Iodometric microdetermination of carboxyl function by indirect and direct procedures

Two iodometric procedures have been described for the microdetermination of certain organic acids which can be adopted for evaluating 0.03–0.1 meq of these acids. These methods consist of treating the acid sample with an excess of neutral potassium iodide and iodate. In the indirect method the iodate used up is measured whereas the direct procedure is based on the titration of the liberated iodine. The latter procedure has been applied to determine acids in a water-alcohol medium also. The effect of various factors influencing the stoichiometry of the reactions involved has also been studied.     

Preparation and characterization of some stereochemically rigid seven-coordinate η-cyclopentadienyltris(N,N-dialkyldithiocarbamato)hafnium(IV) complexes

Summary N,N-Dialkyldithiocarbametohafnium(IV) complexes of the type -CpHf(S₂CNR₂)₃, (R = Me or Et) have been prepared in nonaqueous media by reacting dichlorodicyclopentadienylhafnium(IV) with sodium salts of substituted dithiocarbamic acids. Conductance and i.r. studies show that these complexes are nonelectrolytes in which all of the dithiocarbamate ligands are bidentate. A coordination number of seven may be assigned to hafnium(IV) in these complexes, 'H n.m.r. spectra of the complexes in CDCI₃ at ambient temperature (30°) indicate that the metal centered rearrangement and the S₂C N bond rotation are both slow on the n.m.r. time scale. A capped octahedron configuration is suggested for these complexes.Author to whore all correspondence should be addressed.     

Protective Effect of Hydroxytyrosol Against Oxidative Stress Mediated by Arsenic-Induced Neurotoxicity in Rats

The present study reports beneficial effect of hydroxytyrosol (HT) against arsenic (As)-induced oxidative stress in the rat brain. Rats were orally administered with sodium arsenite dissolved in distilled water (25 ppm, by oral gavage) for 8 weeks or HT (10 mg/kg b. wt.) in combination with As. Results showed increase in protein oxidation and lipid peroxidation, while catalase and superoxide dismutase (SOD) activities as well as GSH content were decreased after As exposure in rat brain. Fourier transform infrared analysis showed significant alteration in peak area values that also validated the oxidative damage to lipids and proteins. In addition, As exposure caused increase in protein expression of caspase-3 and Bax, while Bcl-2 expression was downregulated resulting in translocation of cytochrome c from mitochondria to cytosol. Treatment of HT with As reversed protein oxidation, lipid peroxidation, and increased GSH content as well as catalase and SOD activities. Administration of HT also prevented translocation of cytochrome c from mitochondria and increased mitochondria/cytosol ratio of cytochrome c. Hence, treatment of HT with As improved antioxidant system and efficiently lowered the generation of oxidative stress in rat brain.     

Modeling and analysis of vacuum membrane distillation for the recovery of volatile aroma compounds from black currant juice

A vacuum membrane distillation (VMD) model has been developed and validated with experimental data. The model consists of an extended transport model for the VMD process and is able to predict the effects of concentration and temperature polarization on the overall process performance. To validate the model, first it was tested with few experimental case studies from literature [S. Bandini, G.G. Sarti, Heat and mass transport resistances in vacuum membrane distillation per drop, AIChE J. 45 (7) (1999) 1422–1433; K.W. Lawson, D.R. Lloyd, Membrane distillation. I. Module design and performance evaluation using vacuum membrane distillation, J. Membr. Sci. 120 (1996) 111–121; A.M. Urtiaga, G. Ruiz, I. Ortiz, Kinetic analysis of the vacuum membrane distillation of chloroform from aqueous solutions, J. Membr. Sci. 165 (2000) 99–110]. Then the VMD model has been validated with experimental data collected from the recovery of aroma compounds from black currant [R.B. Jørgensen, A.S. Meyer, C. Varming, G. Jonsson, Recovery of volatile aroma compounds from black currant juice by vacuum membrane distillation, J. Food Eng. 64 (2004) 23–31]. In this work, recovery of 12 characteristic volatile aroma compounds from black currant juice has been studied. The simulated results from the VMD model, in terms of aroma concentration in the permeate have been compared with those obtained from laboratory experiments. The validated model has been used to study the effects of various process and membrane parameters on the concentration factor. The physical properties of various aroma compounds have been predicted using group contribution method as a function of temperature.     

Immobilization of the Gas Signaling Molecule H2S by Radioisotopes: Detection,Quantification, and In Vivo Imaging

Hydrogen sulfide (H₂S) has multifunctional roles as a gas signaling molecule in living systems. However, the efficient detection and imaging of H₂S in live animals is very challenging. Herein, we report the first radioisotope‐based immobilization technique for the detection, quantification, and in vivo imaging of endogenous H₂S. Macrocyclic ⁶⁴Cu complexes that instantly reacted with gaseous H₂S to form insoluble ⁶⁴CuS in a highly sensitive and selective manner were prepared. The H₂S concentration in biological samples was measured by a thin‐layer radiochromatography method. When ⁶⁴Cu–cyclen was injected into mice, an elevated H₂S concentration in the inflamed paw was clearly visualized and quantified by Cerenkov luminescence and positron emission tomography (PET) imaging. PET imaging was also able to pinpoint increased H₂S levels in a millimeter‐sized infarcted lesion of the rat heart.     

Dielectric studies on binary mixtures of systems exhibiting intermediate nematic phase

Two binary phase diagrams of the liquid crystals (4-n-pentylphenyl-4-n-hexyloxybenzoate (PPHB) with 4-nitrophenyl-4-n-pentylbenzoate (NPPB) and 4-n-hexyloxyphenyl-4-n-decyloxybenzoate (HPDB) with NPPB) have been studied. PPHB shows only a nematic phase where as for HPDB trimorphism, with the SmC, SmA and nematic phases, was observed. Substance NPPB which has a strong polar nitro group is non-mesogenic one. Both the phase diagrams show an induction and stabilization of SmA phase and appearance of the nematic state in the high concentration range of polar component. The dielectric measurements confirm the phase transition temperatures and show changes in the short range interaction at the phase transitions.     

Characterization,luminescence and EPR investigations of Eu2+ activated strontium aluminate phosphor

Strong blue-green light emitting Eu doped SrAl₂O₄ phosphor was synthesized by a low-temperature initiated, self-propagating and gas producing combustion process in a very short time (<5 min). The prepared powder was characterized by X-ray diffraction, Fourier-transform infrared spectrometry and scanning electron microscopy. The excitation spectrum shows a peak at 397 nm. Upon excitation at 397 nm, the emission spectrum exhibits a well defined broad band with maximum at 493 nm corresponding to 4f⁶5d → 4f⁷ transition. Electron paramagnetic resonance (EPR) measurements at X-band showed low field signals due to Eu²⁺ ions in SrAl₂O₄:Eu.     

Dopant induced morphologies of ZnS nanoparticles

We have reported the synthesis of cubic (zinc blende) phase ZnS: Ni²⁺ nanoparticles using a simple wet‐chemical method. Synthesized ZnS: Ni²⁺ nanoparticles had been characterized by X‐ray diffraction (XRD) and Energy Dispersive X‐ray (EDX) analysis. Surface morphologies were studied using Scanning Electron Microscopy (SEM). Fourier Transform Infrared (FTIR) spectra of selected samples were also carried out to confirm the presence of capping agent on the surface of the material. We have demonstrated that various morphologies like spherical, tetrapods, sheet and long‐armed multipods are emerged by simple chemical route without any vigorous reaction parameters and changing the concentration of dopant ions only. The probable mechanism for such morphologies has also been suggested.     

Organocatalytic selective benzoylation of alcohols with trichloromethyl phenyl ketone: inverse selectivity in benzoylation of alcohols containing phenol or aromatic amine functionality

Trichloromethyl phenyl ketone benzoylates primary and secondary aliphatic alcoholic groups in compounds also containing a phenolic group in the presence of 2–10 mol % of PMDETA organocatalyst at room temperature in high yields and excellent selectivity. It also shows the potential to selectively benzoylate primary alcoholic groups of aminoarylalkanols and primary-secondary diols as well as primary amino group of alkyl amines in the presence of aryl amines under similar conditions. A rationale for the selectivity and efficiency of the reaction has been provided.