Oxovanadium(IV) and dioxouranium(VI) complexes with thiocarbohydrazones

Oxovanadium(IV) and dioxouranium(VI) complexes with thiocarbohydrazones have been prepared in an ethanolic medium and characterised by elemental analysis and molecular weight determination. They have 1:1 stoichiometry. The IR observations suggest that the ligands have coordinated through azomethine nitrogen atoms and reacted through hydroxy groups. The v(MN) and v(MO) vibrations have been assigned. The PMR spectral information supports the IR inference. The oxovanadium(IV) complexes show magnetic moments in the range of 1.74–1.94 B.M. The electronic spectra have been interpreted in the light of the BG model. Various NSH parameters have been calculated. The ESR spectra also render support for the spectral information. On the basis of this information it is suggested that oxovanadium(IV) complexes exhibit coordination number five and dioxouranium coordination number six.     

Synthesis and spectroscopic studies of paramagnetic molybdenum(V) thioglycolate

A paramagnetic binuclear molybdenum(V) thioglycolate of composition Mo₂(L)₅(H₂O)₂ (H₂L = CH₂SHCOOH, thioglycolic acid) has been synthesized by direct reduction of molybdenum(VI) oxide hydrate (MoO₃ · H₂O) with thioglycolic acid in an argon atmosphere. Based on the combined results of elemental analysis, EPR, IR ¹H NMR, electronic spectra, magnetic susceptibility, cyclic voltametry and x-ray photoelectron spectral measurements, it is concluded that in the title compound, both the molybdenum atoms are in pentavalent state with octahedral coordination through both sulphur and oxygen atoms of thioglycolic acid and water molecules. The two molybdenum ions have slightly different coordination environments due to bridging thioglycolate ions.     

Systematic studies on pH-dependent transformations of dinuclear vanadium(V)-citrate complexes in aqueous solutions. A perspective relevance to aqueous vanadium(V)-citrate speciation

Vanadium(V) involvement in interactions with physiological ligands in biological media prompted us to delve into the systematic pH-dependent synthesis, spectroscopic characterization, and perusal of chemical properties of arising aqueous vanadium(V)-citrate species in the requisite system. To this end, facile reactions led to dinuclear complexes (NH(4))(4)[V(2)O(4)(C(6)H(5)O(7))(2)].4H(2)O (1) and (NH(4))(6)[V(2)O(4)(C(6)H(4)O(7))(2)].6H(2)O (2). Complex 1 and 2 were characterized by elemental analysis, FT-IR and X-ray crystallography. Complex 1 crystallizes in the monoclinic space group C2/c with a=16.998(5) A, b=16.768(5) A, c=9.546(3) A, beta=105.22(1) degrees, V=2625(1) A(3), and Z=4. Complex 2 crystallizes in the triclinic space group P1;, with a=9.795(4) A, b=9.942(4) A, c=9.126(3) A, alpha=90.32(1) degrees, beta=111.69(1) degrees, gamma=108.67(1) degrees, V=774.5(5) A(3), and Z=1. The structures of 1 and 2 were consistent with the presence of a V(V)(2)O(2) core, to which citrate ligands of differing protonation state were bound in a coordination mode consistent with past observations. Ultimately, the aqueous pH dependent transformations of a series of three dinuclear complexes, 1, 2 and (NH(4))(2)[V(2)O(4)(C(6)H(6)O(7))(2)].2H(2)O (3), all isolated at pH values from 3 to 7.5, were explored and revealed an important interconnection among all species. Collectively, pH emerged as a determining factor of structural attributes in all three complexes, with the adjoining acid-base chemistry unfolding around the stable V(V)(2)O(2) core. The results point to the participation of all three species in aqueous vanadium(V)-citrate speciation, and may relate the site-specific protonations-deprotonations on the dinuclear complexes to potential biological processes involving vanadium(V) and physiological ligand targets.     

Neutral mononuclear dioxomolybdenum(VI) and dioxouranium(VI) complexes of oxolinic acid: Characterization and biological evaluation

The interaction of the first-generation quinolone antibacterial drug oxolinic acid (Hoxo) with the dioxomolybdenum(VI) and dioxouranim(VI) ions leads to the formation of the neutral mononuclear complexes MoO₂(oxo)₂ and UO₂(oxo)₂, respectively. The structure of the complexes has been characterized physicochemically and spectroscopically. The lowest energy model structure of the complexes has been determined with molecular modeling calculations. The antimicrobial activity of the complexes has been evaluated against three different microorganisms. The interaction of the complexes with calf-thymus DNA has been investigated with electronic and circular dichroism spectroscopies.     

Proton magnetic resonance study of rotation about carbon-nitrogen bonds in pentakis(1,1-dimethylurea)dioxouranium(VI) and its 1,3-dimethylurea analogue

In CD₃CN solutions the kinetic parameters characterising rotation about the CNMe₂ and CNH₂ bonds in [UO₂(1,1-DMU)₅]²⁺ (1,1-DMU = 1,1- dimethylurea) were determined as: k(265 K) = 39.1 ± 0.4 and 2960 ± 60 s^?1, ΔH3 = 49.1 ± 0.76 and 61.1 ±0.5 kJ mol^?1, ΔS2 = ?28.3 ± 2.7 and 53.1 ± 2.2 J K^?1 mol^?1 respectively from ¹H NMR studies. Resonances arising from the three isomeric 1,3-DMU (= 1,3-dimethylurea) ligands were observed for [UO₂(1,3-DMU)₅]²⁺ in CD₃CN solution and the kinetic parameters characterising their isomerisations were also determined. The three isomers of 1,3-DMU have not previously been detected in solution and it appears that coordination of 1,3-DMU to UO₂²⁺ increases the barrier to rotation about the carbon nitrogen bond, as is also shown to be the case for 1,1-DMU.     

Removal of Cr(VI) from aqueous solutions by adsorption onto hazelnut shell activated carbon: kinetic and equilibrium studies

The adsorption Cr(VI) from aqueous solutions onto hazelnut shell activated carbon was carried out by varying the parameters such as pH, initial Cr(VI) concentration and temperature. The experimental data fitted well to the pseudo first-order kinetic model and then the rate constants were evaluated. The Langmuir isotherm provided the best correlation for Cr(VI) onto the activated carbon. Adsorption capacity was calculated from the Langmuir isotherm as 170 mg/g at an initial pH of 1.0 for the 1000 mg/l Cr(VI) solution. Thermodynamic parameters were evaluated and the adsorption is endothermic showing monolayer adsorption of Cr(VI).     

Dielectric studies of aqueous solutions of poly(L-glutamic acid)

The dielectric features of poly(L -glutamic acid) are studied by the Fourier synthesized pseudorandom noise method in a time domain combined with a four-electrode cell. Polymer concentration dependence, the effect of the solvent viscosity, salt effects, and pH dependence are studied concomitantly with measurements of CD. A helix-to-coil transition occurs near pH 5.6 for a salt-free solution; at higher pH values, the polymer has an ionized random-coil conformation, and at lower pH, it has a deionized α-helical conformation. When it is in the ionized random-coil conformation, with the usual features of an electrolytic polymer, the solution shows a relaxation spectrum with a large dielectric increment at low frequencies. In the deionized α-helical state, no distinct relaxation curves are obtained, which does not deny the existence of a permanent peptide dipole. The pH dependence of the dielectric increment does not mainly correspond to the conformational change from helix to coil, but rather corresponds to the change of chain expansion on account of a charge–charge interaction under low ionic strength, which is conceived of by a viscosity measurement.     

Chromium(VI) sorption efficiency of acid-activated banana peel over organo-montmorillonite in aqueous solutions

In the present study, we examined sorption of chromate (Cr(VI)) to acid-activated banana peel (AABP) and organo-montmorillonite (O-mont) as a function of pH, initial Cr(VI) concentration at a sorbent dose of 4 g L^?1 and at 20 ± 1°C in aqueous solutions. In sorption edge experiments, maximum Cr(VI) removal was obtained at pH 3 after 2 hours by AABP and O-mont (88% and 69%). Sorption isotherm data showed that the sorption capacity of AABP was higher than O-mont (15.1 vs. 6.67 mg g^?1, respectively, at pH 4). Freundlich and Langmuir models provided the best fits to describe Cr(VI) sorption onto AABP (R² = 0.97) and O-mont (R² = 0.96). Fourier transform infrared spectroscopy elucidated that for AABP mainly the –OH, –COOH, –NH₂, and for O-mont intercalated amines and –OH surface functional groups were involved in Cr(VI) sorption. The scanning electron microscopy combined with energy dispersive X-ray spectroscopy (SEM-EDX) analyses, although partly, indicate that the (wt. %) proportion of cations (e.g., Ca, Mg) in AABP decreased after Cr(VI) sorption. This may be due to ion exchange of chromite (Cr(III)) (produced from Cr(VI) reduction) with cationic elements in AABP. Also, Cr(VI) desorption (using phosphate solution) from AABP was lower (29%) than that from O-mont (51%) up to the third regeneration cycle. This bench scale comparative study highlights that the utilization of widely available and low-cost acid-activated biomaterials has a greater potential than organo-clays for Cr(VI) removal in aqueous media. However, future studies are warranted to precisely delineate different mechanisms of Cr(VI) sorption/reduction by acid-activated biomaterials and organo-clays.     

The removal of chromium(VI) from aqueous solutions by Fagus orientalis L

The removal of chromium(VI) from aqueous solution under different conditions using an adsorbent was investigated. This adsorbent is Beech (Fagus orientalis L.) sawdust studied by using batch techniques. Batch studies indicated that the percent adsorption decreased with increasing initial concentration of chromium(VI). A contact time of 80 min was found to be optimum. Maximum chromium(VI) removal was observed near a pH of 1.0. Adsorption conformed to the Freundlich and Langmuir isotherms.     

Infrared spectroscopic analysis of hydrogen-bonding interactions in cryopreservation solutions

BackgroundIn this study we investigated hydrogen bonding interactions in hydrated and frozen solutions of different cryoprotective agents (CPAs) including dimethyl sulfoxide, glycerol, ethylene glycol, propylene glycol, and trehalose. We also investigated the effect of CPAs on ice crystal growth during storage and correlated this with storage stability of liposomes.MethodsFTIR spectroscopy was used to study hydrogen bonding interactions in CPA solutions in H₂O and D₂O, and their thermal response was analyzed using van ’t Hoff analysis. The effect of CPAs on ice crystal growth during storage was investigated by microscopy and correlated with storage stability of liposomes encapsulated with a fluorescent dye.ResultsPrincipal component analyses demonstrated that different CPAs can be recognized based on the shape of the OD band region only. Chemically similar molecules such as glycerol and ethylene glycol closely group together in a principal component score plot, whereas trehalose and DMSO appear as condensed separated clusters. The OH/OD band of CPA solutions exhibits an overall shift to higher wavenumbers with increasing temperature and changed fractions of weak and strong hydrogen interactions. CPAs diminish ice crystal formation in frozen samples during storage and minimize liposome leakage during freezing but cannot prevent leakage during frozen storage.ConclusionsCPAs can be distinguished from one another based on the hydrogen bonding network that is formed in solution. DMSO-water mixtures behave anomalous compared to other CPAs that have OH groups. CPAs modulate ice crystal formation during frozen storage but cannot prevent liposome leakage during frozen storage.     

Biosorption of chromium(VI) in aqueous solutions by chemically modified Strychnine tree fruit shell

Chromium(VI) was removed from aqueous solution using sulfuric- and phosphoric-acid-activated Strychnine tree fruit shells (SSTFS and PSTFS) as biosorbents. Effects of various parameters such as adsorbent dose (0.02–0.1 g/L), temperature (303–333 K), agitation speed, solution pH (2–9), contact time, and initial Cr(VI) concentration (50–250 mg/L) were studied for a batch adsorption system. The optimum pH range for Cr(VI) adsorption was determined as 2. Equilibrium adsorption data were analyzed with isotherm models and the Langmuir and Freundlich models got best fitted values for SSTFS (R² value – 0.994) and PSTFS (R² value – 0.996), respectively. The maximum adsorption capacities of SSTFS and PSTFS were 100 and 142.85 mg/g, respectively. The biosorption process was well explained by pseudo-second-order kinetic model with higher R² value (SSTFS – 0.996, PSTFS – 0.990) for both biosorbents. Characterization of biosorbents was done using Fourier transform infrared spectroscopy, scanning electron microscopy, elemental analysis, energy-dispersive X-ray analysis, and thermogravimetric analysis. Thermodynamic studies revealed the spontaneous, endothermic, and randomness in nature of the Cr(VI) adsorption process. Different concentrations of NaOH solutions were used to perform the desorption studies. The results demonstrated that both SSTFS and PSTFS can be used as an effective and low-cost biosorbent for removal of Cr(VI) from aqueous solutions.     

Vibrational spectroscopic study of glutathione complexation in aqueous solutions

A spectroscopic study of glutathione (GSH) and glutathione disulfide (GSSG) has been performed using Fourier-transformed infrared absorption and Raman scattering in order to pinpoint the sites of complexation of these two species with water and particularly with H2O2. Molecules of GSH and GSSG were studied in KBr pellets, and in aqueous solutions of H2O, D2O, and H2O with H2O2 (1 mol L(-1)) to characterize the specific influence of the solvent molecules. A time-resolved Raman study was performed for GSH/H2O2, in aqueous solution at 1:1 molar ratio in order to observe the formation of GSSG and to discuss the mechanism of this redox reaction.     

The removal of As(III) and As(V) from aqueous solutions by waste materials

The use of different waste materials such as Atlantic Cod fish scale, chicken fat, coconut fibre and charcoal in removing arsenic [As(III) and As(V)] from aqueous solutions was investigated. Initial experimental runs, conducted for both As(III) and As(V) with the aforementioned materials, demonstrated the potential of using Atlantic Cod fish scale in removing both species of arsenic from aqueous streams. Therefore, the biosorbent fish scale was selected for further investigations and various parameters such as residence time, adsorbent dose, initial concentration of adsorbate, grain size of the adsorbent and pH of the bulk phase were studied to establish optimum conditions. The maximum adsorption capacity was observed at pH value 4.0. The equilibrium adsorption data were interpreted by using both Freundlich and Langmuir models. Rapid small-scale column tests (RSSCT) were also performed to determine the breakthrough characteristics of the arsenic species with respect to packed biosorbent columns.     

Removal and recovery of uranium (VI) from aqueous solutions by immobilized Aspergillus niger powder beads

The immobilized Aspergillus niger powder beads were obtained by entrapping nonviable A. niger powder into Ca-alginate gel. The effects of pH, contact time, initial uranium (VI) concentration and biomass dosage on the biosorption of uranium (VI) onto the beads from aqueous solutions were investigated in a batch system. Biosorption equilibrium data were agreeable with Langmuir isotherm model and the maximum biosorption capacity of the beads for uranium (VI) was estimated to be 649.4?mg/g at 30?°C. The biosorption kinetics followed the pseudo-second-order model and intraparticle diffusion equation. The variations in enthalpy (26.45?kJ/mol), entropy (0.167?kJ/mol?K) and Gibbs free energy were calculated from the experimental data. SEM and EDS analysis indicated that the beads have strong adsorption capability for uranium (VI). The adsorbed uranium (VI) on the beads could be released with HNO₃ or HCl. The results showed that the immobilized A. niger powder beads had great potential for removing and recovering uranium (VI) from aqueous solutions.     

Thermodynamic and spectroscopic study of intermolecular association in aqueous dipeptide solutions

Peculiarities of the concentration dependences of apparent molar heat capacities and volumes of aqueous solutions of dipeptides were considered. Possible interpretation of the character of these dependences on the basis of Gibson and Sheraga's model of solvation shell were shown. Three concentration regions corresponding to the existence of various molecular forms of dipeptides in solution were marked out.     

Removal of Cr(VI) from aqueous solutions by fruiting bodies of the jelly fungus (Auricularia polytricha)

The aim of this study was to investigate the potential to remove chromium (Cr) from aqueous solutions using the fruiting body of Auricularia polytricha. Batch experiments were conducted under various conditions, and different models were used to characterize the biosorption process. Results showed that, for both fresh and dried fruiting bodies of A. polytricha, removal efficiencies of Cr(VI) and total Cr reached maximum values at pH values of 1 and 2, respectively. The process of Cr(VI) removal by A. polytricha included the sorption process as well as the reduction of Cr(VI) to Cr(III). Spectra of X-ray photoelectron spectroscopy of the biosorbent revealed that most of the Cr loaded on the biomass surface was in the trivalent form. The Freundlich model fitted the isotherm process better than the Langmuir model in the concentration range examined. The pseudo-second-order model well described the adsorption process of Cr onto the biomass. The biosorption capacity of Cr(VI) by fruiting bodies was much higher than that by most of other biosorbents reported. The results suggest that the fruiting bodies of A. polytricha should be a promising biomaterial for Cr removal from water contaminated by the heavy metal.