四苯基卟啉衍生物半波电位与ELUMO间关系的研究

用ＣＮＤＯ／２和ＨＭＯ方法计算了四苯基卟啉及其吡咯环取代的衍生物,配合物的轨道能级等量子化学数据。经拟合发现这些化合物的半波电位与最低空轨道能级有很姨的相关性。讨论了不同取代基团对这些化合物半波电位的影响。     

Synthesis of substituted 2-amino-4,6-bis(nonafluoro-tert-butyl)-1,3,5-triazines

A procedure was developed for the synthesis of substituted 2-amino-4,6-bis(nonafluoro-tert-butyl)-1,3,5-triazines from 2-chloro-4,6-bis(nonafluoro-tert-butyl)-1,3,5-triazine and aliphatic and aromatic amines. The data of¹⁹F NMR spectroscopy are indicative of the presence of a barrier to internal rotation. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1568–1572, August, 1999.     

光化疗抑瘤剂四苯基卟吩氮芥的合成

首次报道合成了6个四苯基卟吩氮芥化合物,其结构均经波谱及元素分析确证,活性实验表明所有受试化合物均具有对人肝癌细胞株SMMC-7721的化学杀伤和光动力效应双重活性,具有发展为高效低毒光化抗肿瘤药物的前景。     

Evaluation of the possibilities of detecting ejections of nitrogen oxides by an airborne differential absorption lidar operating in the medium ir spectral region

Using numerical simulation, we evaluated the possibilities of detecting ejections of nitrogen oxides by an airborne differential absorption lidar operating in the medium IR spectral region at converted frequencies of CO- and CO₂-lasers. We present results of calculations of random errors in determining the integrated content of nitrogen oxide and dioxide depending on the amount of ejection and the flight altitude of an airplane. It is shown that the use of frequency-converted CO- and CO₂-laser radiation makes it possible to determine ground-level ejections of nitrogen oxides at a level of 0.01 MPC. Institute of Atmospheric Optics, Siberian Branch of the Russian Academy of Sciences, I Akademicheskii Ave., Tomsk, 634055, Russia; e-mail: oleg@losa.iao.tomsk.ru. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 6, pp. 843–845, November–December, 1999.     

Microfluidic platform serves as controllable fabrication of binary Mo/Ir nanodots/carbon hetero-material for efficient electrocatalytic nitrogen reduction

Electrocatalytic nitrogen reduction reaction (NRR) is regarded as a potential routine to achieve environment-friendly ammonia production, because of its abundant nitrogen resources, clean energy utilization and flexible operation. However, it is hindered by low activity and selectivity, in which condition well-designed catalysts are urgently in need. In this work, a binary Mo/Ir nanodots/carbon (Mo/Ir/C) hetero-material is efficiently constructed via microfluidic strategy, of which the nanodots are homogeneously distributed on the carbon skeleton and the average size is approximately 1 nm. Excellent performance for NRR is obtained in 1 mol L⁻¹ KOH, of which the optimized ammonia yield and faradic efficiency are 7.27 μg h⁻¹ cm⁻² and 2.31% respectively. Moreover, the optimized ammonia yield of 6.20 μg h⁻¹ cm⁻² and faradic efficiency of 10.59% are also obtained in 0.005 mol L⁻¹ H₂SO₄. This work achieves the continuous-flow synthesis and controllable adjustment of hetero-materials for favorable morphologies, which provides an innovative pathway for catalyst design and further promotes the development of ammonia production field.     

三氟化氮纯度的分析

介绍三氟化氮中主要杂质组分含量的分析方法、标准物质的正确使用方法、杂质含量分析结果以及三氟化氮纯度测量结果不确定度的评价。     

开区注氮采空区自燃温度场的数值模拟研究

为了研究开区注氮采空区遗煤自燃和被抑制的力学过程,用非均质多孔介质中的渗流连续性方程、气体弥散方程和综合传热方程的联立,建立了采空区注氮非定常数值模型．结合实例,用迎风格式有限元方法求解．给出了采空区的漏风流态、氮气流态,描绘了采空区自燃过程中氧、CO浓度和温度分布的变化过程．计算考虑了瓦斯涌出和工作面推进的影响．得到注氮条件下采空区高温区形状变窄;随着注氮量的提高,使自然发火期逐渐变长,直至不自燃．理论计算与实际情况吻合．     

A New Strategy for the Synthesis of Polytrithiocarbonates Using a Polymeric Support System

A new polymerization strategy, consisting of nucleophilic substitution reaction between CS₃^2‐, immobilized on a polymeric support, and dimethyl α,α′‐dibromoalkylanedioate in solution, leads to the formation of polytrithiocarbonates. When n = 0, 1 in CH₃OOCCHBr(CH₂)_nCHBrCOOCH₃ (α,α′‐dibromoalkylanedioate), only five‐ or six‐membered cyclic trithiocarbonates were obtained; n ≥ 2 resulted in the formation of polytrithiocarbonates.     

Acetylene hydrochlorination over tin nitrogen based catalysts: effect of nitrogen carbon-dots as nitrogen precursor

The catalysts comprising the main active compounds of Sn-Nx were synthesized using trichlorophenylstannane ((C₆H₅)Cl₃Sn), nitrogen carbon-dots (NCDs), and activated carbon (AC) as starting materials, and the activity and stability of catalysts was evaluated in the acetylene hydrochlorination. According to the results on the physical and chemical properties of catalysts (TEM, XRD, BET, XPS and TG), it is concluded that NCDs@AC can increase (C₆H₅)Cl₃Sn dispersity, retard the coke deposition of (C₆H₅)Cl₃Sn/AC and lessen the loss of (C₆H₅)Cl₃Sn, thereby further promoting the stability of (C₆H₅)Cl₃Sn/AC. Based on the characterization results of C₂H₂-TPD and HCl adsorption experiments, we proposed that the existence of Sn-N_x can effectively strengthen the reactants adsorption of catalysts. By combing the FT-IR, C₂H₂-TPD and Rideal-Eley mechanism, the catalytic mechanism, in which C₂H₂ is firstly adsorbed on (C₆H₅)Cl₃Sn to form (C₆H₅)Cl₃Sn-C₂H₂ and then reacted with HCl to produce vinyl chloride, is proposed.