Chemical Constituents from the Root of Antidesma Pentandrum var. Barbatum

Investigation of the root extract of Antidesma pentandrum var. barbatum led to the isolation of seven new compounds, antidesmol ( 1 ), antidesmanins E ( 2 ) and F ( 3 ), antidesnone ( 4 ), antidesnol ( 5 ), barbatumols A ( 6 ) and B ( 7 ), together with 14 known compounds including sodium aristolochate‐I ( 10 ) and aristolochic acid‐I methyl ester ( 11 ).     

Solid-state,optical-rotation measurements on macromolecules using powder-suspensions

Summary We report techniques for measuring optical rotation of suspended solids, including dissymmetric molecular crystals (e.g. sodium chlorate and bromate), synthetic polymers, polypeptides and biopolymers. Examples include poly(triphenylmethyl methacrylate), poly-S-lactide, poly-L-hydroxyproline, hemocyanine, cellulose acetate andRNA. The results indicate that optical rotation measurements are sensitive to differences in secondary structure and can serve as a probe for structural differences between solid-state and solution.

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Messung der optischen Rotation von Makromolekülen im Festzustand unter Verwendung von Pulversuspensionen

Zusammenfassung Es wird über eine Methode zur Messung der optischen Rotation von Festkörpern in Suspensionen berichtet, wobei dissymetrische Kristalle (z. B. Natriumchlorat und -bromat), synthetische Polymere, Polypeptide und Biopolymere behandelt werden. Die Beispiele umfassen Poly(triphenylmethylmethacrylat), Poly-S-lactid, Poly-L-hydroxyprolin, Hemocyanin, Celluloseacetat undRNA. Die Ergebnisse zeigen, daß die optischen Rotationen bezüglich Unterschiede in der Sekundärstruktur empfindlich sind und daß diese Messungen als ein Maß für Strukturunterschiede zwischen Festzustand und Lösung herangezogen werden können.

     

Spectrophotometric resolution of ternary mixtures of pseudoephedrine hydrochloride, dextromethorphan hydrobromide, and sodium benzoate in syrups using wavelength selection by net analyte signals calculated with hybrid linear analysis

Hybrid linear analysis (HLA), as a recent factor-based multivariate calibration technique, was applied for the spectrophotometric determination of ternary mixtures of pseudoephedrine hydrochloride (PSU), dextromethorphan hydrobromide (DXT), and sodium benzoate (BNZ). The utilized HLA was assisted by a wavelength selection procedure which was based on the calculation of the net analyte signal (NAS) regression plot in any considered wavelengths window for each test sample, in addition to a moving window strategy for searching the region with maximum linearity of NAS regression plot (minimum error indicator (EI)). HLA was applied because it was simpler to adapt to the NAS regression plot methodology, and also used less factors than partial least squares (PLS). An orthogonal array design was applied for formation of calibration and prediction sets in the concentration ranges 0-7500 μmol L⁻¹ for PSU, 0-300 μmol L⁻¹ for DXT, and 0-1400 μmol L⁻¹ for BNZ. The method had the ability to select wavelength regions that minimize the effect of non-linearity of the spectral data, in addition to that of non-modeled interferences. The application of the selected wavelength regions improved the obtained relative standard error of predictions for PSU, DXT, and BNZ, respectively, from 5.24, 8.67, and 5.48% to 2.19, 5.21, and 3.62% (using lower number of factors). To check the ability of the proposed method in selection of linear regions of spectra, a test for detecting non-linear regions of spectral data in multivariate spectroscopic assays was also described. Additives in the commercial syrup samples did not interfere with their determinations. The method was successfully applied for the determination of pseudoephedrine HCl, dextromethorphan HBr, and sodium benzoate in cough suppressant syrup samples.     

Electrical Conductance Studies in Aqueous Solutions of Glutaric Acid,Disodium Glutarate and Sodium Hydrogen Glutarate

Conductivity measurements of glutaric acid and disodium glutarate in dilute aqueous solutions were performed in the 288.15 to 323.15 K temperature range. The limiting equivalent conductances of glutarate anions, λ ^o(HGlut⁻,T) and λ ^o(1/2Glut²⁻,T), and the dissociation constants of glutaric acid, K ₁(T) and K ₂(T), were derived by the use of the Onsager and the Quint and Viallard conductivity equations. The applied molecular model was successfully confirmed by analyzing the conductivities of sodium hydrogen glutarate at 298.15 K.     

The solvation of Li and Na in acetonitrile from ab initio-derived many-body ion–solvent potentials

Several Li⁺- and Na⁺-acetonitrile models were derived from ab initio calculations at the counterpoise-corrected MP2/TZV++(d,p) level for distorted ion-(MeCN)_n clusters with n=1, 4 and 6. Two different many-body ion-acetonitrile models were constructed: an effective three-body potential for use with the six-site effective pair model of Böhm et al., and an effective polarizable many-body model. The polarizable acetonitrile model used in the latter model is a new empirical model which was also derived in the present paper. Mainly for comparative purposes, two ion-acetonitrile pair potentials were also constructed from the ab initio cluster calculations: one pure pair potential and one effective pair potential. Using all these potential models, MD simulations in the NPT ensemble were performed for the pure acetonitrile liquid and for Li⁺(MeCN) and Na⁺(MeCN) solutions with 1 ion in 512 solvent molecules and with a simulation time of at least 120 ps per system. Thermodynamic properties, solvation-shell structure and the self-diffusion coefficient of the ions and of the solvent molecules were calculated and compared between the different models and with experimental data, where available. The Li⁺ ion is found to be four-coordinated when the new many-body potentials are used, in contrast to the six-coordinated structure obtained for the pure pair and effective pair potentials. The coordination number of Na⁺ is close to six for all the models derived here, although the coordination number becomes slightly smaller with the many-body potentials. For both ions, the solvent molecules in the first shell point their nitrogen ends towards the cation, while in the second shell the opposite orientation is the most common.     

Sodium Tetrafluoroborate as a New and Highly Efficient Catalyst for One‐Pot Synthesis of 3,4‐Dihydropyrimidin‐2(1H)‐Ones and Thiones

Sodium tetrafluoroborate (NaBF₄) is found to catalyze the three component condensation of an aldehyde, 1,3‐dicarbonyl compound and urea or thiourea to afford the corresponding 3,4‐dihydropyrimidin‐2(1 H)‐ones and thiones in high yields. This method is very useful for the synthesis of a wide range of 3,4‐dihydropyrimidin‐2(1 H)‐ones and thiones from aromatic, heterocyclic, α,β‐unsaturated aldehydes and aliphatic aldehydes.     

Synthesis and Characterization of Methylzinc Tri(tert‐butyl)silylphosphanide as well as Related Sodium and Potassium Phosphanylzincates

The reaction of dimethylzinc and tri(tert‐butyl)silylphosphane in toluene yielded dimeric methylzinc tri(tert‐butyl)silylphosphanide ( 1 ) which crystallized tetrameric. Compound 1 was deprotonated with sodium in DME and the solvent‐separated dimeric ion pair [(dme)₃Na]⁺ [(dme)Na(MeZn)₂(μ‐PSitBu₃)₂]^? ( 2 ) was isolated. The reaction of 1 in THF with two equivalents of potassium and one equivalent of tri(tert‐butyl)silylphosphane gave dimeric [{tBu₃Si(H)P}{(thf)₂K}₂(MeZn)(PSitBu₃)]₂ ( 3 ). Both of these phosphanylzincates contain Zn₂P₂ cycles with Zn‐P bond lengths of approximately 237 pm, whereas in 1 larger Zn‐P bond lengths of 248.5 pm were found due to the larger coordination numbers of the phosphorus and zinc atoms.     

Kinetic Spectrophotometric Determination of Chromium (VI) by Oxidation of Sodium Pyrogallol-5-sulphonate by Hydrogen Peroxide

Summary. A new selective, sensitive, and simple kinetic method is developed for the determination of trace amounts of chromium (VI). The method is based on the catalytic effect of Cr(VI) on the reaction of sodium pyrogallol-5-sulphonate (PS) with hydrogen peroxide. The reaction is followed spectrophotometrically by tracing the oxidation product at 437nm within 1min after addition of H₂O₂. The optimum reaction conditions are PS (1.32·10^–3mol·dm^–3), H₂O₂ (0.32mol·dm^–3), HClO₄ (2.6·10^–3mol·dm^–3) at 25°C. Following this procedure, chromium (VI) can be determined with a linear calibration graph up to 0.25ng·cm^–3 and a detection limit of 0.024ng·cm^–3, based on the 3 criterion. The interference effect of several species was also investigated and it was found that the most common cations and anions do not interfere with the determination. The developed procedure was successfully applied to the determination of Cr(VI) and total Cr in river waters and total Cr in herbal samples.     

Polysulfonylamine. CLXIII [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 12 [1] Das orthorhombische Doppelsalz Na2Cs2[(CH3SO2)2N]4·3H2O: Ein dreidimensionales Koordinationspolymer aus (Caesium‐Anion‐Wasser)‐Schichten und intercalierten Natriumionen

Polysulfonylamines. CLXIII. Crystal Structures of Metal Di(methanesulfonyl)amides. 12. The Orthorhombic Double Salt Na₂Cs₂[(CH₃SO₂)₂N]₄·3H₂O: A Three‐Dimensional Coordination Polymer Built up from Cesium‐Anion‐Water Layers and Intercalated Sodium Ions The packing arrangement of the three‐dimensional coordination polymer Na₂Cs₂[(MeSO₂)₂N]₄·3H₂O (orthorhombic, space group Pna2₁, Z′ = 1) is in some respects similar to that of the previously reported sodium‐potassium double salt Na₂K₂[(MeSO₂)₂N]₄·4H₂O (tetragonal, P4₃2₁2, Z′ = 1/2). In the present structure, four multidentately coordinating independent anions, three independent aquo ligands and two types of cesium cation form monolayer substructures that are associated in pairs to form double layers via a Cs(1)—H₂O—Cs(2) motif, thus conferring upon each Cs⁺ an irregular O₈N₂ environment drawn from two N, O‐chelating anions, two O, O‐chelating anions and two water molecules. Half of the sodium ions occupy pseudo‐inversion centres situated between the double layers and have an octahedral O₆ coordination built up from four anions and two water molecules, whereas the remaining Na⁺ are intercalated within the double layers in a square‐pyramidal and pseudo‐C₂ symmetric O₅ environment provided by four anions and the water molecule of the Cs—H₂O—Cs motif. The net effect is that each of the four independent anions forms bonds to two Cs⁺ and two Na⁺, two independent water molecules are involved in Cs—H₂O—Na motifs, and the third water molecule acts as a μ₃‐bridging ligand for two Cs⁺ and one Na⁺. The crystal cohesion is reinforced by a three‐dimensional network of conventional O—H···O=S and weak C—H···O=S/N hydrogen bonds.     

Voltammetric behavior and determination of bismuth on sodium humate modified carbon paste electrode

The preconcentration and voltammetric behavior of Bi^III on a sodium humate modified carbon paste electrode was studied by means of cyclic voltammetry (CV) and differential pulse stripping voltammetry (DPSV). The proposed measurement involves an initial nonelectrolytic preconcentration step in which Bi^III is complexed by the surface modifier in a solution of 0.05 M KNO₃-0.0106 M HNO₃ (pH 2.0) and a subsequent electrochemical scan step in which the preconcentrated Bi^III was reduced and then oxidized promptly in supporting electrolyte of 0.5 M HNO₃. The resulting DPSV anodic current was proportional to the concentration of Bi^III ion over the range of 4.78 × 10⁻⁸–1.44 × 10⁻⁵ M. The detection limit was 4.78 × 10⁻⁸ M. The proposed method was used to determine bismuth in various samples. Various factors affecting the electrode behavior were also investigated at the same time.