四-(对-十二酰氧基)苯基卟啉过渡金属配合物的合成及其液晶行为研究

合成了5,10,15,20-四-(对-十二酰氧基)苯基卟啉(简称TLPPH₂)及其Mn(Ⅲ),Fe(Ⅲ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ)和Zn(Ⅱ)配合物,通过元素分析、紫外可见光谱、红外光声光谱、核磁共振氢谱和摩尔电导等分析方法表征了它们的组成和结构.用DSC和偏光显微镜研究了配体及其锌配合物的液晶行为.结果表明,锌配合物的液晶相变温度始于-50.67℃,相区宽度达143℃.     

四(对-癸酰氧基)苯基卟啉过渡金属配合物的合成及红外光声光谱解析

合成出相变温度较低、相区宽的卟啉液晶5,10,15,20-四(对-癸酰氧基)苯基卟啉[简称TDPPH₂]及其Mn(Ⅲ),Fe(Ⅲ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ),Zn(Ⅱ)配合物.通过元素分析、紫外可见光谱、红外光声光谱、核磁共振氢谱和摩尔电导等分析方法表征了它们的组成和结构,并用DSC和偏光显微镜研究了配体及其锌配合物的液晶行为.测试并研究了配体及其配合物在3600～190cm^-1范围内的傅里叶变换红外光声光谱,对其主要谱带进行了经验归属.     

四(对-十八酰氧基)苯基卟啉及其过渡金属配合物的合成及红外光声光谱研究

合成了5,10,15,20-四(对-十八酰氧基)苯基卟啉及其Mn(Ⅲ),Fe(Ⅲ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ)和Zn(Ⅱ)配合物,用元素分析和紫外-可见光谱等方法进行了表征.研究了这7种卟啉化合物在3600～190cm^-1范围内的傅里叶变换红外光声光谱,对主要谱带进行了经验归属.结果表明,3318.0及968.4cm^-1处的吸收谱带分别是四(对-十八酰氧基)苯基卟啉N-H键的伸缩振动和面内弯曲振动,生成配合物后这些谱带消失.243cm^-1附近的吸收谱带是M-N键伸缩振动和卟啉环变形振动的复合振动,321cm^-1附近的吸收谱带是M-Cl键的伸缩振动,金属敏感带出现在1350,1018,995,802,740,632和232cm^-1附近.     

卟啉化合物研究(Ⅸ)——聚5-邻丙烯酰胺苯基-10,15,20-三苯基卟啉及其钴配合物的合成

将丙烯酰氯和5-邻氨基苯基-10,15,20-三苯基卟啉(Ⅰ)相连合成了5-邻丙烯酰胺苯基-10,15,20-三苯基卟啉(Ⅱ)。在引发剂作用下,Ⅱ进一步聚合,生成聚5-邻丙烯酰胺苯基-10,15,20-三苯基卟啉(Ⅲ),同时还合成了单体和聚合物的钴配合物。通过元素分析、核磁共振谱、红外光谱和可见吸收光谱对单体和聚合物的结构进行了鉴定。     

四(对-辛酰氧基)苯基卟啉配合物的红外光声光谱

测试并研究了四(对-辛酰氧基)苯基卟啉及其Mn(Ⅲ)、Fe(Ⅲ)、co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Zn(Ⅱ)配合物在3600～190cm^-1范围内的傅立叶变换红外光声光谱,对主要谱带进行了经验归属.结果表明:3318.0和968.0cm^-1处的吸收谱带分别是四(对-辛酰氧基)苯基卟啉N-H键的伸缩振动和面内弯曲振动,生成配合物后这些谱带消失.～243cm^-1处的吸收谱带是M-N键伸缩振动和卟啉环变形振动的复合振动,～320cm^-1处的吸收谱带是M-Cl键的伸缩振动,金属敏感带出现在1504,1350,1022,995,796和235cm^-1处.     

四(对-硝基苯基)卟啉配合物的红外和拉曼光谱

本文研究了四(对-硝基苯基)卟啉及其Cr(Ⅲ)、Mn(Ⅲ)、Fe(Ⅲ)、Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Zn(Ⅱ)配合物的3500～220cm~(-1)的红外光谱和1700～100cm~(-1)的拉曼光谱.谱带归属表明,～250cm~(-1)谱带是M—N伸缩振动和卟啉环变形振动的复合振动.金属敏感带出现在～1600、～1582、～1547、～1284、～1190、～355和～245cm~(-1)处,其中二价金属配合物金属敏感带频率按Ni>Co>Cu>Zn顺序递减.用金属半径和d_x~2 y~2电子排斥作用解释了金属敏感带变化规律.     

FTIR—PAS技术在卟啉类化合物中的应用(Ⅰ)——过渡金属卟啉的傅立叶变换红外光声光谱

研究了四(对-硝基)苯基卟啉及其Cr(Ⅲ)、Mn(Ⅲ)、Fe(Ⅲ)、Co(Ⅱ)、Ni(I)、Cu(Ⅱ)、Zn(Ⅱ)配合物的3500-225 cm-1范围的傅立叶变换红外光声光谱.对主要谱带进行经验归属.金属敏感谱带出现在-1489、-1076、-737和-250 cm-1等附近.-250 cm-1谱带是M—N伸缩振动和卟啉环变形的复合振动.     

噻吩甲酰三氟丙酮和4，5-二氮芴-9-酮及4，5-二氮芴-9-酮连氮铕(Ⅲ)三元配合物的合成和表征

合成了Eu(TTA)₃L1(Ⅰ)和［Eu(TTA)₃］₂L2(Ⅱ)二种新的铕(Ⅲ)三元配合物(TTA=噻吩甲酰三氟丙酮一价阴离子、L1=4,5-二氮芴-9-酮、L2=4,5-二氮芴-9-酮连氮)。用元素分析、IR、UV和溶液荧光光谱对配合物进行了表征。探讨了溶剂对Eu(Ⅲ)三元配合物荧光光谱的影响，发现在CH₃CN中Eu(Ⅲ)三元配合物发光效果最好，而溶剂DMF会使配合物荧光减弱。     

5,10,15,20-四(对氯苯基)卟啉羟基稀土配合物的光谱研究

研究了四(对氯苯基)卟啉及其羟基稀土配合物的紫外-可见光谱、红外光谱和拉曼光谱,对主要谱带进行了经验归属,讨论了中心离子对紫外光谱和共振拉曼光谱结构敏感带频率的影响.     

双脂肪胺钌卟啉的合成、结构表征和晶体结构

本文讨论了一系列双脂肪胺钌卟啉配合物，包括Ru(^Ⅱ)(Por)(H₂NR)₂和Ru(^Ⅱ)(Por)(HNR₂)₂［Por=四苯基卟啉(TPP)，中位-四(对甲苯基)卟啉(TTP)，中位-四(对氯苯基)卟啉(4-Cl-TPP);R=叔丁基，异丙基，环己基，正辛基，正十二烷基，R′=甲基和乙基］的合成，结构表征和晶体结构测定。钌羰基卟啉与间-氯过苯甲酸的反应混合物用过量的脂肪胺处     

Pyrazoles as molecular probes to study the properties of co-crystals by solid state NMR spectroscopy

Equimolar mixtures of 3,5-dimethylpyrazole (1) with four NH-imidazoles (2–5) have been studied by¹³C and ¹⁵N CPMAS NMR and by DSC. In three cases, the solid mixture behaves as the sum of the individual components [imidazole (2), 2-methylimidazole (3) and 2,4(5)-dimethylimidazole (5)]. In one case [4,5-dimethylimidazole (4)], the mixture corresponds to a new species in which the dynamic behavior of1 no longer exists.     

Aqueous p-nitrotoluene oxidation induced with direct glow discharge plasma

A plasma induced degradation process has been studied to treat 4-nitrotoluene (4-NT) present as an aqueous pollutant. The plasma was locally generated from a glow discharge around a tip of a platinum anode in an electrolytic solution. The influence of initial pH and Fe²⁺ on the degradation was examined. Major intermediates resulting from the degradation process were identified. Amongst the aromatic intermediates, p-hydroxybenzoic acid was the predominant degradation product. The formation of oxalic acid, malic acid was also observed. The final products of degradation were NH ₄ ⁺ , NO ₃ ⁻ and CO₂. Based on the analysis of intermediates and the kinetic considerations, the degradation was shown to follow a pseudo-first order reaction hence, a possible reaction pathway was proposed.     

Catalytic air oxidation of manganese in synthetic waters

An attempt was made to study the oxidation of manganese by air in synthetic waters. A series of batch experments were performed at differnet values of concentration, temperature and pH. Unoxidized manganese in the solution was determined by formaldoxime spectrometric method. Results of these studies indicated that the air oxidation of manganese soluble in water can be effectively performed in basic media and that oxidation yield increasedwith an increase in pH and concentration. The yield was very high in the presence of manganese dioxide, sepiolite or clinoptilolite in solution and, the oxidation was almost completed especially at high values of pH and concentration. The reaction was found to be first order with respect to Mn²⁺ with a very low activation energy. A yield of 62% was obtained for the air oxidation of wastewater taken from the treatment plant of Corum Municipality.     

Zur Kenntnis der Reaktionsfähigkeit des Thiomorpholins und alkylsubstituierter Thiomorpholine, 4. Mitt.

Thiomorpholine as well as alkyl substituted thiomorpholines and their Sdioxides, respectively, are transformed into the corresponding N-Aminothiomorpholines by nitrosation (1–5) followed by the reduction with zinc in acetic acid/acetic acid anhydride under simultaneous formation of the corresponding N-acetyl derivates, and hydrolysis by hydrochloric acid (6–9). Examples of this method are described. 4-Aminothiomorpholines and their Sdioxides react with aldehydes or ketones to give azomethines (10–31). Acylation with mono-and dicarbonic acid chlorides leads to the N-acyl derivatives32–44.Mannich condensation is also possible. By oxidation with yellow mercury oxide tetracenes are formed (46–47).

Teil der DissertationM. Schmitz, Techn. Hochschule Aachen, 1975.     

Physico-chemical properties of Chitosan films

Chitosan films obtained by dry phase inversion were prepared from an aqueous solution of chitosan in acetic acid. The films, of thickness less than 20 μm, were transparent, very flexible and had smooth surfaces. Increasing the film thickness induced an increase of the internal tensions and the consequent formation of a rough surface. Structural investigations by X-ray diffraction and Fourier transform IR analysis, showed that the chitosan films, as prepared, are amorphous. Further annealing to evaporate acetic acid and water traces, changed the amorphous phase into a more ordered phase, characterized by diffraction peaks at 2θ values of 9, 17, 20 and 23 degrees. Thermal investigations by TG, DTG, and DTA revealed that the decomposition of the chitosan films as prepared proceeds in two stages, starting from 180°C and 540°C.     

Beiträge zur Chemie der Pyrrolpigmente, 39. Mitt.: Ein Kraftfeldmodell zur konformationsanalytischen Untersuchung von Gallenfarbstoffen

A force field model was designed with respect to the special needs of bile pigments. It is parametrized and tested using partial structures of bile pigments as well as an integral pigment; the solution structures of the molecules were previously deduced using independent experimental methods.

38. Mitt::Falk, H., Schlederer, T., Wolshann, P., Mh. Chem.112, 199 (1981).     

A kinetic method for <Emphasis Type="Italic">para</Emphasis>-nitrophenol determination based on its inhibitory effect on the catalatic reaction of catalase

The inhibitory effect of para-nitrophenol on the catalytic reaction of catalase was investigated. Michaelis-Menten kinetic parameters were determined from Lineweaver-Burk plots obtained in the absence or in the presence of the inhibitor. The inhibitor pattern, revealed by the Lineweaver-Burk plots, suggested a fully mixed inhibition mechanism. Spectrophotometric monitoring of the indicator reaction: in conjunction with initial rate measurements was employed for the kinetic determination of the inhibitor. Calibration plots of initial rate vs. para-nitrophenol concentration were linear in the concentration range 0.9·10⁻⁵–2.5·10⁻⁵ mol/L and the detection limit was 3·10⁻⁶ mol/L (417 μg/L) para-nitrophenol. Interferences from other phenolic compounds like orto-cresole, meta-and orto-nitrophenol were observed.     

Polarographische Untersuchung der Kinetik der Polymerisation von Methylvinylketon

The homogeneous polymerization of methyl-vinyl ketone in diluted methanol solutions in presence of proton donors is studied using the polarographic method. The effect of the cation of the indifferent electrolyte is investigated as well as the influence of small quantities of H₂O. Suggestions were made about the possible mechanisms of these influences in the general scheme of the process proposed byHolleck et al.

     

Aminoalkoholester von Hydroxyboranen,IX Salicylamid-Bor-Mannichbasen als potentielle Antitumorwirkstoffe

A synthesis of new boron containingMannich bases of salicylamide by reaction of salicylamide, formaldehyde and boron-heterocycles is reported.

VIII. Mitteilung:Stump, R. K., Zimmerman jr., H. K., Schleppnik, A. A., Gutsche, C. D., Liebigs Ann. Chem.667, 18 (1963).     

A unique geometry of the active site of angiotensin-converting enzyme consistent with structure-activity studies

Summary Previous structure-activity studies of captopril and related active angiotensin-converting enzyme (ACE) inhibitors have led to the conclusion that the basic structural requirements for inhibition of ACE involve (a) a terminal carboxyl group; (b) an amido carbonyl group; and (c) different types of effective zinc (Zn) ligand functional groups. Such structural requirements common to a set of compounds acting at the same receptor have been used to define a pharmacophoric pattern of atoms or groups of atoms mutually oriented in space that is necessary for ACE inhibition from a stereochemical point of view. A unique pharmacophore model (within the resolution of approximately 0.15 Å) was observed using a method for systematic search of the conformational hyperspace available to the 28 structurally different molecules under study. The method does not assume a common molecular framework, and, therefore, allows comparison of different compounds that is independent of their absolute orientation.Consequently, by placing the carboxyl binding group, the binding site for amido carbonyl, and the Zn atom site in positions determined by ideal binding geometry with the inhibitors' functional groups, it was possible to clearly specify a geometry for the active site of ACE.