太空育种射干的X射线荧光及X射线衍射分析和表征

联用X射线荧光光谱(XRF)和粉末X射线衍射(PXRD)方法,对我国独创的第4代太空诱变育种射干中多种元素种类和含量及晶态物质进行了研究。结果表明:太空组射干K元素含量比地面组、对照品分别提高了1.03和0.31倍,Mg元素分别提高了1.44和0.06倍,Ca,Mn和Fe元素含量比地面组分别提高了0.95,0.30和0.29倍,Al元素比地面组、对照组分别降低了38.5%和85.5%,并在射干中鉴别出一水草酸钙(CaC2O4.H2O)晶体,晶体含量是地面组<太空组<对照品。从而可得出结论:太空射干中人体必需的矿质元素比地面组都更接近或优于对照品。文章研究结果和方法对筛选品质优良的太空药材籽种和推广种植太空药材以及建立中药材质量评价标准,有积极的作用和重要意义。     

常见客体分子对笼型水合物晶格常数的影响

Natural gas hydrates are considered as ideal alternative energy resources for the future, and the relevant basic and applied research has become more attractive in recent years. The influence of guest molecules on the hydrate crystal lattice parameters is of great significances to the understanding of hydrate structural characteristics, hydrate formation/decomposition mechanisms, and phase stability behaviors. In this study, we test a series of artificial hydrate samples containing different guest molecules (e.g. methane, ethane, propane, iso-butane, carbon dioxide, tetrahydrofuran, methane + 2, 2-dimethylbutane, and methane + methyl cyclohexane) by a low-temperature powder X-ray diffraction (PXRD). Results show that PXRD effectively elucidates structural characteristics of the natural gas hydrate samples, including crystal lattice parameters and structure types. The relationships between guest molecule sizes and crystal lattice parameters reveal that different guest molecules have different controlling behaviors on the hydrate types and crystal lattice constants. First, a positive correlation between the lattice constants and the van der Waals diameters of homologous hydrocarbon gases was observed in the single-guest-component hydrates. Small hydrocarbon homologous gases, such as methane and ethane, tended to form sI hydrates, whereas relatively larger molecules, such as propane and iso-butane, generated sⅡ hydrates. The hydrate crystal lattice constants increased with increasing guest molecule size. The types of hydrates composed of oxygen-containing guest molecules (such as CO₂ and THF) were also controlled by the van der Waals diameters. However, no positive correlation between the lattice constants and the van der Waals diameters of guest molecules in hydrocarbon hydrates was observed for CO₂ hydrate and THF hydrate, probably due to the special interactions between the guest oxygen atoms and hydrate "cages". Furthermore, the influences of the macromolecules and auxiliary small molecules on the lengths of the different crystal axes of the sH hydrates showed inverse trends. Compared to the methane + 2, 2-dimethylbutane hydrate sample, the length of the a-axis direction of the methane + methyl cyclohexane hydrate sample was slightly smaller, whereas the length of the c-axis direction was slightly longer. The crystal a-axis length of the sH hydrate sample formed with nitrogen molecules was slightly longer, whereas the c-axis was shorter than that of the methane + 2, 2-dimethylbutane hydrate sample at the same temperature.     

Effect of Yb3+ concentration on photoluminescence properties of cubic Gd2O3 phosphor

Yb³⁺ doped phosphor of Gd₂O₃ (Gd₂O₃:Yb³⁺) have been prepared by solid state reaction method. The structure and the particle size have been determined by X-ray powder diffraction measurements. The average particle size of the phosphor is in between 35 and 50 nm. The particle size and structure of the phosphor was further confirmed by TEM analysis. The visible and NIR luminescence spectra were recorded under the 980 nm laser excitation. The visible upconversion luminescence of Yb³⁺ ion was due to cooperative luminescence and the presence of rare earth impurity ions. The cooperative upconversion and NIR luminescence spectra as a function of Yb³⁺ ion concentration were measured and the emission intensity variation with Yb³⁺ ion concentration was discussed. Yb³⁺ energy migration quenched the cooperative luminescence of Gd₂O₃:Yb³⁺ phosphor with doping level over 5%, while the NIR emission luminescence continuously increases with increasing Yb³⁺ ion concentration.     

Host–guest interactions between niobocene dichloride and α-, β-, and γ-cyclodextrins: preparation and characterization

The possible inclusion complexes of Cp₂NbCl₂ into α-, β-, and γ-CD hosts have been investigated. The existence of a true inclusion complex in the solid state was confirmed by a combination of thermogravimetric analysis, FTIR, PXRD, and ¹³C CP-MAS NMR spectroscopies. The solid-state results demonstrated that α-cyclodextrin does not form inclusion complexes with Cp₂NbCl₂ whereas β- and γ-cyclodextrins do form such complexes. PXRD, NMR, and thermal analysis showed that the organometallic molecules of Cp₂NbCl₂OH are included in the cavities of β- and γ-cyclodextrins, possibly adopting a symmetrical conformation in the complex, with each glucose unit in a similar environment. In solution, ¹H NMR experiments suggest that niobocene has a shallow penetration on the β-CD leading to upfield shift on H-3 signal with a minor perturbation on the H-5 proton while for γ-CD, both H-3 and H-5 are shifted upfield substantially. This suggests that niobocene penetrates deeper into the γ-CD cavity than in the β-CD cavity, as a result of the cavity size. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Iso-structural phase transition in tetramethylammonium nickel（Ⅱ） nitrite [（CH3）4N][Ni（NO2）3]

The title compound, tetramethylammonium nickel nitrite [（CH3）4N][Ni（NO2）3], has a hexagonal perovskite-type structure with formula ABX3. It undergoes two reversible phase transitions occurring at about 409.1 and 428.4 K, associated with dielectric transitions. DSC measurement and dielectric measurement confirm the transition. The variable-temperature X-ray structural determinations and the powder X-ray diffraction （PXRD） experiments reveal that this compound has the same space group P3ml （No. 164） at 293 K, 413 K and 438 K. The phase transitions are caused by the rotation of the [（CH3）4N]＋ cation.     

5种丹参主要成分及微结构的检测及综合表征

利用X射线荧光(XRF)、粉末X射线衍射(PXRD)和傅里叶变换红外光谱(FTIR)分析技术,对安国栽培的5个不同种质丹参主要成分及微结构检测,对各样品中多种元素种类及含量、晶体及非晶体成分以一套综合特征图的方式对其表征;该谱将同种属不同种质丹参中的共有成分和细微差异之处给与直观地描述。3种技术共有制样简单,测定速度快,再现性和客观性好的特点;可用于药材优良品种的选育、中药材GAP种植条件的指导、药材产地特征、主要成分及微结构的检测及表征、质量稳定性的控制及真伪鉴别。     

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.     

A three‐dimensional twofold interpenetrated cobalt(II) MOF containing a flexible carboxylate‐based ligand: synthesis,structure and magnetic properties

The design and synthesis of coordination polymers (CPs) have attracted much interest due to the intriguing diversity of their architectures and topologies. The functional solid catena‐poly[μ₂‐aqua‐triaqua{μ₄‐5‐[4‐carboxyphenoxy)methyl]benzene‐1,3‐dicarboxylato}{μ₃‐5‐[4‐carboxyphenoxy)methyl]benzene‐1,3‐dicarboxylato}dicobalt(II)], [Co₂(C₁₆H₁₀O₇)₂(H₂O)₄]_n or [Co₂(HL)₂(μ₂‐H₂O)(H₂O)₃]_n, was synthesized successfully by self‐assembly of Co^II ions with 5‐[(4‐carboxyphenoxy)methyl]isophthalic acid (H₃L). The title compound was obtained under hydrothermal conditions and exhibits a twofold interpenetrated three‐dimensional skeleton with hms 3,5‐conn topology according to the cluster representation for valence‐bonded metal–organic frameworks (MOFs). It has been characterized by single‐crystal X‐ray diffraction, IR spectroscopy, powder X‐ray diffraction (PXRD), thermogravimetric analysis and susceptibility measurements. The antiferromagnetic coupling between adjacent Co^II centres occurs via superexchange through the ligands.     

Synthesis,spectroscopic (IR,electronic, FAB-mass,and PXRD), magnetic,and antimicrobial studies of new iron(III) complexes containing Schiff bases and substituted benzoxazole ligands

Mixed ligand complexes of iron(III), [Fe(sb)₂(py)Cl]?·?2H₂O (1–9) [where sbH?=?Schiff bases (derived from condensation of 2-aminopyridine (sapH), 2-aminophenol (saphH), o-toluidine (o-smabH), aminobenzene (sabH), p-toluidine (p-smabH), 3-nitroaniline (snabH), and anthranilic acid (saaH) with salicylaldehyde and substituted (mercapto-)benzimidazole (mbzH), {2-(o-hydroxyphenyl)}benzoxazole, (pboxH)], have been synthesized by the interactions of iron(III) chloride with corresponding ligands in 1?:?2 molar ratio in refluxing pyridine. These complexes have been characterized by elemental analyses, melting points, spectral, and magnetic studies. Powder X-ray diffraction studies of some representative complexes are also reported herein. The antibacterial and antifungal activities of the free ligands and their iron(III) complexes were found in vitro. The complexes showed good antibacterial and antifungal effect to some bacteria and fungi. Two standard antibiotics (chloromphenicol and terbinafine) were used for comparison with these complexes.