Studies on Spiroheterocycles,Part III: Synthesis of Diazaspiroundecanetetraone Derivatives Containing Biologically Active Heterocycles

Barbituric acid 2 upon Michael addition with dibenzal acetones 1a–c afforded the corresponding diazaspiro derivatives 3a–c . The base-catalyzed condensation of 3a–c with various aromatic aldehydes produces diarylidine derivatives 4a–l . The diarylidene compounds 4a–l on condensation with hydrazine, phenyl hydrazine, hydroxylamine, urea, guanidine carbonate, and hydrazine hydrate with acetic acid afforded their respective in situ oxidized products 5, 6, 7, 8, 9 , and 10 . The structures of the compounds are ascertained from their analytical and spectral data. Some of the compounds are screened for their biological activities against E. coli, B. cirroflagellosus, A. niger, and C. albicans.     

芳香醛与硫代巴比妥酸的缩合反应研究

通过微波辐射、用水作溶剂及在醋酸铵催化下的固相研磨等，研究了芳香醛与 硫代巴比妥酸的缩合反应。在三种反应条件下都得到了5-芳亚苄基硫代巴比妥酸， 并通过IR，~1H NMR和元素分析确定了产物的结构。     

硫代巴比妥酸光度法测定香草醛

香草醛在强酸性介质中与硫代巴比妥酸（ＴＢＡ） 反应生成黄绿色的化合物,建立了可见光分光光度法测定香草醛方法。线性范围１×１０－ ６～１５×１０－ ４ｍ ｏｌ／Ｌ,检出限为４４７×１０－ ８ｍ ｏｌ／Ｌ。对冰淇淋、麦片等进行了其中香草醛含量测定,结果满意     

The Effects of High-Pressure Processing on pH,Thiobarbituric Acid Value,Color and Texture Properties of Frozen and Unfrozen Beef Mince

In this study, beef mince (approximately 4% fat longissmus costarum muscle of approximately 2-year-old Holstein cattle) was used as a material. High-pressure processing (HPP) was applied to frozen and unfrozen, vacuum-packed minced meat samples. The pH and thiobarbituric acid (TBA) values of the samples were examined during 45 days of storage. Color values (L*, a* and b*) and texture properties were examined during 30 days of storage. After freezing and HPP (350 MPa, 10 min, 10 °C), the pH value of minced meat increased (p > 0.05) and its TBA value decreased (p < 0.05). The increase in pH may be due to increased ionization during HPP. Some meat peptides, which are considered antioxidant compounds, increased the oxidative stability of meat, so a decrease in TBA may have been observed after freezing and HPP. While the color change in unpressurized samples was a maximum of 3.28 units during storage, in the pressurized sample, it exceeded the limit of 10 units on the first day of storage and exceeded the limit of 10 units on the third day of storage in the frozen and pressurized sample. Freezing and HPP caused the color of beef mince to be retained longer. The hardness, gumminess, chewability, adherence, elasticity, flexibility values of the pressurized and pressurized after freezing samples were higher than those of the unpressurized samples during storage. On the other hand, the opposite was the case for the adhesiveness values. In industrial applications, meat must be pressurized after being vacuum packed. If HPP is applied to frozen beef mince, some of its properties such as TBA, color, and texture can be preserved for a longer period of time without extreme change.     

新4(或5)-取代不对称变色酸双偶氮胂酸型显色剂与稀土的显色反应研究

本文对二十一种新型的4(或5)-取代不对称变色酸双偶氮肿酸型显色剂与稀土的显色反应进行了研究,从中找出了一些结构与性能关系的规律,并筛选出性能优良的稀土显色剂。     

硼酸与多羟基化合物配位反应的热化学研究

用量热法在298.2 K测定了B(OH)~-_4与多羟基化合物的反应焓。计算了硼酸与多羟基化合物的配位焓和配离子的标准生成焓。根据配位焓确定了B(OH)~-_4与甘露醇、山梨醇、丙三醇、葡萄糖等多羟基化合物配位反应的配位数，B(OH)~-_4与甘露醇、山梨醇的配位数是2；与丙三醇、葡萄糖的配位数是1．     

Action of Nucleophilic Reagents. 5. Interaction of 2-Iminocoumarin-3-carboxamide with Anthranilic Acid and its Derivatives

N-Substituted 2-iminocoumarins are formed on reacting 2-iminocoumarin-3-carboxamide with anthranilic acid, methyl anthranilate, anthranilamide, and anthranilonotrile. Depending on the reaction conditions these recyclize into the corresponding 3-substituted coumarins or are hydrolyzed to coumarin-3-carboxamide. An alternative synthesis of some of the compounds has been effected.     

稀土－谷氨酸配合物的pH电位法研究

报道了在生理条件（３７℃，Ｉ＝０．１５ｍｏｌ·Ｌ－１ＮａＣｌ）下用ｐＨ电位法对１５种稀土元素与Ｌ－谷氨酸配合物稳定常数的测定结果。玻璃电极校正用ＭＡＧＥＣ程序进行，各体系中配合物物种的选择及其稳定常数的计算用程序ＭＩＮＩＱＵＡＤ－８２Ａ完成，讨论了“四分组效应”及钇的位置。     

静电离子色谱用于硼酸溶液中硼不同形态组分分离的研究

改进了把胆汁酸诱导体胶束(CHAPSO)涂覆在ODS载体上制备静电离子色谱固定相的方法.以纯水为流动相,采用示差折光检测器,研究了硼酸溶液中硼的形态、分离条件,并对色谱峰进行了解析.此外,还对硼酸溶液中硼离子、硼分子的色谱保留行为进行了探讨.     

具有生理活性的含氧、氮、硫杂原子螺环化合物的研究进展

综述了近年来部分具有生理活性螺环化合物的研究进展, 重点介绍了这类化合物的结构特征、生理活性和部分化合物的合成方法. 展望了该类螺环化合物的应用前景.     

吡咯喹啉醌模型化合物与氨亲核加成的理论探讨

为了揭示辅酶PQQ结构与反应性的关系,在B3LYP/D95(d, p)水平上对一系列PQQ模型化合物及其类似物与氨的亲核加成进行了理论计算.结果表明:对单羰基体系,羰基碳的亲电性对反应能垒有重要的影响;对双羰基体系,过渡态中邻位羰基氧与亲核试剂氨上的H形成的氢键对反应的活化能起着关键的作用;稠合芳香环本身对反应的能垒影响不大,但当稠合杂环的1-位为可提供氢键受体的N原子时,由于N1与氨上H原子间可形成氢键而进一步降低反应的活化能.发现过渡态中被进攻羰基与氨上N原子之间形成的夹角(OCN)与活化能有良好的线性关系.     

Chemistry of N-Heterocyclic Sulphur Compounds: Part II: Regioselective Synthesis of N,N'-Diaminotriazolophanes Containing Oxygen and Sulphur Heteroatoms

4-Amino-3,5-dimercapto-1,2,4-triazole has been selectively S-alkylated by bis (2-iodoethyl) ether followed by intramolecular cyclization through regioselective S-alkylation with 1,ω-dihaloalkanes to afford 16-20 membered N,N'-diamino-triazolophanes.     

两个含双配体的银(Ⅰ)配合物的晶体结构和光学性能

室温下,AgNO3、4,4′-联吡啶(bpy)/1,2-二(4-吡啶基)乙烯(dpe)与联苯二甲酸(H2da)在乙酸/乙醇水溶液中反应数周后分别得到块状晶体[Ag2(bpy)2(Hda)2](HAc)2.2H2O(1)和[Ag2(dpe)2(da)]·4H2O(2)。上述两种晶体均包含无限扩展的一维阳离子链[AgL]∞(L=bpy和dpe),而穿插其中的有机阴离子da2-起到了平衡电荷的作用。结晶水分布于离子链之间并形成氢键,对晶体堆积起到了定位作用。UV/Vis/NIR漫反射光谱测定结果表明化合物1和2的光学能隙Eg均约为3.3 eV。     

Synthesis, Mass Spectrometric Studies, and Biological Evaluation of 3,5-Dimethoxyhomophthalic Acid and Related Compounds

3,5-Dimethoxyhomophthalic acid was synthesized in four steps from 3,5-dimethoxycinnamic acid via a series of reactions including cyclization of 3-(3',5'-dimethoxyphenyl)propionic acid to 5,7-dimethoxy-1-indanone and oxidative decomposition of methyl-2-hydroxy-2-[5,7-dimethyoxy-1-oxo-1H-inden-2(3H)-ylidene]acetate to 3,5-dimethoxyhomophthalic acid.The synthesized compounds were characterized by elemental analysis,IR,1H NMR,and MS.The biological evaluation experiments of 3,5-dimthoxyhomophthalic acid and the related synthesized compounds were also carried out.Naturally occurring biologically active isocoumarins were prepared in a single step by the condensation of the homophthalic acid with appropriate acid chlorides.     

Heterocyclization Reactions of 2-(2-Propynylthio)-4(1H)-quinazolinone Derivatives when Treated with Electrophilic and Nucleophilic Reagents

Reaction of the potassium salt of 2-thioquinazolin-4-one with propargyl halides leads to formation of 2-propargylthioquinazolin-4-one derivatives, which undergo heterocyclization when they are treated with electrophilic or nucleophilic reagents and, depending on the nature of the cyclization agent, leads to formation of tricyclic systems with angular or linear structure.     

抗癌金属络合物与脱氧核糖核酸作用的谱学研究比较

利用紫外可见光谱、荧光光谱、表面增强拉曼光谱研究了抗癌金属络合物与ＤＮＡ的相互作用,首次提出将荧光光谱与表面增强拉曼光谱结合作了化合物是否具有抗癌活性筛选法的可能性。     

Luminescent Platinum(II) Complexes with Bidentate Diacetylide Ligands: Structures,Photophysical Properties and Application Studies

A series of platinum(II) complexes supported by terphenyl diacetylide as well as diimine or bis-N-heterocyclic carbene (NHC) ligands have been prepared. The diacetylide ligands adopt a cis coordination mode featuring non-planar terphenyl moieties as revealed by X-ray crystallographic analyses. The electrochemical, photophysical and photochemical properties of these platinum(II) complexes have been investigated. These platinum(II) diimine complexes show broad emission with peak maxima from 566 nm to 706 nm, with two of them having emission quantum yields >60% and lifetimes <2 μs in solutions at room temperature, whereas the platinum(II) diacetylide complexes having bis-N-heterocyclic carbene instead of diimine ligand display photoluminescence with quantum yields of up to 28% in solutions and excited state lifetimes of up to 62 μs at room temperature. Application studies revealed that one of the complexes can catalyze photoinduced aerobic dehydrogenation of alcohols and alkenes, and a relatively non-toxic water-soluble Pt(II) complex displays anti-angiogenic activity.     

Studies on the Interaction of Poly(I:C) with Heterocyclic Compounds Containing Iodine

The iodine heterocvclic compound with trivalent-iodine as the cation has a specially remarkable antitumor activityii^[1]. Although 3, 6-bis (dimethylamino)-dibenzopyriodonium formate([I⁺]) inhibits DNA biosynthesis of cancer cells in vitro, the way of [I⁺] depressing DNA synthesis has not been studied. It is significant to investigate the mechanism of the interaction of [I⁺] with nucleic acids.     

含硫代酰胺新三唑类化合物的合成、结构表征及生物活性研究

以三唑、芳香基苯乙酮和异硫氰酸苯酯为原料合成了4个含硫代酰胺的芳香三唑类化合物, 对四个化合物进行了IR, EA, ¹H NMR和MS谱学表征. 培养了1-[1-苯胺硫化碳-1-(4-氟苯甲酰基)甲基]-1,2,4-三唑的单晶. 同时对这四个化合物进行了初步的生物活性测试, 结果表明它们具有一定的杀菌活性.     

不同形态抗坏血酸的分离及其变异速度的研究

提出了应用静电离子色谱法（EIC）同时分离测定抗坏血酸、脱氢抗坏血酸和变异脱氢抗坏血酸的方法。在自制的（EIC）固定相表面上，由于存在着微螺旋状胶束和均匀分布的正、负电荷，使几种形态的抗坏血酸得到了很好的分离。使用示差－折光检测器，测定抗坏血酸的线性范围为0．2－2mg.mL^-1。维生素C片溶液（1mg.mL^-1）在常温下被空气氧化而失活的速度为0．045mg.mL^-1.d^-1。该方法克服了样品测试过中，由于抗坏血酸的变异而引起的系统误差，可为生活活性物质的动态分析，有机酸化学反应机理和速度的研究提供新的手段。