Correlation of the position of the bond functions in H-X with electronegativity

S type Gaussian bond functions are optimized for HF, H₂O, NH₃, and CH₄. The optimization is carried out with respect to the exponent and position in the H-X bond. The position is found to correlate well with the electronegativity of Pauling and Allred-Rochow.     

钌（Ⅱ）－联吡啶－巴比妥酸－Ce（Ⅳ）化学发光体系测定巴比妥酸的研究

利用巴比妥酸对Ｃｅ（Ⅳ）氧化钌（Ⅱ）－联吡啶化学发光反应的增强作用，建立了痕量巴比妥酸的自动脉冲注射化学发光测定法方法的检出限为１０×１０－９ｇ／ｍＬ，线性范围为５０×１０－８－６．２×１０－５ｇ／ｍＬ巴比妥酸的衍生物如巴比妥、苯巴比妥和戊巴比妥对Ｃｅ（Ⅳ）氧化钌（Ⅱ）联吡啶化学发光反应无增强作用据此对合成样中巴比妥酸作选择性检测探讨了巴比妥酸的增强机理     

Captodative olefins: methyl 2-aryloxy-3-dimethyl-aminopropenoates and their application in a new synthesis of benzofurans

The β-substituted captodative olefins methyl 2-aryloxy-3-dimethylaminopropenoates 4a-h were synthesized, via aminomethylenation of the corresponding 2-phenoxyacetic esters 9a-h. Lewis acid promoted intramolecular cyclization of alkenes 4 led to benzofurans 7a-h, in an efficient synthetic approach to the benzofuran frame.     

Phosphorylthioacetamides in the synthesis of annulated quinoxalines

Diethoxyphosphorylthioacetamide in the reaction with 2,3-dichloroquinoxaline acted as a thionating reagent, giving diethoxyphosphorylacetonitrile and 2-chloro-3-[(3-chloro-2-quinoxalinyl)thio]quinoxaline. Reactions of phosphorylthioacetamides with N-methylquinoxalinium iodide in alcohol media in the presence of a base proceeded stereoselectively to afford cis-3-phosphoryl-1,3,3a,4,9,9a-hexahydro-2H-pyrrolo[2,3-b]quinoxaline-2-thiones. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1010–1013, May, 2007.     

Synthesis of stable azomethine ylides by the rearrangement of 1,3-dipolar cycloadducts of 3,4-dihydroisoquinoline-2-oxides with DMAD

1-Aryl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolines were prepared according to a one-pot procedure involving the reaction of 2-(3,4-dimethoxyphenyl)-ethylamine with aromatic aldehydes in TFA at reflux. The tetrahydroisoquinolines were treated with H₂O₂-WO₄²⁻ in methanol at room temperature to give the corresponding 3,4-dihydroisoquinoline-2-oxides. Treatment of these cyclic nitrones with DMAD in toluene at room temperature gave the corresponding isoxazolo[3,2-a]isoquinolines. These compounds were heated in toluene at reflux to give the corresponding ylides in high yields (Method A). The effect of the substituents on the rate of the rearrangement of such compounds prompted us to discuss a new mechanism involving consecutive C-C bond heterolysis and 1,3-sigmatropic shift. A one-pot reaction involving the treatment of the nitrones with equimolar amounts of DMAD in refluxing toluene also gave the ylides (Method B). The structures of the prepared compounds were elucidated by spectral means and elemental analyses.     

Concentrated electrolyte solutions at high temperatures and pressures

A survey is given of recent experimental results obtained from high-temperature, high-pressure investigations with water, aqueous solutions, and ionic fluids. Data on the static dielectric constant of water to 550°C and 5 kbar are given and discussed with respect to their relation to water structure. Infrared and Raman spectra of HDO in pure water have been obtained to 400°C and 4 kbar, which give information on hydrogen bonding. Xe–H₂O and CO₂–H₂O mixtures were investigated in the infrared. Ni(II) and Cu(II) complexes were investigated by absorption spectroscopy in aqueous solutions of high chloride content to 350°C and 2–6 kbar. The gas-liquid critical point of ammonium chloride was found at 880°C and 1635 bars. This fluid appears to be predominantly ionic even in the critical region. The possibility of converting pure polar fluids such as ammonia and water into concentrated ionic solutions by self-ionization at very high pressures is mentioned.This paper was presented at the symposium, The Physical Chemistry of Aqueous Systems, held at the University of Pittsburgh, Pittsburgh, Pennsylvania, June 12–14, 1972, in honor of the 70th birthday of Professor H. S. Frank.     

Complexation of Ni (II) and Zn(II) ions by 3-(1-naphthyI)-2-mercaptopropenoic acid

The complexation equilibria between Ni(II) and Zn(II) metal ions with 3-(1-naphthyl)-2-mercaptopropenoic acid (H₂NMP) were studied by glass electrode potentiometry, at 25 °C and 1.0 mol·dm^–3 in NaClO₄ as constant ionic medium in 50% (v/v) water-ethanol solutions. Formation constants for the complexes Ni(NMP), Ni(NMP) ₂ ^2– , Zn(NMP) and Zn(NMP) ₂ ^2– , refined by the MINIGLASS program, are reported.     

鄂尔多斯盆地长7储层致密油水平井CO2补充能量与吞吐参数优化

长7储层是鄂尔多斯盆地主要的致密区块,近一半的致密油分布其中。针对长7储层开采渗透率低、开采难度大、依靠弹性开采产能较低、能量衰竭较快等问题,通过数值模拟的方法,构建水平井分段压裂数值模拟模型,首先对比不同吞吐方式对油田产能的影响,优选出CO₂吞吐为首选的补充能量方式。其次对井网形式、井网参数及吞吐参数进行优化研究。最终优选出合适的吞吐方案,达到提高生产效率的目的。结果表明,该储层的最优注采吞吐参数为：周期注入量为2 673 t、注入压力为21 MPa、注入速度为90 t/d、焖井时间为10 d。研究对鄂尔多斯盆地长7储层提高采收率具有一定的参考意义。     

高岭土负载绿色合成纳米铁的制备及其对孔雀石绿和铅离子的去除性能研究

红背桂树叶提取物绿色合成铁纳米颗粒（Fe NPs）在水环境修复领域具有很高的应用潜力。但由于Fe NPs存在团聚、易氧化等不稳定因素,在去除污染物时抑制了反应活性。为了解决这一问题,使用一步法制备了高岭土负载Fe NPs （K-Fe NPs）,并系统地检测了其对孔雀石绿和Pb²⁺混合污染物的去除反应活性。采用X射线衍射（XRD）和傅里叶红外光谱（FTIR）对Fe NPs、高岭土和K-Fe NPs进行表征和分析。3种材料对比实验结果表明,K-Fe NPs对单独的孔雀石绿和Pb²⁺的去除效率（99.10%和93.41%）优于Fe NPs（93.67%和85.33%）和高岭土（32.54%和12.50%）。此外,K-Fe NPs经过4次重复循环对孔雀石绿和Pb²⁺的去除率仍分别为74.02%和55.48%。结果表明,K-Fe NPs在染料和重金属离子复合污染修复领域具有一定应用前景。     

超高压高CO2气藏偏差系数图版扩展与应用

Standing-Katz图版法确定天然气偏差系数是目前最常用、最基础的方法之一,但存在人工读值误差大、在超高压（拟对比压力大于15）和高CO₂含量天然气使用受限等问题。设计单组分偏差系数测定实验,结合Standing-Katz图版曲线变化规律,将图版拟对比压力扩展到30,拟对比温度扩展到3.6,并将图版数字化;基于不同CO₂含量偏差系数测定实验结果,推导了考虑不同CO₂含量的天然气拟临界压力、拟临界温度计算新模型,与常规非烃校正模型相比,新模型计算精度更高,适用范围更广。进一步将新临界参数校正模型嵌入到偏差系数扩展图版中,得到不同CO₂含量的偏差系数扩展图版,该图版在南海西部超高温高压、高CO₂含量天然气偏差系数计算中误差较小（不超过3%）,应用效果良好。