Crystal structures of two isostructural compounds: a second polymorph of dipotassium hydrogen citrate,K2HC6H5O7, and potassium rubidium hydrogen citrate,KRbHC6H5O7

The crystal structures of a new polymorph of dipotassium hydrogen citrate, 2K⁺·HC₆H₅O₇^2?, and potassium rubidium hydrogen citrate, K⁺·Rb⁺·HC₆H₅O₇^2?, have been solved and refined using laboratory powder X‐ray diffraction and optimized using density functional techniques. In the new polymorph of the dipotassium salt, KO₇ and KO₈ coordination polyhedra share corners and edges to form a three‐dimensional framework with channels parallel to the a axis and [111]. The hydrophobic methylene groups face each other in the channels. The un‐ionized carboxylic acid group forms a strong charge‐assisted hydrogen bond to the central ionized carboxylate group. The hydroxy group forms an intermolecular hydrogen bond to a different central carboxylate group. In the potassium rubidium salt, the K⁺ and Rb⁺ cations are disordered over two sites, in approximately 0.72:0.28 and 0.28:0.72 ratios. KO₈ and RbO₉ coordination polyhedra share corners and edges to form a three‐dimensional framework with channels parallel to the a axis. The un‐ionized carboxylic acid group forms a strong charge‐assisted hydrogen bond to an ionized carboxylate group. The hydroxy group forms an intermolecular hydrogen bond to the central carboxylate group. Density functional theory (DFT) calculations on the ordered cation structures suggest that interchange of K⁺ and Rb⁺ at the two cation sites changes the energy insignificantly.     

Tin powder‐promoted diastereoselective allylation of chiral acylhydrazones

An efficient method for the allylation of chiral acylhydrazones derived from aldehydes has been developed to give the corresponding allylic hydrazides in good yields and diastereoselectivities. The method uses a combination of tin powder and allylic bromide as allylation system, which avoids the use of toxic allylic stannanes while retaining their merits.     

Powder‐XRD and 14N magic angle‐spinning solid‐state NMR spectroscopy of some metal nitrides

Some metal nitrides (TiN, ZrN, InN, GaN, Ca₃N₂, Mg₃N₂, and Ge₃N₄) have been studied by powder X‐ray diffraction (XRD) and ¹⁴N magic angle‐spinning (MAS) solid‐state NMR spectroscopy. For Ca₃N₂, Mg₃N₂, and Ge₃N₄, no ¹⁴N NMR signal was observed. Low speed (ν_r = 2 kHz for TiN, ZrN, and GaN; ν_r = 1 kHz for InN) and ‘high speed’ (ν_r = 15 kHz for TiN; ν_r = 5 kHz for ZrN; ν_r = 10 kHz for InN and GaN) MAS NMR experiments were performed. For TiN, ZrN, InN, and GaN, powder‐XRD was used to identify the phases present in each sample. The number of peaks observed for each sample in their ¹⁴N MAS solid‐state NMR spectrum matches perfectly well with the number of nitrogen‐containing phases identified by powder‐XRD. The ¹⁴N MAS solid‐state NMR spectra are symmetric and dominated by the quadrupolar interaction. The envelopes of the spinning sidebands manifold are Lorentzian, and it is concluded that there is a distribution of the quadrupolar coupling constants Q_cc's arising from structural defects in the compounds studied. Copyright © 2015 John Wiley & Sons, Ltd.     

Residual determination and risk assessment of buprofezin in plum (Prunus domestica) grown in open‐field conditions following the application of three different formulations

This study was conducted to characterize the residual level and perform a risk assessment on buprofezin formulated as an emulsifiable concentrate, wettable powder, and suspension concentrate over various treatment schedules in plum (Prunus domestica). The samples were extracted with an AOAC quick, easy, cheap, effective, rugged, and safe, ‘QuEChERS’, method after major modifications. As intrinsic interferences were observed in blank plum samples following dispersive‐solid phase extraction (consisting of primary secondary amine and C₁₈ sorbents), amino cartridges were used for solid‐phase extraction. Analysis was carried out using liquid chromatography with diode array detection and confirmed by liquid chromatography–tandem mass spectrometry. The method showed excellent linearity with determination coefficient (R² = 1) and satisfactory recoveries (at two spiking levels, 0.5 and 2.5 mg/kg) between 90.98 and 94.74% with relative standard deviation (RSD) ≤8%. The limit of quantification (0.05 mg/kg) was considerably lower than the maximum residue limit (2 mg/kg) set by the Codex Alimentarius. Absolute residue levels for emulsifiable concentrates were highest, perhaps owing to the dilution rate and adjuvant. Notably, all formulation residues were lower than the maximum residue limit, and safety data proved that the fruits are safe for consumers. Copyright © 2016 John Wiley & Sons, Ltd.     

Measuring powder flowability with a modified Warren Spring cohesion tester

The measurement of powder flowability is a major concern for most industrial processes that deal with the handling of bulk solids as raw materials,intermediates,or products.The development of devices that measure the flowability of non-aerated powders has not progressed as rapidly as might have been hoped since most research activities have been based on various types of shear testers intended to aid the design of hoppers.A new flowability indicator named as weighted cohesion (WS) is established using newly...     

ESR EVIDENCE OF AN ELECTRON TRANSFER BETWEEN ARYLPHOSPHINES AND ARYLNITROSO COMPOUNDS

Abstract

Electron transfer between arylphosphines and arylnitroso compounds gives rise to the formation of free radicals which have been characterized by esr     

Interaction of Naproxen with Crystalline and Amorphous Methylated β-Cyclodextrin in the Liquid and Solid State

Abstract

Interactions of naproxen (NAP) with amorphous, randomly methylated β-cyclodextrin at a degree of substitution per anhydroglucose unit of 1.8 (RAMEB) and with crystalline heptakis-(2,6-di-O-methyl)-β-cyclodextrin (DIMEB) were studied in aqueous solution and in the solid state using, respectively, phase-solubility analysis (at 25 °C, 37 °C and 47 °C) and differential scanning calorimetry (DSC) supported by X-ray powder diffractometry. RAMEB and DIMEB displayed similar solubilizing and complexing abilities towards NAP, suggesting analogous inclusion modes of the drug in the host cavity in aqueous solution. Differences were instead observed in interactions in the solid state, where the amorphizing capacity of RAMEB toward NAP (evaluated by DSC) was about twice that of DIMEB at each drug-to-carrier ratio. Assuming that inclusion complexation is also involved in solid-state interactions, molecular modelling accounted for the experimental results in terms of structural features of DIMEB, i.e. the particular inwards orientation of O-6-C-8 groups of three alternate glucoses on the primary hydroxyl side which hampers a deep penetration of NAP in the DIMEB cavity in the solid state. On the contrary, no obstruction of the cavity apparently occurs with RAMEB due its noncrystalline state. The aqueous dissolution rate of NAP from NAP-RAMEB and NAP-DIMEB blends containing 0.59, 0.73, 0.85, and 0.92 mass fraction of carrier linearly increased at decreasing drug-to-carrier ratios. The improvement was 5 to 20 times (from powders) and 50 to 200 times (from discs) the dissolution rate of NAP alone for both carrier. Therefore the choice of the amorphous RAMEB in pharmaceutical formulations can be recommended mainly for economic reasons, though the anhydrous and non-hygroscopic nature of crystalline DIMEB might be of particular advantage in case of moisture sensitive formulations.     

溶剂热法制备立方状ITO粉体及其电性能

以乙二醇、乙醇为溶剂通过溶剂热法制备出立方状ITO纳米粉体,研究了反应时间、NaOH浓度对ITO纳米粉体形貌的影响,并讨论了溶剂体积比、NaOH浓度对ITO粉体导电性的影响及机理。结果表明：采用乙二醇与乙醇做溶剂,V_EG：V_EtOH=4：1时,制备出分散性良好的立方状ITO纳米粉体,平均粒径为10.7 nm,且其XRD衍射峰强度比I₄₀₀/I₂₂₂最高为0.380;乙二醇与乙醇做溶剂,V_EG：V_EtOH=4：1,且NaOH浓度为0.275 mol·L^-1时,粉体电导率最高为46.75 mS·cm^-1。     

Aryl Nitro Reduction with Iron Powder or Stannous Chloride under Ultrasonic Irradiation

The selective reduction of aryl nitro compounds in the presence of sensitive functionalities, including halide, carbonyl, nitrile, and ester substituents, under ultrasonic irradiation at 35 kHz is reported in yields of 39–98%. Iron powder proved superior to stannous chloride with high tolerance of sensitive functional groups and high yields of the desired aryl amines in relatively short reaction times. Simple experimental procedure and purification also make the iron reduction of aryl nitro compounds advantageous over other methods of reduction.