N—二茂铁酰胺酸的红外光谱研究

研究了七种Ｎ－二茂铁酰胺酸的红外光谱，讨论了分子中氢键对一些主要吸收峰的影响，并对某些构象异构体和互变异构现象用红外光谱作了定性分析和研究。     

N－二茂铁酰胺酸的红外光谱研究

研究了七种Ｎ－二茂铁酰胺酸的红外光谱，讨论了分子中氢键对一些主要吸收峰的影响，并对某些构象异构体和互变异构现象用红外光谱作了定性分析和研究。     

N-(苯基,二茂铁基)甲基-β-羟乙胺与Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Cd(Ⅱ), Hg(Ⅱ)配合物的红外光谱研究

二茂铁基苯基甲醇与三氟化硼-乙醚溶液在二氯甲烷中作用,形成相应的二茂铁苯基甲基碳正离子,无需从反应混合物中分离出来,该离子便可与乙醇胺作用得到N-(苯基, 二茂铁基)甲基-β-羟乙胺(FcY),用该氨基醇分别与氯化镍,氯化铜,氯化锌,氯化镉,氯化汞反应,制备了氨基醇-镍(Ⅱ)、 氨基醇-铜(Ⅱ)、 氨基醇-锌(Ⅱ)、 氨基醇-镉(Ⅱ)、 氨基醇-汞(Ⅱ)五种二茂铁基氨基醇-重金属配合物(用通式M-FcY表示)。 用Nexus670FTIR红外光谱仪对二茂铁基氨基醇和五种配合物在4 000～400 cm-1范围内测定傅里叶变换红外光谱,对各M-FcY的FTIR主要吸收峰做了经验归属,并将各M-FcY的特征吸收峰与FcY的相应吸收峰作对比分析,结果表明：配合物中—OH , —NH—键的吸收峰位置均向低波数方向移动;C—O, C—N键吸收峰位置向高波数方向移动。说明二茂铁基氨基醇中的氨基、羟基与重金属离子之间形成了配位键。     

金属配合物（pq）2Ir（N-phMA）发光材料的合成及光谱性质

设计出一种酰胺类金属铱有机配合物磷光电致发光材料,该材料是以2-苯基喹啉(pq)为主配体,N-苯基甲基丙烯酰胺(N-phMA)为辅助配体的金属配合物(pq)2Ir(N-phMA).该化合物的结构由核磁,红外表征确定,它在586nm处的强荧光发射,表明它是一种可用于OLED的黄光发光材料.     

2-羟基-2-二茂铁基丙胺与Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Cd(Ⅱ), Hg(Ⅱ)配合物的红外光谱研究

乙酰基二茂铁与三甲基腈硅烷反应制得α-氰基-α-二茂铁基乙氧三甲硅烷,经四氢铝锂还原后得到2-羟基-2-二茂铁基丙胺(FcA),用该氨基醇分别与氯化镍,氯化铜,氯化锌,氯化镉,氯化汞反应,制备了氨基醇-镍(Ⅱ)、氨基醇-铜(Ⅱ)、氨基醇-锌(Ⅱ)、氨基醇-镉(Ⅱ)、氨基醇-汞(Ⅱ)五种二茂铁基氨基醇-重金属配合物(用通式M-FcA表示)。用Nexus670FTIR红外光谱仪对二茂铁基氨基醇和五种配合物在4 000～400 cm-1范围内测定傅里叶变换红外光谱,对各M-FcA的FTIR主要吸收峰做了经验归属,并将各M-FcA的特征吸收峰与FcA的相应吸收峰作对比分析,结果表明：配合物中—OH, —NH₂键的吸收峰位置均向低波数方向移动;C—O, C—N键吸收峰位置向高波数方向移动。说明二茂铁基氨基醇中的氨基、羟基与重金属离子之间形成了配位键。     

不同体系下氢键对聚丙烯酰胺光谱的影响

采用红外,紫外光谱分析不同体系下氢键对部分水解高分子聚丙烯酰胺光谱的影响。研究表明,高分子聚丙烯酰胺中的酰胺基与部分水解的羧酸基能形成分子内氢键导致酰胺基中游离-NH₂特征吸收峰向低频方向移动;聚丙烯酰胺在水溶液中随浓度的增大主要形成分子内氢键使最大吸收波长发生红移;在含中等浓度钠离子和钙离子的水溶液体系下,分子内氢键和分子间氢键同时存在,在含高浓度钠离子和钙离子体系下,则主要形成分子间氢键。不同体系下,氢键对聚丙烯酰胺光谱的影响不同：在水溶液体系下,其最大吸收波长红移8 nm,在钠离子单独存在的体系下,最大吸收波长红移4 nm,在钙离子和钠离子同时存在的体系下,最大吸收波长红移2 nm。     

DTPA—PNIPAAm的合成及热敏性实验

水溶性高分子近年来引起了科学界的广泛关注，己广泛用在药物合成、作血浆替代物和药物输运载体。自1968年Heskins发现聚N-异丙基丙烯酰胺（PNIPAAm）水溶液具有最低临界溶液温度的特性以来，热敏高分子成为国际上的研究热点之一。基于聚N-异丙基丙烯酰胺和聚N-异丙基甲基丙烯酰胺的热敏高分子因其独特的温度敏感性还可应用于控制释放、酶的固化、循环吸收和免疫分析等领域，这种高分子的一个显著特点就是有一个固定的较低相转变温度（约30-31℃），在很窄的温度范围内其溶解度会发生显著变化，而且在高温时溶解度降低。     

2-丙烯酰胺基-2-甲基-1-丙烷磺酸过渡金属化合物红外光谱研究

利用FTIR和X－射线粉末衍射方法研究了三种2－丙烯酰胺基－2－甲基－1－丙烷酸过渡金属化合物（Co^2 ,Ni^2 ,Cu^2 )。钴、镍两种化合物红外光谱与铜化合物存在明显差别。钴、镍两种化合物红外光谱相近,但晶体结构不同。     

二茂铁有机锡衍生物的13C,119Sn NMR研究

本文测定了几种二茂铁有机锡衍生物的¹¹⁹Sn,¹³C NMR谱。对其中几种衍生物的¹³C NMR谱进行了归属,从而进一步验证了这类化合物的结构。着重讨论了结构如化合物中取代基X的改变对¹¹⁹Sn化学位移的影响。并对结构如 类化合物N→Sn异侧配位的问题进行了讨论。     

二茂铁基化合物的ESR研究进展

二茂铁基化合物因具有独特的氧化还原、电、光、磁和催化性能,而被广泛研究与应用.电子自旋共振(ESR)技术是观察物质顺磁性最直接的手段,在研究二茂铁基化合物的电子结构、电子转移和分子间相互作用等方面具有独特的优势.ESR技术还具有灵敏度高、样品处理简单、直接检测不破坏样品等优点.该文综述了二茂铁基化合物的ESR研究进展.     

Elastic Properties of Lithium and Sodium Amides

Russian Physics Journal - This paper presents the optimization of the structural parameters of tetragonal and orthorhombic crystals α-LiNH2 and α-NaNH2 and computation of elastic...     

Infrared Spectra of Negative Ions of Amides

Abstract

The anionic derivatives of a series aliphatic, arylaliphatic and aromatic compounds containing amide group were investigated by means of infrared spectroscopy. The stretching vibration frequencies of the amide C=O, the ketone C=O and the N-C(Ph) in the N-anions of the studied compounds were assigncd: the amide C=O shifts 76-180 cm^?1 downward depending on the substituents; the band intensity increases 2.5-3 times. It was found an excellent correlation between the carbonyl stretching vibration frequencies of the studied N-anions with the Hamrnett CJ constants of the substituents.     

Pseudo five-component synthesis of bis-α-acyloxy-β-diketo amides from diimide-dicarboxylic acids

Diimide-dicaboxylic acids derived from condensation of α-amino acids with the 2,3,5,6-bicyclo[2.2.2] oct-2-enetetracarboxylic-2,3:5,6-dianhydride or 1,2,4,5- bezenetetracarboxylic-1,2:4,5-dianhydride react with ninhydrin and isocyanides to produce some novel interesting bis-α-acyloxy-β-diketo amides.     

Intramolecular Hydrogen Bonding in Bilirubin Amides as Detected by Circular Dichroism Spectroscopy

Analysis of the circular dichroism spectra of bilirubin-IXα amides of S'-(-)-1 -phenylpropylamine reveals a preference in organic solvents for folded, intramolecularly H-bonded conformations involving the amide N-H hydrogen.     

吡啶酰胺类化合物中酰胺键异构化的变温核磁共振研究

合成了一系列六氢吡啶酰胺化合物以研究酰胺键的双键性质. 采用¹H 及¹³C NMR 技术确证了不同取代的酰胺化合物中酰胺键的双键性质. 进一步采用变温核磁共振技术对2-(3,5- dinitrophenyl)-1-(piperidin-1-yl)ethanone(化合物1)进行了¹H 及¹³C NMR研究. 结果表明,在20 ℃（293 K）时,a, b及c, d上的氢和碳原子具有不同的化学位移,且距酰胺键越近,化学位移的差异越大. 随着温度的升高,两种异构体的转换速率增加,酰胺双键的性质越来越不明显,导致化学位移的差异逐渐减小,直至融合为一个峰. 经计算,在融合温度下两种异构体的相互转换的速率常数是380 s-¹,能垒约为67 kJ• mol^-1.       

Does the five‐member hydrogen bond ring in quinoline carboxamides exist?

The presence of intramolecular NHN hydrogen bond in 4‐R‐quinoline‐2‐(N‐R′‐carboxamides) was investigated by AIM methodology. Values of electron density, elipticity, and total energy density at the bond critical point of H···N in amides were compared with respective values of H···O in their N‐oxides. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis,spectral studies,and catalytic and antibacterial activity of Ru(II) complexes with coordinated amides

Twelve Ru(II) complexes with coordinated amides were synthesized and characterized by elemental, IR, ¹H, ¹³C, ³¹P NMR, mass, and electronic spectral analysis, along with magnetic and conductance measurements. Molecular formulas and octahedral structures have been tentatively proposed. These complexes were used as catalysts for the hydrolysis of rivastigmine and neostigmine. The hydrolyzed products were coupled with 3-methyl benzothiazolinone hydrazone reagent in the presence of sodium metaperiodate and the resulting colored products were determined spectrophotometrically. The yields of hydrolyzed products were found to be 98.47% and 99.75% respectively. All the ligands and Ru(II) complexes were screened for antibacterial activity. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 867–874, November–December, 2008.     

Formation and decomposition of N‐alkylnaphthalimides: experimental evidences and ab initio description of the reaction pathways

The kinetics of hydrolysis of 1,8‐N‐butyl‐naphthalimide (1,8‐NBN) to 1,8‐N‐butyl‐naphthalamide (1,8‐NBAmide) and of 2,3‐N‐butyl‐naphthalimide (2,3‐NBN) to 2,3‐N‐butyl‐naphthalamide (2,3‐NBAmide), as well as the formation of the respective anhydrides from the amides were investigated in a wide acidity range. 1,8‐NBN equilibrates with 1,8‐NBAmide in mild alkali. Under the same conditions 2,3‐NBN quantitatively yields 2,3‐NBAmide. Over a wide range of acidities the reactions of the 1,8‐ and 2,3‐N‐butyl‐naphthalamides (or imides) yield similar products but with widely different rates and at distinct pH's. Anhydride formation in acid was demonstrated for 1,8‐NBAmide. The reactions mechanisms were rationalized in the manifold pathways of ab initio calculations. The differences in rates and pH ranges in the reactions of the 1,8‐ and 2,3‐N‐butyl‐naphthalamides were attributed to differences in the stability of the tetrahedral intermediates in alkali as well as the relative stabilities of the five and six‐membered ring intermediates. The rate of carboxylic acid assisted 1,8‐N‐Butyl‐naphthalamide hydrolysis is one of the largest described for amide hydrolysis models. Copyright © 2010 John Wiley & Sons, Ltd.     

Photophysical and Electrochemical Studies of 4-Dicyanomethylene 2,6-Dimethyl-4H-Pyran (DDP) Dye with Amides in Water

Photophysical and electrochemical studies of DDP dye with Formamide and alkyl substituted amides were carried out in water. Addition of Formamide (F), Acetamide (ACM), N,N-Dimethylformamide (DMF), Dimethylacetamide (DMAC) to DDP dye result in an isosbestic point. A fluorescence enhancement of DDP dye is observed on the addition of amides. Apart from the fluorescence enhancement, the addition of formamide result in no significant shift in the position of emission maxima of DDP dye whereas addition of ACM and DMF result in a shift towards the blue and red region respectively. DDP dye exhibits three lifetime components which are unique in lifetime and amplitude. The fluorescence lifetime and relative amplitude of DDP dye varies significantly by addition of amides in aqueous solution which are influenced by amidewater hydrogen-bonding network and hydrophobic influences of the alkyl substituted amides. The nature of interaction between dye and amide be predominantly through hydrogen-bonding wherein the carbonyl oxygen (C=O) of amides are bonded to N-H hydrogen of DDP dye through water molecule. The existence of more than one microenvironment of DDP dye in aqueous phase is elucidated by Electrochemical Impedence Spectroscopy (EIS) through Nyquist plots wherein it signifies that there exist at least three different micro environments which support the existence of different fluorescence lifetimes. Fluorescence spectral technique is used as an efficient tool to elucidate the nature of interaction of water soluble probe with hydrogen-bonding solutes is established in our studies.     

Conformational Evaluation of Indol-3-yl-N-alkyl-glyoxalylamides and Indol-3-yl-N,N-dialkyl-glyoxalylamides

Restricted rotation in indol-3-yl-N-alkyl- and indol-3-yl-N,N-dialkyl-glyoxalylamides can in principle give the syn-periplanar and anti-periplanar rotamers. In asymmetrically disubstituted glyoxalylamides, steric effects lead to the occurrence of both rotamers, as observed by NMR spectroscopy. The predominant peak corresponds with the anti rotamer, in which the bulkier alkyl group is orientated trans to the amide carbonyl group. In monoalkylated glyoxalylamides, only one set of peaks is observed, consistent with the presence of only one rotamer. Crystal structures of 5-methoxyindole-3-yl-N-tert-butylglyoxalylamide, indole-3-yl-N-tert-butylglyoxalylamide, and indole-3-yl-N-isopropylglyoxalylamide reported here reveal a syn conformation held by an intramolecular N–H…O hydrogen bond.