Iminic N-bound iminophosphorano versus nitrilic n-bound iminophosphorano Os(IV) complexes: a new double derivatization of the nitrido ligand

The reactions between trans-[Os(IV)(tpy)(Cl)(2)(NCN)] (1) and PPh(3) and between trans-[Os(IV)(tpy)(Cl)(2)(NPPh(3))](+) (2) and CN(-) provide new examples of double derivatization of the nitrido ligand in an Os(VI)-nitrido complex (Os(VI)N). The nitrilic N-bound product from the first reaction, trans-[Os(II)(tpy)(Cl)(2)(NCNPPh(3))] (3), is the coordination isomer of the first iminic N-bound product from the second reaction, trans-[Os(II)(tpy)(Cl)(2)(N(CN)(PPh(3)))] (4). In CH(3)CN at 45 degrees C, 4 undergoes isomerrization to 3 followed by solvolysis and release of (N-cyano)iminophosphorane, NCNPPh(3). These reactions demonstrate new double derivatization reactions of the nitrido ligand in Os(VI)N with its implied synthetic utility.     

The use of bathoferroine for extraction-spectrophotometric determinations of microamounts of perchlorate and perrhenate

Bathoferroine can be used for anion determinations by a method based on selective ion-pair extraction if the selectivity of extraction has been enhanced by addition of nonelectrolyte to the water phase. The method of perchlorate and perrhenate determinations characterizes parameters similar to those obtained by methods in which other cation complexes have been used. The advantage of the proposed method is the possibility of considerable concentration of ion association compound extracts by nitromethane reextraction.     

Manganese/Bicarbonate-catalyzed epoxidation of lipophilic alkenes with hydrogen peroxide in ionic liquids

[reaction: see text] Effective epoxidation of lipophilic alkenes using hydrogen peroxide was accomplished with the manganese sulfate/bicarbonate catalytic system in an ionic liquid at room temperature.     

Ab initio potential energy surface, variational transition state theory, and quasiclassical trajectory studies of the F+CH4-->HF+CH3 reaction

In this work we present a study of the F+CH(4)-->HF+CH(3) reaction (DeltaHdegrees(298 K)=-32.0 kcal mol(-1)) using different methods of the chemical reaction theory. The ground potential energy surface (PES) is characterized using several ab initio methods. Full-dimensional rate constants have been calculated employing the variational transition state theory and using directly ab initio data. A triatomic analytical representation of the ground PES was derived from ab initio points calculated at the second- and fourth-order M?ller-Plesset levels with the 6-311+G(2df,2pd) basis set, assuming the CH(3) fragment to be a 15 a.m.u. pseudoatom in the fitting process. This is suggested from experiments that indicate that the methyl group is uncoupled to the reaction coordinate. A dynamics study by means of the quasiclassical trajectory (QCT) method and employing this analytical surface was also carried out. The experimental data available on the HF internal states distributions are reproduced by the QCT results. Very recent experimental information about the reaction stereodynamics is also borne out by our QCT calculations. Comparisons with the benchmark F+H(2) and analogous Cl+CH(4) reactions are established throughout.     

Terpenoids of the oleoresin of Pinus pumila

Summary 1. The composition of the acid fraction of the oleresin ofPinus pumila (Pall.) Regel. has been studied, and from it has been isolated, in addition to known compounds, the methyl ester of a new labdane acetoxy acid.2. In the hydrocarbon fraction of the oleoresin 11 monoterpenes and 26 sesquiterpenes have been found (and 17 of the latter have been identified).3. The composition of the fraction of neutral oxygen-containing diterpenoids fromP. pumila differs considerably in its diterpenoid components from the corresponding fractions of the oleoresins of botanically related species-P. sibirica andP. koraiensis. Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 299–302, May–June, 1976.     

Poly[(μ2‐1,3‐di‐4‐pyridylpropane‐κ2N:N′)(μ3‐glutarato‐κ3O:O′:O′′)dizinc(II)]

The title compound, [Zn₂(C₅H₆O₄)₂(C₁₃H₁₄N₂)]_n or [Zn₂(glu)₂(bpp)]_n, is a novel zinc polymer based on mixed flexible glutarate (glu) and 1,3‐di‐4‐pyridylpropane (bpp) ligands. The Zn^II center has a distorted tetra­hedral geometry and the central atom of the bpp ligand is located at a special site with a C₂ axis passing through it. A layer is formed by Zn–glu bonding. Such layers are pillared by bpp ligands, forming a three‐dimensional framework with large channels. The inverted inter­penetration of two three‐dimensional frameworks completes the mol­ecular structure.     

Plasma quantification of quazepam and its 2-oxo and N-desmethyl metabolites by capillary gas chromatography

The authors have developed a gas chromatographic method for the simultaneous quantification of quazepam in plasma and its two main metabolites, 2-oxoquazepam and N-desmethylquazepam. This method involves an extraction from plasma using butyl acetate, and an analysis by electron-capture detection on a CP-Sil 5 WSCOT capillary column. Intra- and inter-day precision and accuracy were better than 10% for each of these three compounds, even near their detection limit estimated at 0.2 ng/ml. Linearity proved satisfactory between 0.2 and 60-70 ng/ml. For endogenous plasma components, adequate specificity was achieved. Despite some inconveniences, a long analysis time, a progressive saturation of the column owing to a low oven temperature, and a relatively short life-span of the CP-Sil 5 columns, this method was the only one available in the literature for the quantification of quazepam and its metabolites from the same plasma sample. It was successfully applied to phase I studies in healthy volunteers.     

Prototype of immunochromatographic assay strips using colloidal CdTe nanocrystals as biological luminescent label

Colloidal semiconductor nanocrystals have attracted considerable attention as a novel biological luminescent label. The bioinorganic conjugates of luminescent CdTe nanocrystals and protein, including CdTe/BSA (bovine serum albumin) and CdTe/MAB (mouse monoclonal antibody against hepatities B surface antigen), were formed via electrostatic/coordination self-assembly. Pure CdTe nanocrystals, CdTe/BSA and CdTe/MAB were used in the immunochromatographic assay experiments, respectively. And the results indicated that CdTe nanocrystals could be used and developed as a novel label with good stability, high sensitivity and facile determination of several analytes in immunochromatographic assay strips.     

Biocompatible hydrogels based on chitosan,cellulose/starch,PVA and PEDOT:PSS with high flexibility and high mechanical strength

Fabricating mechanically strong hydrogels that can withstand the conditions in internal tissues is a challenging task. We have designed hydrogels based on multicomponent systems by combining chitosan, starch/cellulose, PVA, and PEDOT:PSS via one-pot synthesis. The starch-based hydrogels were homogeneous, while the cellulose-based hydrogels showed the presence of cellulose micro- and nanofibers. The cellulose-based hydrogels demonstrated a swelling ratio between 121 and 156%, while the starch-based hydrogels showed higher values, from 234 to 280%. Tensile tests indicated that the presence of starch in the hydrogels provided high flexibility (strain at break?>?300%), while combination with cellulose led to the formation of stiffer hydrogels (elastic moduli 3.9–6.6 MPa). The ultimate tensile strength for both types of hydrogels was similar (2.8–3.9 MPa). The adhesion and growth of human osteoblast-like SAOS-2 cells was higher on hydrogels with cellulose than on hydrogels with starch, and was higher on hydrogels with PEDOT:PSS than on hydrogels without this polymer. The metabolic activity of cells cultivated for 3 days in the hydrogel infusions indicated that no acutely toxic compounds were released. This is promising for further possible applications of these hydrogels in tissue engineering or in wound dressings.

Graphical abstract

     

Elimination of SAS Interferences in Catalytic Adsorptive Stripping Voltammetric Determination of Cr(VI) by Means of Fumed Silica

In the work the procedure of chromium(VI) determination by catalytic adsorptive stripping voltammetry (CAdSV) with application of fumed silica, is presented. Two variants of the method are proposed: in the first fumed silica is put directly to the electrolytic cell containing tested solution, in the second the silica is shaken with the sample and next centrifuged. The effectiveness of many surface‐active substances removal from synthetic solutions as well as natural water samples, is studied. In the experiments the fumed silica (Sigma‐Aldrich) of the specific surface area in the range 200–390 m² g^?1 was used. Two types of the working electrodes were applied, i.e., hanging mercury drop electrode (HMDE) and cyclic renewable mercury film electrode (Hg(Ag)FE). In the silica presence i) the relative standard deviation (RSD) for 0.1 μg L^?1 Cr(VI) is <2% (HMDE) and <5% (Hg(Ag)FE), n=7, ii) the detection limits estimated deposition time 20 s were respectively 14 ng L^?1 (HMDE) and 22 ng L^?1 (Hg(Ag)FE). The accuracy of the method was tested by studying the recovery of Cr(VI) from spiked natural water samples.