1,3-Bis(2-alkyltetrazol-5-yl)triazenes and their Fe(II), Co(II) and Ni(II) complexes: Synthesis,spectroscopy, and thermal properties. Crystal structure of Fe(II) and Co(II) 1,3-bis(2-methyltetrazol-5-yl)triazenide complexes

Complexes ML¹₂ and ML²₂, with M = Fe^II, Co^II, Ni^II, and 1,3-bis(2-R-tetrazol-5-yl)triazenide ligands L¹ (R = Me) and L² (R = ^tBu), have been synthesized by the reaction of corresponding 1,3-bis(2-R-tetrazol-5-yl)triazenes with metal(II) salts in basic media and characterized by IR, UV–Vis spectroscopy, thermal and X-ray diffraction analyses. Both 1,3-bis(2-R-tetrazol-5-yl)triazenes were found to deprotonate on coordination and act as tridentate chelating ligands forming distorted MN₆ octahedra around metal(II) cations.     

β修正光度法测定食品中的微量锰

在pH=8．6的硼砂-磷酸二氢钾缓冲溶液中,锰(Ⅱ)-铬黑T-吐温80显色体系的最大吸收波长为550nm,利用此显色体系,用卢修正光度法测定食品中的微量锰,Mn(Ⅱ)含量在0．45～35μg／(25mL)内服从比耳定律,线性方程为A。=0．0281X-0．0026,相关系数r=0．9997,用该方法测定调味料八角和奶粉中的微量锰。测定结果的相对标准偏差为0．52％～2．86％,回收率为96．21％～102．2％。     

Analysis of highly resolved x‐ray photoelectron Cr 2p spectra obtained with a Cr2O3 powder sample prepared with adhesive tape

By using modern XPS systems it is possible to obtain spectra with well‐resolved spin orbit, multiplet and field splitting even with powder samples mounted using adhesive tape. Measurement of Cr₂O₃ powder with the latest generation of XPS spectrometers, which are able to analyse non‐conductive powders with ultimate energy resolution, revealed multiplet splitting features and satellite emission in the Cr 2p spectrum. Therefore, peak‐fit analysis of Cr 2p XPS spectra of Cr(III) compounds requires a more appropriate approach and common practice has to be reconsidered. One possible way to analyse this spectrum is proposed, based on the experimental and theoretical work of other authors. Copyright © 2004 John Wiley & Sons, Ltd.     

YIHn: A New Family of Metal‐rich Hydride Halides

The graphite‐like yttrium hydride halides, YIH_n (0.8 ? n ? 1.0), have been prepared in quantitative yields by heating either YI₃, YH₂ (1:2) or stoichiometric YI₃, YH₂, Y mixtures in sealed Ta ampoules at 900°C. A lower limit of the homogeneity range, n ≈ 2/3, has been determined from dehydrogenation experiments. All YIH_n phases adopt the ZrBr‐type heavy‐atom structure. The hydrogen variation is accompanied by a change in the c lattice constant from 31.162(3) to 31.033(1) Å for n = 0.61(3) to 1.02(3). The YIH_n phases reversibly react with hydrogen at 400‐600°C to form the light green transparent compound YIH₂. However, increasing the reaction temperature above 700°C causes decomposition to an unidentified phase being in equilibrium with YH₂ and YI₃. The arrangement of the heavy atoms in YIH₂ (P m1; a = 3.8579(3) Å, c = 10.997(1) Å) corresponds to a four‐layer I‐Y‐Y‐I slab with the stacking sequence (AbaB) as was found by x‐ray powder diffraction data refinement with the Rietveld method. A miscibility gap exists between YIH and YIH₂. Samples YIH_n (n ? 1.0) show metallic conductivity at room temperature, which changes into semiconducting behavior with decreasing temperature as n approaches its lower value ≈ 2/3.     

高效液相色谱-质谱联用测定婴幼儿配方奶粉中的左旋肉碱

建立了婴幼儿配方奶粉中左旋肉碱含量的高效液相色谱-质谱联用测定方法。采用C4色谱柱(4.6mm×250 mm,5μm)进行分离,以甲醇-水(10∶90)为流动相,柱温25℃,流速1.0 mL.min-1,进样量为10μL,柱后分流比为1∶3,质谱采用多离子反应监测(MRM)方式进行检测,正离子模式,定量离子为m/z 162.2→103.1。在优化条件下,样品在10 min内完成分析,左旋肉碱在0.40～10.0 mg.L-1范围内线性关系良好(r=0.999 3)。方法的加标回收率为87%～106%,检出限(S/N=3)和定量下限(S/N=10)分别为39.0、116.9 ng。该方法操作简便、灵敏度高、重复性好,可用于婴幼儿配方奶粉中左旋肉碱的测定。     

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.     

K2NiF4型结构的A2－xSrxBO4(A＝La, Dy, B＝Mn, Fe, Co, Ni)希土复合氧化物的合成

以典型的轻希土镧和重希土镝及碱土金属锶作为Ａ位离子，以过渡金属锰、铁、钴、镍作为Ｂ位离子，合成了Ｋ２ＮｉＦ４型结构的Ａ２－ｘＳｒｘＢＯ４希土复合氧化物，采用粉末Ｘ射线衍射技术考察了反应条件等因素对生成Ｋ２ＮｉＦ４型四方（Ｔ）结构上析影响，实现结果表明，四方结构的形成不仅与几何因素有关，而且与各组分的物理化学性质有关。各个不同的组成，生成四方相的温度范围也有所不同。适当地提高反应温度以及延长灼烧时间     

四黄散外敷结合封包照射技术对术后早期炎性肠梗阻的影响及机制研究

目的 探讨在常规治疗的基础上,加用四黄散（Si-Huang-San,SHS）外敷和封包照射技术相结合的治疗手段对术后早期炎性肠梗阻的治疗效果及其作用机制。方法 从临床和动物实验两个层面进行研究。临床病人分为临床常规（c-convention）组和临床四黄散（c-SHS）组两个组：c-convention组患者给予常规西医治疗;c-SHS组在临床常规组的基础上加用腹部外敷四黄散行封包及神灯-TDP照射治疗。大鼠EPISBO造模成功后,将其分为3组,分别为对照（control）组、常规治疗（convention）组、常规治疗加四黄散（SHS）组。结果 c-SHS组病人腹痛缓解时间、胃肠减压引流量、肛门恢复排气时间均较c-convention组减少,有统计学意义（P<0.05）;SHS组大鼠的回肠粘膜损伤显著低于control组和convention组;与大鼠control组、convention组相比,SHS组的24 h小肠推进比明显增加,差异有统计学意义（P<0.05）;与大鼠control组、convention组相比,SHS组大鼠CRP、IL-8 和TNF-α的血清浓度显著降低（P<0.01或P<0.05）。结论 加用腹部外敷四黄散行封包及神灯-TDP照射治疗,可提高对EPISBO的临床疗效,促进小肠蠕动,减轻回肠粘膜损伤,降低炎性肠梗阻大鼠的血清炎症因子水平,为EPISBO的临床治疗提供新的理论基础与实践依据。     

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.     

Infrared and Raman spectra of magnesium ammonium phosphate hexahydrate (struvite) and its isomorphous analogues. IX: Spectra of protiated and partially deuterated cubic magnesium caesium phosphate hexahydrate

Infrared and Raman spectra of cubic magnesium caesium phosphate hexahydrate, MgCsPO₄·6H₂O (cF100), and its partially deuterated analogues were analyzed and compared to the previously studied spectra of the hexagonal analogue, MgCsPO₄·6H₂O (hP50). The vibrational spectra of the cubic and hexagonal dimorphic analogues are similar, especially in the regions of HOH stretching and bending vibrations. In the difference IR spectrum of the slightly deuterated analogue (<5% D), one distinctive band appears at 2260 cm⁻¹ with a small shoulder at around 2170 cm⁻¹, but only one band is expected in the region of the OD stretchings of isotopically isolated HDO molecules. The small weak band could possibly result from second-order transitions (a combination of HDO bending and some libration of the same species) rather than statistical disorder of the water molecules. By comparing the IR spectra in the region of external vibrations of water molecules of the protiated compound recorded at RT (room temperature) and at LNT (liquid nitrogen temperature) and those in the series of the partially deuterated analogues, it can be stated with certainty that the bands at 924 and 817 cm⁻¹ result from librations of water molecules, rocking and wagging respectively. And the band at 429 cm⁻¹ can be safely attributed to a stretching Mg–O_w mode. In the ν₃(PO₄) and ν₄(PO₄) region in the infrared spectra, one band in each is observed, at 995 and 559 cm⁻¹, respectively. In the region of the ν₁ modes, in the Raman spectrum of the protiated compound, one very intense band was observed at 930 cm⁻¹ which is only insignificantly shifted to 929 cm⁻¹ in the spectrum of the perdeuterated compound. The band at 379 cm⁻¹ in the Raman spectrum could be assigned to the ν₂(PO₄) modes. With respect to the phosphate ion vibrations, the comparison between the two polymorphic forms of MgCsPO₄·6H₂O and their deuterated compounds shows that ν₁(PO₄) and ν₃(PO₄) appear at lower wavenumbers in the cubic phase than in the hexagonal phase. These data are in full agreement with the lower repulsion potential at the cubic lattice sites compared with that for the hexagonal lattice sites.