The structure of the diazonium coupling products of phenacyl thiocyanate and phenacyl selenocyanate with diazotized 3-phenyl-5-aminopyrazole

The reaction of diazotized 3-phenyl-5-aminopyrazole with phenacyl thiocyanate 1a and phenacyl selenocyanate 1b afforded directly 2-imino-3-(3-phenyl-5-pyrazolyl)-5-benzoyl-2,3-dihydro-1,3,4-thiadiazole monohydrate 9a and 2-imino-3-(3-phenyl-5-pyrazolyl)-5-benzoyl-2,3-dihydro-1,3,4-selenadiazole monohydrate 9b , respectively. The products 9a and 9b were also obtained from the reaction of C-benzoyl-N-(3-phenyl-5-pyrazolyl)formohydrazidoyl bromide 10 with potassium thiocyanate and potassium selenocyanate, respectively. Acetylation, benzoylation, and nitrosation of 9 afforded the corresponding diacetyl, dibenzoyl, and nitroso derivatives 11-13 , respectively. Cyclization of C-benzoyl-N-(3-phenyl-5-pyrazolyl)-nitrilimine 6 was shown to give the pyrazolo [5,1-d]triazole 8 and not the pyrazolo[5,1-c]-as-triazine derivative 7 , as previously reported.     

Reduction of soluble colloidal MnO<Subscript>2</Subscript> by <Emphasis Type="SmallCaps">DL</Emphasis>-malic acid in the absence and presence of nonionic TritonX-100

Kinetics of oxidation of DL-malic acid by water soluble colloidal MnO₂ (prepared from potassium permanganate and sodium thiosulfate solutions) have been studied spectrophotometrically in the absence and presence of nonionic Triton X-100 surfactant. The reaction is autocatalytic and manganese(II) (reduction product of the colloidal MnO₂) may be the autocatalyst. The order of the reaction is first in colloidal [MnO₂] as well as in [malic acid] both in the absence and presence of the surfactant. The reaction has acid-dependent and acid-independent paths and, in the former case, the order is fractional in [H⁺]. The effect of externally added manganese(II) is complex. The results show that the rate constant increases as the manganese(II) concentration is increased. It is not possible to predict the exact dependence of the rate constants on manganese(II) concentration, which has a series of reactions with other reactants. In the presence of TX-100, the observed effect on k is catalytic up to a certain [TX-100]; thereafter, an inhibitory effect follows. The catalytic effect is explained in terms of the mathematical model proposed by Tuncay et al. (in Colloids Surf A Physicochem Eng Aspects 149:279 3). Activation parameters associated with the observed rate constants (k_obs/k) have also been evaluated and discussed.     

Heavy-metal remediation by a fungus as a means of production of lead and cadmium carbonate crystals

We show here that reaction of the fungus, Fusarium oxysporum, with the aqueous heavy-metal ions Pb2+ and Cd2+ results in the one-step formation of the corresponding metal carbonates. The metal carbonates are formed by reaction of the heavy-metal ions with CO2 produced by the fungus during metabolism and thus provide a completely biological method for production of crystals of metal carbonates. The PbCO3 and CdCO3 crystals thus produced have interesting morphologies that are shown to arise because of interaction of the growing crystals with specific proteins secreted by the fungus during reaction. An additional advantage of this approach is that the reaction leads to detoxification of the aqueous solution and could have immense potential for bioremediation of heavy metals. Under conditions of this study, the metal ions are not toxic to the fungus, which readily grows after exposure to the metal ions.     

A sensitive and rapid liquid chromatography tandem mass spectrometry method for quantitative determination of 7-ethyl-10-hydroxycamptothecin (SN-38) in human plasma containing liposome-based SN-38 (LE-SN38)

7-Ethyl-10-hydroxycamptothecin (SN-38) is an active metabolite of Irinotecan (CPT-11), an anticancer pro-drug. To support clinical pharmacokinetic studies for liposome based formulation of SN-38 (LE-SN38) in cancer patients, a rapid, simple and sensitive liquid chromatography tandem mass spectrometry (LC-MS/MS) method has been developed and validated for the quantification of total SN-38 in human plasma. Sample preparation was carried out by one-step protein precipitation using cold acetonitrile with 0.5% acetic acid (v/v). Camptothecin was used as an internal standard (IS). Chromatographic separation of SN-38 and IS was achieved using a Synergi Hydro-RP column (C(18), 50 x 2 mm, 4 micro m), with a gradient elution of acetonitrile and 0.1% acetic acid. After ionization in electrospray source (positive ions), the acquisition was performed in the multiple reactions monitoring mode. Quantitation was accomplished using the precursor-->product ion combinations of m/z 393.1-->349.2 for SN-38 and 349.1-->305.1 for IS. The quantification limit of 0.05 ng/mL was achieved by using much lower volume (0.2 mL) of plasma and in the presence of LE-SN38. The method was validated over the concentration range of 0.05-400 ng/mL. Accuracy was within +/-12% of nominal at all concentration levels. Inter-day and intra-day precisions expressed as percentage coefficient of variation (%CVs) for quality control (QC) samples were less than 14 and 5%, respectively.     

Ligand-assisted reduction of osmium tetroxide with molecular hydrogen via a [3+2] mechanism

Osmium tetroxide is reduced by molecular hydrogen in the presence of ligands in both polar and nonpolar solvents. In CHCl3 containing pyridine (py) or 1,10-phenanthroline (phen), OsO4 is reduced by H2 to the known Os(VI) dimers L2Os(O)2(mu-O)2Os(O)2L2 (L2 = py2, phen). However, in the absence of ligands in CHCl3 and other nonpolar solvents, OsO4 is unreactive toward H2 over a week at ambient temperatures. In basic aqueous media, H2 reduces OsO4(OH)n(n-) (n = 0, 1, 2) to the isolable Os(VI) complex, OsO2(OH)4(2-), at rates close to that found in py/CHCl3. Depending on the pH, the aqueous reactions are exergonic by deltaG = -20 to -27 kcal mol(-1), based on electrochemical data. The second-order rate constants for the aqueous reactions are larger as the number of coordinated hydroxide ligands increases, k(OsO4) = 1.6(2) x 10(-2) M(-1) s(-1) < k(OsO4(OH)-) = 3.8(4) x 10(-2) M(-1) s(-1) < k(OsO4(OH)2(2-)) = 3.8(4) x 10(-1) M(-1) s(-1). The observation of primary deuterium kinetic isotope effects, k(H2)/k(D2) = 3.1(3) for OsO4 and 3.6(4) for OsO4(OH)-, indicates that the rate-determining step in each case involves H-H bond cleavage. Density functional calculations and thermochemical arguments favor a concerted [3+2] addition of H2 across two oxo groups of OsO4(L)n and argue against H* or H- abstraction from H2 or [2+2] addition of H2 across one Os=O bond. The [3+2] mechanism is analogous to that of alkene addition to OsO4(L)n to form diolates, for which acceleration by added ligands has been extensively documented. The observation that ligands also accelerate H2 addition to OsO4(L)n highlights the analogy between these two reactions.     

Effect of ionic and non-ionic surfactants on the reduction of water soluble colloidal MnO<Subscript>2</Subscript> by glycolic acid

Kinetics of the redox reaction between colloidal MnO₂ and glycolic acid have been studied spectrophotometrically by monitoring the decay in the absorbance of colloidal MnO₂ in absence and presence of surfactants. Anionic sodium dodecyl sulfate has no effect, non-ionic Triton X-100 catalyzed the reaction and experiments were not possible in presence of cationic cetyltrimethylammonium bromide due to the precipitation of MnO₂.The reaction followed the same type of kinetic behavior, i.e., fractional-, first- and fractional-order dependencies, respectively, in [glycolic acid], [MnO₂] and [H⁺ ] in both the media. Effects of gum arabic and manganese(II) have also been studied and discussed. Mechanisms in accordance with the experimental data are proposed for the reaction.     

Preparation,properties and x-ray crystal structure of a complex of bis(triphenylphosphoranylidene)ammonium iodide with 7,7,8,8-tetracyano-P-quinodimethane: (PPN)2(TCNQ)3(CH3CN)2

Bis(triphenylphosphoranylidene)ammonium iodide (PPN⁺I^?) forms a 2:3 complex with TCNQ [(PPN)₂(TCNQ)₃(CH₃CN)₂] that provides an example of a TCNQ complex containing acetonitrile in the crystal lattice; the material is a semi-conductor with trimerised TCNQ stacks.     

A chemo-enzymatic route to diastereoisomers of 2-methyl-1-phenyl-1,3-butanediol: the dual role of microorganisms

Diastereoisomers (1S,2R,3S)-, (1R,2R,3S)-, (1R,2S,3S)- and (1S,2S,3S)-2-methyl-1-phenyl-1,3-butanediols were prepared by simple and convenient strategies using two different chemo-enzymatic approaches for the reduction of racemic 2-methyl-1-phenyl-1,3-butanedione, both involving in situ racemization. The first method comprised a one-pot microbial reduction coupled with a chemical reduction, while in the second method, stepwise chemo-enzymatic reductions were performed.     

Thermal decomposition of basic cobalt and copper carbonates

Basic cobalt and copper carbonates were prepared by precipitation from solutions of their nitrates using KHCO₃ at room temperature in CO₂ atmosphere. The thermal decomposition of the prepared basic carbonates was studied by means of TG and DTA techniques and the phases produced were identified by XRD measurements. The products obtained at 400C were subjected to different doses of gamma-rays (40–160 M rad) and the thermal stabilities of these solids were investigated.The results obtained revealed that basic cobalt carbonate decomposed at 335C to produce Co₃O₄ which remained stable up to 850 and then decomposed above this temperature giving CoO which transformed into Co₃O₄ on cooling to room temperature. Basic copper carbonate dissociated at 290C yielding CuO which yielded Cu₂O and metallic copper at 1060 and 1150C, respectively. However, the produced cuprous oxide and metallic copper solids were converted into CuO and CU₂O, respectively by cooling in air to room temperature.Gamma-irradiation decreased the thermal stability of Co₃O₄ to an extent proportional to the dose employed. On the other hand, this treatment increased the thermal stability of both CuO and Cu₂O.     

The synthesis and ligand properties of the dihydro-bis-(1-indazolyl)borate anion

Summary Potassium dihydro-bis-(1-indazolyl)borate, synthesized from potassium borohydride and indazole, has been used as a reagent to yield complexes with copper(II), nickel(II), cobalt(II), manganese(II) and iron(III) ions. From i.r. spectral studies the ligand is uninegative and bidentate and coordination occurs through the nitrogen atom at position 2 of the indazole ring system in all cases. With the sole exception of the copper(II) complex, the nitrogen atom at position 1 is also involved in forming a bridge with an adjacent metal ion. On the basis of electronic spectral studies and magnetic susceptibility measurements a distorted square planar structure involving chlorine bridges has been proposed for the copper complex. An octahedral geometry with ligand bridges for all complexes is tentatively proposed and it appears that all are polymers.