds are luminescent in the solid state.     

In silico molecular docking analysis of the human Argonaute 2 PAZ domain reveals insights into RNA interference

RNA interference (RNAi) is a critical cellular pathway activated by double stranded RNA and regulates the gene expression of target mRNA. During RNAi, the 3′ end of siRNA binds with the PAZ domain, followed by release and rebinding in a cyclic manner, which deemed essential for proper gene silencing. Recently, we provided the forces underlying the recognition of small interfering RNA by PAZ in a computational study based on the structure of Drosophila Argonaute 2 (Ago2) PAZ domain. We have now reanalyzed these data within the view of the new available structures from human Argonauts. While the parameters of weak binding are correlated with higher (RNAi) in the Drosophila model, a different profile is predicted with the human Ago2 PAZ domain. On the basis of the human Ago2 PAZ models, the indicators of stronger binding as the total binding energy and the free energy were associated with better RNAi efficacy. This discrepancy might be attributable to differences in the binding site topology and the difference in the conformation of the bound nucleotides.     

Study Kinetics of Thermal Decomposition and Electrochemical Oxidation by Using Nanocomposite Paste of Novel Poly(amide-ether)s Derived from Asymmetric Diamine

A new asymmetric diamine containing diarylimodazole pendant was synthesized from the nucleophilic substitution reaction of 1-fluoro-4-nitrobenzene and 2,4-dihydroxy benzaldehyde in the presence of K₂CO₃, followed by reaction with benzil and ammonium acetate for the preparation of imidazole ring. This novel diamine was used to prepare poly(amide-ether) (PAE) in reaction with different commercially available dicarboxylic acids via direct polycondensation using triphenyl phosphite and pyridine (Py) as catalyst. The PAEs were fully characterized and their properties such as inherent viscosity, solubility, optical, thermal and kinetics of thermal decomposition, and electrochemical oxidation were investigated. The polymers had inherent viscosity in the range of 0.47–0.65 dL/g and were noncrystalline with excellent solubility in various polar aprotic organic solvents. Their T_g values ranged from 200 to 355°C and 10% weight loss temperature above 450°C in nitrogen and left more than 70% residue at 650°C. The kinetic parameters of thermal degradation such as activation energy, entropy, enthalpy and Gibbs free energy of thermal decomposition have been evaluated using different equations. We also report electrochemical oxidation of the resulting polymers in aqueous solution by using cyclic voltammetry technique on the multi-walled carbon nanotube-modified glassy carbon electrode.     

Thermodynamics and molecular bases of the interaction of ampicillin and streptomycin at their binding sites of bovine serum albumin

Among the biological parameters of chemotherapeutics, serum albumin binding is a critical factor in determining drug distribution and bioavailability. In this study, the binding properties as well as the interaction of ampicillin and streptomycin at their binding sites of bovine serum albumin (BSA) were investigated. The binding constant varied from 3.2 × 10³ M^?1 at 298 K to 37.5 × 10³ M^?1 at 313 K for ampicillin, and from 10.7 × 10³ M^?1 at 298 K to 3.5 × 10³ M^?1 at 313 K for streptomycin. By increasing the temperature, from 298 to 313 K, the binding affinity decreased by about 11-fold for ampicillin. Conversely, streptomycin showed stronger binding at higher temperature, which is decreased by threefold at 298 K. Interestingly, the affinity of ampicillin with the free BSA was ~4-fold higher than the binding with BSA/streptomycin complex. In contrast, the affinity of streptomycin with the free BSA was ~6-fold lower than the binding with BSA/ampicillin complex. Mutual binding experiments indicate that ampicillin and streptomycin are sharing both of common and different binding sites on BSA. Dissection of the forces of interactions indicated that rigid-body binding was the mode of binding of ampicillin and streptomycin with BSA with minor degree of conformational changes. Both of ampicillin and streptomycin can bind with free BSA. Furthermore, the binding of ampicillin with BSA improves the binding of streptomycin, while the binding of streptomycin with BSA adversely affect the binding of ampicillin.     

Three-Component Reaction Between Trivalent Phosphorus,Dimethyl Acetylenedicarboxylate,and Amide Derivatives

Stabilized phosphoranes were synthesized from the reaction between dimethyl acetylenedicarboxylate and amide derivatives in the presence of triphenylphosphine. Dimethylurea containing a phosphorus ylide underwent a smooth reaction in boiling toluene to produce hydantoin and oxo-oxazolidin containing stable phosphorus ylides in good yields. Phosphorus ylides derived from (PhO)₃P were not stable and converted to diastereoisomeric phosphonates and phosphorimidate. The nature of the amide derivatives and type of trivalent phosphorus compounds, as well as solvents, determined the distribution of products.     

Evidences for Chelating Complexes of Lithium with Phenylphosphinic and Phenylphosphonic Acids: A Spectroscopic and DFT Study

Abstract

Lithium complexes were prepared with phenylphosphinic and phenylphosphonic acids. The complexes were studied in the solid state using Fourier transform infrared spectroscopy spectroscopy and in solution (methanol) using ¹H, ¹³C, and ³¹P Nuclear magnetic resonance spectroscopy (NMR) spectroscopy; the most preferred structures of the complexes were determined by density functional theory (DFT) computational method. Although methanol has a strong solvation effect on lithium ions and ligands, which causes dissociation of the complexes, significant changes of the NMR spectra of the complexes (relative to those of the free ligands) were observed. The new spectroscopic results indicate the presence of the phenylphosphinic acid tautomer (I: C₆H₅PH(?O)OH) rather than that of phenyl-phosphorous acid (II: C₆H₅P(OH)₂) in deuterated methanol showing PH/PD exchange. On the other hand, tautomer I predominates in the complex with lithium without showing PH/PD exchange. The DFT calculations predict that tautomer I is the preferred structure in the case of free ligand and lithium complex. The absence of a PH/PD exchange in the complex is due to the formation of a chelating complex, rather than of a simple salt between lithium ion and the two oxygen atoms of I, which prevent tautomerization of I into II. DFT calculations support the formation of lithium chelating complexes. The lithium ion was found to affect the spectroscopic properties of phenylphosphinic acid more dramatically than those of phenylphosphonic acid.