Fourier transform Raman spectral measurements of powdered quaternary mixtures of organic compounds: Exceptional pure component spectral reconstruction using band-target entropy minimization (BTEM)

Fourier transform Raman spectra of eight mixtures of four organic solids, namely dicyandiamide, melamine, acetamide and urea were measured. Matrices formed from these spectra were first subjected to singular value decomposition to obtain the right singular vectors. The right singular vectors were then subjected to blind source separation using band-target entropy minimization (BTEM), thus no a priori information (i.e. involving the nature of the components present, their spectra, nor their concentrations) was included in the analysis. The recovered pure component spectra are of exceptionally high quality and are consistent with pure reference spectra. Various empirical and statistical tests, such as the Euclidean norm and target transform factor analysis, were employed to assess the quality of the recovered spectra. The present results indicate the applicability of combined Raman and BTEM analysis for solid mixtures.     

Alternate synthesis of olanexidine base employing phase transfer catalysis

The traditional methods of synthesis of biguanide drugs generally result in the formation of high levels of waste. In this study, we have developed a simple and green route for the synthesis of olanexidine, the novel antimicrobial compound developed by Otsuka Pharmaceutical Factory Inc. This molecule has been clinically explored in Japan for pre-operative skin preparations. The proposed synthesis scheme is beneficial as it has obviated the use of harmful sodium dicyanamide and has employed the readily available dicyandiamide to facilitate cyanoguanidylation of 3,4-dichlorobenzylamine into 3,4-dichlorobenzylbiguanide. This intermediate was further condensed with 1-bromooctane, using tetrabutyl ammonium bromide as the phase transfer catalyst, in a biphasic solvent system comprising of water and ethyl acetate. The developed method resulted in an overall yield of 76% of olanexidine.     

表面增强拉曼光谱法同时检测奶粉中三聚氰胺和二聚氰胺

本文建立了奶粉中同时检测三聚氰胺及二聚氰胺的表面增强拉曼光谱法.奶粉样品经15％三氯乙酸溶液提取,中性氧化铝吸附杂质后进行拉曼光谱检测.三聚氰胺线性范围为0.0050～0.075 mg/L,检出限为0.0015 mg/L,回收率在79.5％～124％之间,相对标准偏差小于8.8％(n=5);二聚氰胺线性范围为0.50～l0mg/L,检出限为0.15 mg/L,回收率在76.5％～112％之间,相对标准偏差小于9.4％(n=5).该方法相比常规表面增强拉曼光谱法,仅通过一种样品前处理手段即可对奶粉中的三聚氰胺或二聚氰胺进行定性检出及定量分析,相比色谱等检测方法具有样品前处理过程简单、耗时短等优点,在奶粉质量监控方面具有良好的应用前景.     

Guide for Authors

The effects of epoxidized natural rubber (ENR) on the curing behaviors and adhesive strengths of an epoxy (diglycidyl ether of bisphenol-A) and dicyandiamide/2-methyl imidazole system are studied with differential thermal calorimetry (DSC), scanning electron microscopy (SEM), and Instron tensile testing instrument. From DSC analyses of specimens prepared with unsealed aluminum pans, it is obtained that the reaction exotherm, the time to maximal curing rate, the glass transition temperature, the rate constant, and the reaction order of the epoxy system change with respect to the content of ENR added because of the reaction of ENR with the epoxy system. The results obtained from SEM micrographs indicate that the particle size of the rubber phase increases with increasing the curing temperature and the ENR content. The volume fraction of the separated rubber phase also follows the similar trend except at the high curing temperature which implying that the dissolution of epoxy resin in the ENR phase also depends on the curing temperature and the amount of ENR present. The lap shear strengths of specimens prepared with etched aluminum substrates increase with increasing the curing temperature because of a better cure at a higher temperature, but decrease with increasing the ENR content resulting from an adverse effect of ENR on the mechanical properties of the cured resins.     

含柔性间隔基的扩链脲增韧环氧树脂性能研究——环氧树脂／扩链脲／双氰双胺体系性能研究

合成了含不同分子量柔性间隔基的扩链脲（Ｕｉ），并对其与双氰双胺共同固化环氧树脂体系的反应活性、抗冲击性能、动态力学性能、形态结构及贮存性能进行了考察。结果表明：含分子量为４００的聚乙二醇柔性链的扩链脲／双氰双胺／环氧树脂固化体系的抗冲击强度较单纯双氰双胺／环氧树脂固化体系提高了７倍左右，其冲击试样断面电镜照片呈韧性断裂的特征。扩链脲的反应活性基本不受分子中聚乙二醇链段分子量的影响。环氧树脂／扩链脲／双氰双胺体系在５０℃下贮存期可达１～２天。     

Synthesis and Characterization of Novel Template Complexes

Novel neutral polynuclear Ni^II chelates of L ‐cysteine (L ‐cyst) or D ‐penicillamine (D ‐pen) with dicyandiamide (dcda) were synthesized and characterized using elemental analysis, UV, CD, reflectance, and IR spectroscopy and/or thermogravimetric and X‐ray analysis. The obtained dinuclear compounds add important information about the chemistry of nickel(II) ions, which form types of bonds that cannot be obtained with other metal ions such as Co^II. These dinuclear nickel compounds contain four‐membered rings with two sulfur and two nickel atoms. Electronic transitions were elucidated from reflectance, CD and absorbance spectroscopy and confirm a distorted square planar arrangement of the nickel ions. Because the same structure with Co^II ions could not be obtained directly, dimethylglyoxime was added to a suspension of the template complex with D ‐pen in water to separate the nickel ions. The separation of the ligand was confirmed by elemental analysis, IR, and ¹H NMR spectroscopy. It reacted with Co^II to give a different mononuclear crystalline complex that was studied by X‐ray single crystal diffraction. The crystals are orthorhombically with space group C222₁, a = 0.11769(4) pm, b = 0.13632(4) pm, c = 0.25239(8) pm, V = 0.0040490(2) pm³, and Z = 8.     

双氰胺高效液相色谱检测方法的研究进展

介绍了目前国内外对双氰胺的一些检测方法,包括凯氏定氮法、水解法、红外光谱法、薄层色谱法、分光光度法和高效液相色谱法,并对这些方法的优缺点进行了比较,采用高效液相色谱法更为方便和有效.综述了双氰胺运用高效液相色谱检测方法的研究进展,为双氰胺的检测提供参考和帮助.     

Effect of tertiary amine accelerators with different substituents on curing kinetics and reactivity of epoxy/dicyandiamide system

Non-isothermal Differential Scanning Calorimetry and gel time measurements were employed to study the effects of four different tertiary amine accelerators with different molecular structure and substituents on the curing behavior and reactivity of epoxy/dicyandiamide (DICY) system. Results showed that the acceleration behavior depends on three factors: the bulkiness, the number of nitrogen atoms in molecular structure and the electron density of accelerator. Among these, the former two factors demonstrated stronger effect. The results of model fitting kinetic demonstrated that Šesták–Berggren model can well simulate the reaction rates especially for the samples accelerated by 2,4,6-tris(dimethylaminomethyl)-phenol and (Dimethylaminomethyl)phenol. The activation energy projected by Flynn-Wall-Ozawa and Kissinger–Akahira–Sunose methods exposed different amounts for each accelerator while both models revealed similar trends. Moreover, 1-methylimidazol-accelerated samples showed shortest storage life and gel time mainly due to the presence of two nitrogen atoms in a compact structure of accelerator.     

液相电化学沉积法制备高氮含量CNx薄膜及性能的研究

采用液相电化学沉积法,以二氰二胺的丙酮溶液为沉积液,以镀有ITO(铟锡氧化膜)的导电玻璃为衬底制备了CNx薄膜.初步探讨了沉积温度和沉积电压对薄膜中氮含量的影响.通过XPS、FTIR光谱、SEM和US-Vis光谱对得到的CNx薄膜的化学结合状态、结构形貌和光学性质进行了表征,并用高电阻仪对薄膜的绝缘性进行了分析.XPS结果表明,CNx薄膜中碳氮主要以单键连接,sp3杂化的C—N键占85%.在IR光谱中,仅出现了C—N键和CN双键的吸收峰.SEM图谱显示CNx薄膜呈颗粒状,粒径平均为80nm左右.在水浴加热条件下沉积的CNx薄膜在200～300nm近紫外区为非线性吸收.薄膜的电阻率随氮含量的增加而增大,测量值在1012～1016Ω·cm之间.     

Synthesis and Crystal Structure of Ammonium Cyanimide NH4HCN2

The compound NH₄HCN₂ ( 1 ) was prepared by the reaction of H₂CN₂ with liquid ammonia. The ammonium salt 1 was characterized by a low temperature single‐crystal X‐ray structure analysis. The anionic part of the structure consists of HCN₂^? anions, which are connected via N–H···N bonds (H···N distance: 2.47Å, DHA: 165°). The N–H···N hydrogen bonds of the ammonium ion to the anions range from 2.00 to 2.14Å (DHA = Donor···Acceptor angles: 165–176°), all N–H···N interactions together give rise to a three‐dimensional network. 1 decomposes quantitatively to dicyandiamide at room temperature.