Computer simulations of the solvation dynamics of Coumarin 153 in dimethylsulfoxide

We report molecular dynamics (MD) simulations of the solvation dynamics of Coumarin 153 in liquid dimethylsulfoxide using two distinct sets of partial charges for the coumarin probe. The excited state dipole moment of the coumarin and the dynamic Stokes shift in solution depend significantly on the type of charge distributions used. Nevertheless, the overall characteristics of the solvation responses obtained from both sets of charges are very similar and show good agreement with time-dependent Stokes shift experiments. Microscopic details of the solvent reorganization around the probe are discussed in light of the charge transfer upon photoexcitation.     

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.     

Total synthesis of (+)-xyloketal D, a secondary metabolite from the mangrove fungus Xylaria sp.

(+)-Xyloketal D was prepared in a one-pot multistep domino reaction by heating optically active 5-hydroxy-4-methyl-3-methylenepentan-2-one (R) in toluene with 2,4-dihydroxyacetophenone. The absolute configuration of the natural product was confirmed by preparation of the starting enone from a lactone of established absolute configuration.     

Synergic effect of triphenylphosphine oxide (TPPO) on the extraction of Hg(II), Se(IV), Co(II) and Mn(II) with fluorinated pyrazolone (HPMTFP)

Extraction of Hg(II), Se(IV), Mn(II) and Co(II) has been carried out with 1-phenyl-3-methyl-4-trifluoroacetyl-2-pyrazolin-5-one (HPMTFP) and triphenylphosphine oxide (TPPO) into chloroform from pH 1–10. Quantitative extraction of Hg(II), Mn(II) and Co(II) at pH 4 with equimolar 0.05M (PMTFP+TPPO) in chloroform was observed. Se(IV) remains unextracted at this pH range. The stoichiometric composition of the extracted complexes M(PMTFP)₂·nH₂O (M=Mn, Hg), M(PMTFP)₂·2TPPO (M=Mn and Co) and Co(PMTFP)₂·TPPO·H₂O at less than 0.1M TPPO has been established. The formation constantsK _m,0 andK _m,n and stability constants _m,n have been computed. The analytical method developed was applied to the IAEA standard reference material (SRM) potato fluor V-4 for the determination of these elements using NAA technique.     

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.     

Facile synthesis and characterization of monocrystalline cubic ZrO2 nanoparticles

Crystalline ZrO₂ nanoparticles were prepared from zirconium isopropoxide by slow hydrolysis and subsequent hydrothermal treatment of solutions containing various amounts of sodium hydroxide at 180 °C. Whereas moderately basic solutions lead to the formation of nanoparticles of monoclinic ZrO₂ with plate-like morphology, and nanoparticles of the cubic ZrO₂ high-temperature polymorph with diameters of approx. 5 nm were obtained from strongly basic solutions. The morphology, structure and properties of as-synthesized nanoparticles were characterized using HRTEM, XRD, Raman spectroscopy, UV–vis, PL spectroscopy and BET measurements. The formation of both, the monoclinic and the cubic polymorph, was confirmed by electron microscopy and Raman spectroscopy. The crystallinity and morphology of the resulting ZrO₂ nanoparticles can be adjusted by the choice of the reaction conditions. The cubic ZrO₂ nanoparticles have a high surface area (300 m²/g) and exhibit a strong photoluminescence in the UV region.     

The decomposition of iron(III) sulfate in air

The decomposition of initially hydrated powders of iron(III) sulfate was carried out in air over the temperature range 823–923 K. The decomposition process, which gave Fe₂O₃ as a solid product, was seen to have zero-order kinetics and an activation energy of 219 kJ·mol^–1. The nature of the product and the kinetics of decomposition were the same for samples decomposed in air and in argon. Sulfate samples with additives of FeS and Fe₂O₃ were also decomposed under similar conditions and the results confirmed the zero-order kinetics (for the case of the Fe₂O₃ additives) and the lack of effect of FeS on the decomposition of iron(III) sulfate.

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Zusammenfassung Anfänglich hydratiertes Eisen(III)-sulfatpulver wurde in Luft im Temperaturbereich 823–923 K zersetzt. Für die Reaktionsordnung des Zersetzungsprozesses, der als Endprodukt festes Fe₂O₃ lieferte, wurde Null und für die Aktivierungsenergie 219 kJ·mol^–1 ermittelt. Die Art des Produktes und der Kinetik der Zersetzung war in Luft und Argon gleich. Unter den gleichen Bedingungen wurden auch Sulfatproben mit Zusätzen von FeS und Fe₂O₃ zersetzt. Die Ergebnisse bekräftigen sowohl die nullte Reaktionsordnung (im Falle von Fe₂O₃ Zusätzen) als auch einen fehlenden Einfluß von FeS auf die Zersetzung von Eisen(III)-sulfat.

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823–923 . , , , 219 · ^–1. . FeS Fe₂O₃ . ( Fe₂O₃) - .

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This work was supported by a grant from the U.S. Department of Energy, Office of Basic Energy Sciences. The authors gratefully acknowledge this support.     

Sorptive potential of sunflower stem for Cr(III) ions from aqueous solutions and its kinetic and thermodynamic profile

The sorptive potential of sunflower stem (180-300 μm) for Cr(III) ions has been investigated in detail. The maximum sorption (≥85%) of Cr(III) ions (70.2 μM) has been accomplished using 30 mg of high density sunflower stem in 10 min from 0.001 M nitric and 0.0001 M hydrochloric acid solutions. The accumulation of Cr(III) ions on the sorbent follows Dubinin-Radushkevich (D-R), Freundlich and Langmuir isotherms. The isotherm yields D-R saturation capacity X_m = 1.60 ± 0.23 mmol g⁻¹, β = −0.00654 ± 0.00017 kJ² mol⁻², mean free energy E = 8.74 ± 0.12 kJ mol⁻¹, Freundlich sorption capacity K_F = 0.24 ± 0.11 mol g⁻¹, 1/n = 0.90 ± 0.04 and of Langmuir constant K_L = 6800 ± 600 dm³ mol⁻¹ and C_m = 120 ± 18 μmol g⁻¹. The variation of sorption with temperature (283-323 K) gives ΔH = −23.3 ± 0.8 kJ mol⁻¹, ΔS = −64.0 ± 2.7 J mol⁻¹ K⁻¹ and ΔG_298k = −4.04 ± 0.09 kJ mol⁻¹. The negative enthalpy and free energy envisage exothermic and spontaneous nature of sorption, respectively. Bisulphate, Fe(III), molybdate, citrate, Fe(II), Y(III) suppress the sorption significantly. The selectivity studies indicate that Cr(III), Eu(III) and Tb(III) ions can be separated from Tc(VII) and I(I). Sunflower stem can be used for the preconcentration and removal of Cr(III) ions from aqueous medium. This cheaper and novel sorbent has potential applications in analytical and environmental chemistry, in water decontamination, industrial waste treatment and in pollution abatement. A possible mechanism of biosorption of Cr(III) ions onto the sunflower stem has been proposed.     

Synthesis and extraction properties of new chromogenic azo-calix[4]dibenzothiacrown ethers

Two novel chromogenic cone calix[4]dibenzothiacrown ethers 3 and 4 in which nitrophenylazo groups attached at the phenyl ring of dibenzothiacrown unit were described. The extraction properties of 3 and 4 toward different transition metal ions have been studied using conductometric technique and found to exhibit Cu²⁺ and Hg²⁺ selectivity with very high stability constants range from log K _assoc = 5.19 to log K _assoc = 8.72.     

Phosphodiesterase‐Inhibiting Glycosides from Symplocos racemosa

Phytochemical investigation of Symplocos racemosa resulted in the isolation of two new glycosides, symploracemoside ( 1 ) and symplomoside ( 2 ), which are structurally related to the reported benzoylsalireposide ( 3 ) and salireposide ( 4 ). The structure elucidation of the isolated compounds was based primarily on 1D‐ and 2D‐NMR analysis, including COSY, NOESY, HMQC, and HMBC correlations. These glycosides showed inhibitory activity against snake‐venom phosphodiesterase I.