Neon‐Bearing Ammonium Metal Formates: Formation and Behaviour under Pressure

The incorporation of noble gas atoms, in particular neon, into the pores of network structures is very challenging due to the weak interactions they experience with the network solid. Using high‐pressure single‐crystal X‐ray diffraction, we demonstrate that neon atoms enter into the extended network of ammonium metal formates, thus forming compounds Ne_x[NH₄][M(HCOO)₃]. This phenomenon modifies the compressional and structural behaviours of the ammonium metal formates under pressure. The neon atoms can be clearly localised within the centre of [M(HCOO)₃]₅ cages and the total saturation of this site is achieved after ～1.5 GPa. We find that by using argon as the pressure‐transmitting medium, the inclusion inside [NH₄][M(HCOO)₃] is inhibited due to the larger size of the argon. This study illustrates the size selectivity of [NH₄][M(HCOO)₃] compounds between neon and argon insertion under pressure, and the effect of inclusion on the high‐pressure behaviour of neon‐bearing ammonium metal formates.     

Quantification of flupirtine maleate polymorphs using X-ray powder diffraction

Flupirtine maleate,a pharmaceutical compound for treating psychotic disease in clinics,has seven polymorphs.Form A,with better crystal stability and bioavailability,has been widely used as the pharmaceutical crystal form.Unfortunately,it is usually found in a polymorphic mixture with form B.In this study,pure crystal forms of A and B were prepared and characterized by X-ray powder diffraction (XRPD),Fourier transform infrared spectroscopy (FT-IR) and thermal analysis.An XRPD-based method for the quantitative determination of the amount of the flupirtine maleate polymorphs form A and form B was also established through a systematic optimization of instrumental parameters.The results of the analytical methodology validation showed that the XPRD method had a broad quantitative range of 0-100%(w/w),good linear relationship,with R²=0.999,excellent repeatability and precision and low limits of detection (LoD) of 0.15%(w/w) and quantification (LoQ) of 0.5%(w/w).The results also showed that the single-peak method was not as good as the whole pattern in reducing the influence of the preferred orientation,but this can be compensated for by a systematic optimization of instrumental parameters and validating the analytical methodology to reduce errors and obtain a good,repeatable,sensitive,and accurate method.This XRPD method can be used to analyze mixtures of flupirtine maleate polymorphs (forms A and B) quantitatively and control the quality of the bulk drug.     

A Novel Method for the Detection of Chlorpyrifos by Combining Quantum Dot-labeled Molecularly Imprinted Polymer with Flow Cytometry

Uniform-sized fluorescent molecularly imprinted polymers were prepared by one-step swelling and suspension polymerization, while chlorpyrifos, methacrylic acid, ethylene glycol dimethacrylate, and oil-soluble CdSe/ZnS quantum dots were used as the carrier, template molecule, functional monomer, cross-linker, and fluorophor, respectively. The morphology, adsorption dynamics, binding ability, and selectivity of quantum dot-labeled molecularly imprinted polymers were evaluated. The dosage of quantum dots for labeling the molecularly imprinted polymers was optimized. The results showed that the optimized dose of quantum dots was 200?µL using a concentration of 8.0?µM. The microsphere size was approximately 10?µm with a honeycombed surface. The quantum dot-labeled molecularly imprinted polymers had an even brightness and a high selectivity. In the presence of different concentrations of chlorpyrifos, a decrease in the fluorescence intensity of the quantum dot-labeled molecularly imprinted polymer was clearly identified by flow cytometry. The whole detection process was accomplished within 2?h including pretreatment. This method was used for the determination of chlorpyrifos in tap water samples.     

Ni(II), Co(II), and Cu(II) complexes incorporating 2-pyrazinecarboxylic acid：Synthesis,characterization, electrochemical evaluation,and catalytic activity for the synthesis of 2H-indazolo[2,1-b]phthalazine-triones

Three complexes containing 2-pyrazinecarboxylate (pzca–), including [Ni(pzca)2(H2O)2], [Co(pzca)2(H2O)2], and [Cu(pzca)2(H2O)2], have been synthesized and characterized using physico-chemical and spectroscopic methods. Furthermore, the structure of each complex was determined by single-crystal X-ray diffraction. All three complexes have an octahedral geometry, where the metal ion chelated by two carboxylate oxygens, two nitrogen atoms belonging to pyrazinic acid molecules, and two oxygen atoms of two water molecules. The catalytic activities of these complex-es were also investigated in the green synthesis of 2H-indazolo[2,1-b]phthalazine-triones by the reaction of hydrazine hydrate with an arylaldehyde, phthalic anhydride, and dimedone in acetic acid.     

Novel Highly Energetic Pyrazoles: N‐Trinitromethyl‐Substituted Nitropyrazoles

A new family of energetic compounds, nitropyrazoles bearing a trinitromethyl moiety at the nitrogen atom of the heterocycle, was designed. The desirable high‐energy dense oxidizers 3,4‐dinitro‐ and 3,5‐dinitro‐1‐(trinitromethyl)pyrazoles were synthesized in good yields by destructive nitration of the corresponding 1‐acetonylpyrazoles. All of the prepared compounds were fully characterized by multinuclear NMR and IR spectroscopy, as well as by elemental analysis. Single‐crystal X‐ray diffraction studies show remarkably high density. Impact sensitivity tests and thermal stability measurements were also performed. All of the pyrazoles possess positive calculated heats of formation and exhibit promising energetic performance that is the range of 1,3,5‐trinitroperhydro‐1,3,5‐triazine and pentaerythritol tetranitrate. The new pyrazoles exhibit positive oxygen balance and are promising candidates for new environmentally benign energetic materials.     

Li2B4O7坩埚内预氧化熔融铸片XRF法测定含还原物耐火材料中主量和次量组分

在四硼酸锂坩埚中,以碳酸锂和硝酸铵为氧化剂,在铂金坩埚外对含还原物耐火材料进行预氧化和烧结。在高温氧化过程中,由于样品表面包裹有含氧化剂为主的烧结物,在继续熔融氧化产生的气体浮力作用下,样品在未被氧化前,不与铂金坩埚接触。因此,避免了熔融过程中铂金坩埚腐蚀问题。实验结果表明,氧化温度控制在730℃以下,时间15min内,含还原物耐火材料样品与氧化剂发生氧化烧结反应,四硼酸锂坩埚不会熔穿。确定的预氧化温度为720℃,时间为5~15min。结合现有的报道,确定了熔融铸片所需氧化剂和脱模剂的用量、熔融温度和时间。按拟定的方法,用国家和行业标准样品绘制工作曲线,对含还原物耐火材料样品进行了测定。与湿法分析结果进行比较表明,准确度与湿法分析相当。     

基于迭代小波变换的光谱信号本底扣除方法研究

本底会对光谱分析结果产生很大的干扰作用,为获取特征峰的有效信息,必须首先去除本底。该文提出了一种基于小波变换的本底扣除算法,通过对光谱及后续光谱迭代进行小波变换,利用逼近系数估计本底,直到本底收敛。提出了判断多次估计的本底最大误差是否足够小的收敛准则。利用该算法去除本底后,即可进行特征峰信息的提取。分别利用仿真光谱和实验能量色散X射线荧光光谱对算法进行了验证,并与传统小波变换和多项式拟合法进行了对比。结果表明,该算法能够更准确扣除光谱本底,对其他光谱的本底扣除也具有借鉴意义。     

Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α′-P3N5, δ-P3N5 and PN2

Non-metal nitrides are an exciting field of chemistry, featuring a significant number of compounds that can possess outstanding material properties. These properties mainly rely on maximizing the number of strong covalent bonds, with crosslinked XN₆ octahedra frameworks being particularly attractive. In this study, the phosphorus–nitrogen system was studied up to 137 GPa in laser-heated diamond anvil cells, and three previously unobserved phases were synthesized and characterized by single-crystal X-ray diffraction, Raman spectroscopy measurements and density functional theory calculations. δ-P₃N₅ and PN₂ were found to form at 72 and 134 GPa, respectively, and both feature dense 3D networks of the so far elusive PN₆ units. The two compounds are ultra-incompressible, having a bulk modulus of K₀=322 GPa for δ-P₃N₅ and 339 GPa for PN₂. Upon decompression below 7 GPa, δ-P₃N₅ undergoes a transformation into a novel α′-P₃N₅ solid, stable at ambient conditions, that has a unique structure type based on PN₄ tetrahedra. The formation of α′-P₃N₅ underlines that a phase space otherwise inaccessible can be explored through materials formed under high pressure.     

DKDP晶体的柱面形貌与缺陷分析

采用原子力显微镜观测全方位生长的DKDP晶体的{100}面形貌,发现有螺旋位错,由此推断DKDP晶体{100}面以螺旋位错机制生长;利用同步辐射X射线白光形貌术观测了DKDP晶体缺陷,探讨了不同生长条件及生长阶段对晶体完整性的影响.     

多晶薄膜X-射线衍射

作者在普通X-射线衍射仪上实施了样品倾斜X-射线衍射(STD)技术,不需要专用薄膜附件(TFA)也能很好地进行薄膜结构的测定,并且给出其衍射能量方程和方位角方程,从而使理论、实验和结构解析结合为一体。目前,应用该技术已经成功地解决了一些其它简便方法所无法解决的诸如物相纵向分布变化测量等问题。本文还通过几种摩擦学用膜的测定结果阐明了该技术的应用及功能。