Investigation on hexamethyldisilazane vapor treatment of plasma-damaged nanoporous organosilicate films

Hexamethyldisilazane (HMDS) vapor treatment of plasma-damaged nanoporous organosilicate thin films has been studied as a function of treatment temperature in this work. Although, the HMDS vapor treatment facilitated incorporation of methyl (CH₃) groups subsequent to the removal of free hydroxyl (OH) groups in the damaged films at treatment temperature as low as 55 °C, the bonded OH groups were not removed. More significantly, detailed analysis of the results reveals that HMDS vapor modified only the surface of the plasma-damaged samples and not the entire film as expected. This is attributed to the formation of a thin solid layer on the surface, which effectively prevents penetration of HMDS vapors into the bulk. The Fourier transform-infrared (FT-IR) absorption and dielectric constant measurements confirm that the vapor treatment assists only partial curing of the plasma-damaged films. Alternative processes of curing the films with HMDS dissolved in supercritical carbon dioxide (SCCO₂) as a medium of reaction in static and pulsed modes were also attempted and the results are presented in this paper.     

Laser cooling of vibrational degrees of freedom of a molecular system

We consider the cooling of vibrational degrees of freedom in a photoinduced excited electronic state of a model molecular system. For the various parameters of the potential surfaces of the ground and excited electronic states and depending on the excitation frequency of a single-mode laser light, the average energy or average vibrational temperature of the excited state passes through a minimum. The amount of cooling is quantified in terms of the overlap integral between the ground and excited electronic states of the molecule. We have given an approach to calculate the Franck-Condon factor for a multimode displaced-distorted-rotated oscillator surface of the molecular system. This is subsequently used to study the effect of displacement, distortion, and Duschinsky rotation on the vibrational cooling in the excited state. The absorption spectra and also the average energy or the effective temperature of the excited electronic state are studied for the above model molecular system. Considering the non-Condon effect for the symmetry-forbidden transitions, we have discussed the absorption spectra and average temperature in the excited-state vibrational manifold.     

Determination of ethyl glucuronide in urine using reversed-phase HPLC and pulsed electrochemical detection (Part II)

A direct, versatile method for the determination of ethyl glucuronide (EtG), a biomarker of ethanol consumption, in urine has been developed using reversed-phase liquid chromatography with pulsed electrochemical detection (PED). EtG and methyl glucuronide (MetG), which serves as an internal standard, are readily separated using a mobile phase consisting of 1% acetic acid/acetonitrile (98/2, v/v). Post-column addition of NaOH allows for the detection of all glucuronides using PED at a gold working electrode. Upon optimization, EtG was found to have a limit of detection of 0.03 μg/mL (7 pmol; 50 μL injection volume) and repeatability at the limit of quantitation of 1.7%R.S.D. (relative standard deviation). Solid-phase extraction (SPE) using an aminopropyl phase was used to remove interferents in urine samples prior to their analysis. Compound recovery following SPE was approximately 50 ± 2%. The forensic utility of this method was further validated by the analysis of 29 post-mortem urine specimens, whose results agreed strongly with certified determinations.     

Thermal Studies on Ionic Derivatives of Hafnium(IV) Involving Maltol Ligand

A number of ionic chelate complexes of maltol(A) and hafnium(IV) the type[(η₅−C₅H₅)₂HfL]⁺[MCl3]⁻ (B) [HL=maltol; M=Zn(II), Cd(II), Hg(II), Cu(II)]have been synthesized and characterized by spectral studies (IR, UV, ¹H NMR and ¹³C NMR). The stoichiometry of the complexes has been confirmed by conductance measurements. Thermogravimetric (TG) and differential thermal analytical (DTA) studies have been carried out for these complexes and from TG curves, the order, apparent activation energy and apparent activation entropy of the thermal decomposition reactions have been elucidated .The order in each case has been determined to be one and the degree of spontaneity and lability have been inferred from the apparent activation energy and entropy, respectively. Thermal parameters have been correlated with some structural aspects of the complexes concerned. From differential thermal analysis curves, the heat of reaction has been calculated. This revised version was published online in August 2006 with corrections to the Cover Date.     

Kinetics and mechanism of the reaction oftrans-cyclohexane-1,2-diamine-N N N' N'-tetra-acetatomanganate(III) with substituted thioureas in aqueous medium

Summary The kinetics of reduction of [Mn^III(cydta)]^– (where H₄cydta=trans-cyclohexane-1,2-diamine-N N N' N'-tetraacetic acid) by some thiourea reductants have been studied in aqueous solution by stopped-flow techniques in the pH ranges 2.5–4.5 and 9.2–10.2. An initial increase in absorbance followed by a steady decrease indicated the formation of a precursor complex prior to the electron transfer step. The reactions are first order in both oxidant and reductant. The observed increase in rate in going from low to high pH is attributed to the difference in reactivities of the aqua and hydroxo species of the Mn^III complex; the higher reactivity of the latter is consistent with the formation of a ligand-bridged activated species prior to electron transfer. The reactivity order for the thiourea derivatives follows the order of their reported substituent effects.     

Thermodynamic and lfer studies for the oxidation of anilines by the periodate ion

The various thermodynamic parameters for the periodate oxidation of six anilines, viz. aniline, p-chloroaniline, p-ethoxyaniline, o- and p-methoxyanilines and p-methylaniline have been reported and discussed. The validity of the isokinetic relationship and various linear free energy relationships (LFERs) have been tested and discussed. An attempt has been made to correlate these findings with the mechanism operative in these reactions.     

Intramolecular nitrone cycloaddition reaction on carbohydrate-based precursors: application in the synthesis of spironucleosides and spirobisnucleosides

A simple synthesis of chiral spironucleosides and spirobisnucleosides is described. Intramolecular 1,3-dipolar nitrone cycloaddition reaction of d-glucose-derived precursors having olefin at C-3 and nitrone at C-5, C-1, or C-2 (in nor-series) furnished bisisoxazolidinospirocycles 4-7, 11, and 12 in good yields. Reductive ring opening of the isoxazolidine moieties in 4-6 followed by construction of a nucleoside base upon the generated amino groups smoothly yielded spirobisnucleosides 17 and 18 and spironucleosides 20 and 21.     

Pose scoring by NMR

Recently, we have developed a fast approach to calculate NMR chemical shifts using the divide and conquer method at the semiempirical level. To demonstrate the utility of this approach for characterizing protein-ligand interactions, we used the deviation of calculated chemical shift perturbations from experiment to determine the orientation of a ligand (GPI-1046) in the binding pocket of the FK506 binding protein (FKBP12). Moreover, we were able to select the native state of the ligand from a collection of decoy poses. A key hydrogen bond between O1 and HN in Ile56 was also identified. Our results suggest that ligand-induced chemical shift perturbations can be used to refine protein/ligand structures.     

Studies on the determination and degradation of pyrimethamine in mammals

Treatment of pyrimethamine with blood plasma in vitro yields a metabolite which is also produced when the drug is administered through intravenous injection in the rat. A thin layer liquid chromatographic method for quantitative and qualitative determination of pyrimethamine and its metabolite in plasma and biological tissues is described.