环糊精与抗癌药物HMBA相互作用的谱学研究

α－,β－,γ－ＣＤ与抗癌药ＨＭＢＡ相互作用的ＮＭＲ研究表明ＨＭＢＡ分子大小与α－ＣＤ内腔尺寸最为匹配,相互作用力最强。１３Ｃ－ＮＭＲ研究表明α－ＣＤ与ＨＭＢＡ形成了包结物,而且两者之间还有氢键存在。ＨＭＢＡ上的α－Ｃ,在与α－ＣＤ作用后产生的较大低场位移,说明在ＨＭＢＡ·α－ＣＤ体系中包结作用较强,使ＨＭＢＡ上α－Ｃ化学位移变化大。而ＨＭＢＡ上的－Ｃ＝Ｏ,在与α－,β－ＣＤ作用后产生高场位移,位移程度ＨＭ－ＢＡ．β－ＣＤ＞ＨＭＢＡ．α－ＣＤ,则氢键作用在ＨＭＢＡ．β－ＣＤ体系中较强些。     

水溶性铑膦配合物HRh(CO)(TPPTS)_3及其相关体系的~1H-NMR研究

在液体高分辨ＮＭＲ谱仪上, 测定并比较了具有高效烯烃氢甲酰化活性的水溶性铑膦配合物ＨＲｈ（ＣＯ）（ＴＰＰＴＳ）３ 及与此有关的配体ＴＰＰＴＳ和ＯＴＰＰＴＳ分别在Ｄ２Ｏ、混合溶剂Ｄ２Ｏ－ＴＨＦ（ｄ８）－ＣＤ３ＯＤ中的１Ｈ－ＮＭＲ谱图, 并借助１Ｈ－１Ｈ ＣＯＳＹ谱对上述３ 种化合物的１Ｈ－ＮＭＲ谱峰进行了指认; 讨论了影响化学位移和偶合常数的因素, 为水溶性铑膦配合物催化剂的结构与催化性能的关联及新催化剂设计研究提供了基础数据．     

酞侧基聚芳醚砜的核磁共振研究──PES－C的氢谱归属及碳谱峰的确认

用１３Ｃ－ＮＭＲ谱和二维异核化学位移相关谱（ＨＥＴＣＯＲ）归属了酞侧基聚芳醚砜（ＰＥＳ－Ｃ）的１Ｈ－ＮＭＲ谱峰，并经二维同核化学位移相关谱（ＣＯＳＹ）验证．对原１３Ｃ－ＮＭＲ谱峰归属作了部分修正．二维同核及异核相关谱为ＰＥＳ－Ｃ的碳、氢核磁谱峰归属提供了重要信息．由ＰＥＳ－Ｃ的核磁谱图可见其链结构的规整性     

用核磁共振和红外光谱构造煤抽提物的结构模型

用￣（１３）Ｃ－ＮＭＲ和￣１Ｈ－ＮＭＲ联合解析法和￣１Ｈ－ＮＭＲ／ＴＩＲ解析法分别求取了平朔煤镜质组吡啶抽提物中七个馏分的平均分子结构参数，并参考其它化学分析和测试结果，构造了以上七个馏分的平均分子结构模型。结果表明：平朔煤镜质组吡啶抽提物中存在着脂肪取代形式各异、芳碳率、芳环数不同，杂原子形式有别的各种芳烃混合物。     

环化聚丁二烯链结构的NMR研究

用Ｈ－ＨＣＯＳＹ谱证实环化聚丁二烯的多环序列末端存在三取代双键。解析Ｃ－ＮＭＲ谱表明残存的线形分子中仍然含有丁二烯的反１，４和１，２－单元。利用Ｈ－ＨＣＯＳＹ谱提供的信息对环化聚丁二烯的Ｈ－ＮＭＲ谱峰进行了归属，定义了参数Ｐ，Ｑ推导出环化度Ｘ和环化率Ｙ的计算公式，讨论了环化度Ｘ环化率Ｙ与参数Ｐ，Ｑ之间的关系，用上述方法处理了几个环化聚丁二烯的Ｈ－ＮＭＲ谱。     

中孔硅酸盐材料MCM-41的合成与表征研究(英文)

以十六烷基三甲基溴化铵为模板剂,硅酸钠为硅源,铝酸钠为铝源,在水热条件下成功地合成出了ＭＣＭ－４１中孔硅酸盐材料。采用ＸＲＤ、低温Ｎ２吸附脱附等测试手段对合成的ＭＣＭ－４１样品进行了表征。通过优化合成条件,合成出孔径３.２ ｎｍ、比表面９０４ｍ２／ｇ和孔壁厚约１.４６ ｎｍ的ＭＣＭ－４１分子筛。催化活性测定采用微反应活性实验来评价其活性和选择性。     

煤裂解过程中负载铁化学形态的变化

应用ＥＸＡＦＳ、ＸＡＮＥＳ和ＸＲＤ方法研究了褐煤中负载铁在裂解过程中化学形态的变化规律。结果表明，在载ＦｅＣｌ３．６Ｈ２Ｏ煤中，铁与煤表面碳－氧官能团发生强烈的相互作用。随热处理温度的升高，铁化学形态以如下顺序递变：高分散Ｆｅ－Ｏ／Ｃ络合物，超细ＦｅＯＯＨ，晶态Ｆｅ３Ｏ４，晶还原态铁（α－Ｆｅ，（Ｆｅ，Ｃ））《     

用Mo（Ⅲ）络合物分裂N_2分子

用Ｍｏ（Ⅲ）络合物分裂Ｎ_２分子麻省理工学院的Ｃ．Ｅ．Ｌａｐｌａｚａ和Ｃ．Ｃ．Ｃｕｍｍｉｎｓ用配位数为３的Ｍｏｔ（Ⅲ）络合物Ｍｏ（ＮＲＡｒ）３［Ｒ＝Ｃ（ＣＤ３）２ＣＨ３；Ａｒ＝３，５－Ｃ６Ｈ３Ｍｅ２（Ｍｅ，－ＣＨ３）与Ｎ２反应，实现了将Ｎ２分子裂开还?..     

六氟磷酸二（4,4‘—二甲基—2,2’—联吡啶）.（2,2‘—联吡啶—4,4’—二羧？…

用＾１Ｈ ＮＭＲ和＾１３Ｃ ＮＭＲ谱研究了新型电化学发光探针六氟磷酸二（４,４’;－二甲基－２,２‘－联吡啶）．（４．４’－二羧酸－２,２‘－联吡啶）合钌的立体结构,通过＾１Ｈ ＾１Ｈ ＣＯＳＹ,＾１３Ｃ－＾１Ｈ ＨＥＴＣＯＲ谱对其氢谱和碳谱中的各谱峰进行了归属,并给出了氢谱和碳谱峰的化学位移值。     

对甲氧基偶氮苯衍生物的核磁共振表征

用一维１ Ｈ ＮＭＲ、１３Ｃ ＮＭＲ 方法研究了对甲氧基偶氮苯衍生物的结构, 并通过二维１ Ｈ－ １ Ｈ 同核相关谱（ＣＯＳＹ） 、１３ Ｃ－ １ Ｈ 异核相关谱（ ＨＥＴＣＯＲ） 及１３Ｃ－ １ Ｈ 异核远程相关谱进一步地确定了该类衍生物的１ Ｈ 谱和１３ Ｃ 谱中各谱峰的归属, 为研究侧链液晶聚合物结构提供了有价值的数据。     

XPS研究低温等离子体聚苯乙烯表面改性

用氮气、二氧化碳和空气等离子体技术处理聚苯乙烯表面 ,并用X光电子能谱 (XPS)测定了聚合物表面的元素组成 ,相对含量和表面功能团的类型 .结果表明 ,经过不同条件处理后的聚合物表面引入了含氮和含氧基团 ,这对改善材料的沾润性和粘着性将起着明显作用 ;另外 ,不同处理条件对PS表面的氮、氧含量有很大影响     

Reactions of nitrogen and oxygen surface groups in nanoporous carbons under inert and reducing atmospheres

The reactions of surface functional groups have an important role in controlling conversion of char nitrogen to NOx during coal combustion. This study involved an investigation of the thermal stability and reactions of nitrogen surface functional groups in nanoporous carbons. Four suites of carbons, which were used as models for coal chars, were prepared with a wide range of nitrogen and oxygen contents and types of functional groups. The porous structures of the carbons were characterized by gas adsorption methods while chemical analysis, X-ray photoelectron spectroscopy, and X-ray near edge structure spectroscopy were used to characterize the surface functional groups. Temperature programmed desorption and temperature programmed reduction methods were used to study the reactivity of the surface functional groups during heat treatment under inert and reducing conditions. Heat treatment studies show that the order of stability of the functional groups is quaternary nitrogen > pyridinic > pyrrolic > pyridine N-oxide. Pyridine N-oxide surface groups desorb NO and form N2 via surface reactions at low temperature. Pyrrolic and pyridinic functional groups decompose and react with surface species to give NH3, HCN, and N2 as desorption products, but most pyrrolic groups are preferentially converted to pyridinic and quaternary nitrogen. The main desorption product is N2. Approximately 15-40 wt % of the original nitrogen was retained in the carbons mainly as quaternary nitrogen after heat treatment to 1673 K. The results are discussed in terms of decomposition ranges for surface functional groups and reaction mechanisms of surface species.     

Piperidone synthesis using amino acid: A promising scope for green chemistry

Piperidone is a family of organic chemicals characterized by a 6-carbon ring substituted with nitrogen and a double-bonded oxygen atom. Piperidones are named by the location of the nitrogen or amine group on the ring. It differs from piperidine by the presence of oxygen molecule (from ketone). It is used in pharmaceutical companies and chemical manufacturers as intermediates having anti microbial activity. It is usually synthesized using ammonia both in laboratory and industry. In present study, amino acid namely aspartic acid is used instead of ammonia. The amino acid incorporated piperidones is purified and analyzed using NMR spectroscopy. It has antimicrobial activity against Pseudomonas aeruginosa and Salmonella aboni.     

煤的化学降解研究——Ⅰ.煤的氯化降解

用水介质中氯化的方法对煤进行降解研究,考察了降解后煤的化学组成和在有机溶剂中抽提性质的变化。降解后,煤中碳、氢含量下降,氯、氧含量增加,腐植酸及活性官能团增多,使煤具有一系列新的性质。如在极性溶剂中抽出量显著增加,其中丙酮抽出率高达86.4%。     

Structure–activity relationship and the mechanism of analgesia of the analgesic drug 3-methyl-fentanyl and its analogs

The semiempirical self-consistent field MO (CNDO /2) calculations have been undertaken for 13 compounds involving 3-methyl-fentanyl and its analogs. Various quantum chemical indices were obtained. The relationships between the biological activity and quantum chemical indices of molecules of these compounds were investigated and it was found that there are remarkable relationships between the activity and some important quantum chemical indices such as the α-electron density of β substituent and the electron density of piperidyl nitrogen. The nature of interaction between the analgesics' molecule and the receptor was discussed on the basis of the relationships between the activity and quantum chemical indices and it was proposed that the β-substituent functions not only as a hydrophobic group, but also its electronic property has important effect on the activity. It may act as an electron acceptor and form acceptor–donor complex with receptor through the charge transfer process. The piperidyl nitrogen interacts with receptor forming quaternary ammonium ion and acting as positive charge center, and its electron density also has an important effect on the activity. The amide oxygen and nitrogen may be other active centers which function as donors when they interact with the receptor. The influence on activity through introduction of the hydroxyl group to the β-position of the 1-substituent of the piperdyl ring has also been discussed.     

在位红外光谱法研究丙烯腈、二丙酮丙烯酰胺和丙烯酸甲酯三元共聚物的低温热解

本文用傅里叶变换红外光谱法在位连续测定了丙烯腈(AN)、二丙酮丙烯酰胺(DAA)和丙烯酸甲酯(MA)三元共聚物在不同气氛中低温热解时化学结构的变化。据光谱峰的变化规律,发现共聚物在空气中热解时脱氢和氧化主要在环化反应发生之后;在氧气中热解时脱氢和氧化主要发生在环化反应之前;在氮气中热解时仅有环化和脱氢反应。在比较各气氛中的成环序列长度时,在氮气中热解环序列在275℃以下稍短;275℃以上稍长。共聚物羰基增加的相对含量与热解时间的平方根成正比。     

Study of metal ions (Na+, K+) interaction with different conformations of glycine molecule

Interaction of metal ions (Na⁺, K⁺) with different binding sites, such as amino nitrogen, hydroxyl oxygen, and carbonyl oxygen for all gaseous conformers of glycine molecule were investigated using Density Functional Theory (B3LYP/6‐311++G**, B3PW91/6‐311++G**) methods. It was found that the order of stability of the conformers was changed due to the binding of the metal ion. The relative energy values show that the 7p conformer is more stable than the 1p conformer when a metal ion binds with the carbonyl oxygen. The intensity of interaction on hydroxyl oxygen is very low due to the low basicity of hydroxyl oxygen. The binding affinities of the complexes were calculated using the thermochemical properties. The relative energy and chemical hardness values predicted the most stable complex. The calculated condensed Fukui functions predict the favorable reactive site among the three binding sites. It is concluded that the reactivity of each binding site varies for each conformation due to the presence of intramolecular hydrogen bonding. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Simulation of Molecular Dynamics of the Tetrapeptide Ala-Gly-Asp-Pro

A quantum-chemical calculation procedure intended for studying geometries and electronic structures of various peptides was tested using the tetrapeptide Ala-Gly-Asp-Pro as example. The trajectory of the molecular dynamics of the Ala-Gly-Asp-Pro molecule in the surrounding of water molecules was followed for a period of 1500 ps. The conformation of the peptide molecule does not change within this period. The water surrounding of the Ala-Gly-Asp-Pro molecule prevents formation of an intramolecular salt bridge between the nitrogen atom of the terminal amino group and oxygen atoms of the side carboxy group of Asp. It is suggested that the mechanism of the physiological action of Ala-Gly-Asp-Pro may involve hydrogen bonding with one or several functional groups of this molecule.     

活性炭纤维的脱硫性能

活性炭纤维作为一种新型高效吸附剂，在环保领域尤其是在烟气脱硫方面显示了广阔的应用前景。本文在作者所做工作和分析别人实验结果的基础上，综述了包括前驱体材料、制备条件以及活性炭纤维表面物理化学性能等影响活性炭纤维脱除烟气中SO2的主要因素，阐述了活性炭纤维脱硫的反应机理。认为含有较多量氮元素的前驱体材料具有较高的脱硫性能，类似的结果也出现在用不同方法制备的活性炭纤维中；众多的研究结果表明，活性炭纤维表面化学性能的影响尤其是表面物理性能的影响，其中表面含氧官能团对活性炭纤维脱除SO2不利，但用热处理方法脱除掉以CO形式释出的含氧官能团后可显著增强活性炭纤维的脱硫活性；此外，含氮官能团引入到活性炭纤维表面后也可显著增强活性炭纤维的脱硫活性。     

凝结热对低阶煤低温氧化过程的影响

选用Pulse Calorimeter仪器，研究了低阶煤在干燥氧气下低温氧化过程的反应热和相对湿度为80％的氮气下凝结热与温度的变化，以研究凝结热对低阶煤低温氧化过程的影响。结果表明,随着温度的上升体系的反应热增加，而凝结热减少。在26℃~60℃的低温下，体系的凝结热明显高于反应热。因此，低温下凝结热是影响低阶煤的低温氧化过程的重要因素。研究还得到了低阶煤在干燥氧气下低温氧化过程的动力学方程及活化能。