Synthesis, Crystal Structure and DNA-Binding Property of a Mn(Ⅱ) Complex Based on 5-(Tri-fluoromethyl)pyridine-2-carboxylic Acid

A new complex Mn(Htpc)2(H2O)2(1, Htpc = 5-(trifluoromethyl)pyridine-2-carboxylic acid) has been synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. 1 belongs to triclinic system, space group P■ with a = 5.0885(10), b = 6.5574(13), c = 14.016(3) ?, β = 90.67(3)o, V = 436.34(17) ?3, Z = 1, Dc = 1.793 g·cm-3, μ = 0.855 mm-1, Mr = 471.18, F(000) = 235, the final R = 0.0454 and wR = 0.1134 for 1998 observed reflections with I > 2σ(I). The Mn(Ⅱ) ion is coordinated by two N and two O atoms from two Htpc as well as two O atoms from two coordinated water molecules, forming a 0D motif with distorted octahedral coordinate geometry. The adjacent 0D units are linked into 1D chains through hydrogen bond O(1W)–H(1 WB)···O(2), and via the O(1 W)–H(1 WA)···O(1) hydrogen bond the neighboring 1D chains are connected into a 2D supramolecular layer. Moreover, the interactions between the ligand and its complex with CT-DNA were studied by EtBr fluorescence probe, which suggested that these compounds bind to CT-DNA through an intercalation mode. The binding constants were 0.41 and 0.64 for Htpc and complex 1, respectively. It indicates that the interaction between complex 1 and CT-DNA is stronger than Htpc.

Synthesis and Crystal Structure of 1-H-Pyrrole-2-carboxylic Acid [2-(Naphthalen-1-ylamino)-ethyl]-amide

1-H-Pyrrole-2-carboxylic acid [2-（naphthalen-1-ylamino）-ethyl]-amide has been synthesized and characterized. Its crystal is of monoclinic, space group P2 1/n with a = 5.930（6）, b = 12.144（13）, c = 20.10（2） , A, β = 95.709（17）°, V= 1441（3） ,A, Z= 4, C17H17N3O, Mr= 279.34, Dc= 1.288 g/cm^3, F（000） = 592, μ（MoKa） = 0.083 mm^-1, S = 1.019, R = 0.0473 and wR = 0.1181 for 1713 observed reflections with I 〉 2 σ（I）. X-ray diffraction reveals that two molecules of the title compound form a dimer through a pair of N-H…O hydrogen bonds.

Synthesis of (2S,4S)-2-Substituted-3- (3-Sulfanylpropanoyl)-6- Oxohexahydropyrimidine-4-Carboxylic Acids as Potential Antihypertensive Drugs

Proceeding from natural amino acid L-asparagine and commercially available aldehydes a stereoselective synthesis was developed of (2S,4S)-2-alkyl(aryl)-3-(3-sulfanylpropanoyl)-6-oxohexahy- dropyrimidine-4-carboxylic acids, potential antihypertensive drugs, inhibitors of the angiotensin converting enzyme.

Synthesis,Structure,and Magnetic Property of One Snake-shaped Copper(Ⅱ)-organic Compound:Cu[Cu_2(PP)_2](CBPC)_2]·2(H_2O)

One novel copper（II）-organic compound,namely Cu[Cu2（PP）2]（CBPC）2]·2（H2O）（1,H2CBPC = 1-[（2＇-carboxybiphenyl-4-yl）methyl]-2-propylimidazole-4-carboxylic acid,HPP = 3-（2-pyridyl）pyrazole）,was designed and synthesized under hydrothermal conditions.X-ray diffraction analysis reveals that two Cu（II）ions in the quasi-planar dimmer of [Cu2（PP）2] are linked by the carboxylate oxygen atoms on the phenyl ring and the imidazole ring,respectively,yielding one snake-shaped structure.Magnetic measurements reveal that compound 1 shows the strongly antiferromagnetic property.Crystal data of 1：C58H52Cu3N10O10,Mr = 1239.72,monoclinic,P21/c,a = 14.900（7）,b = 15.029（7）,c = 12.308（6）,β = 102.519（9）o,V = 2691（2）3,Z = 2,Dc = 1.530 g/cm3,F（000）= 1274,μ = 1.246 mm-1,R = 0.0416,wR = 0.0780（I 2σ（I））and S = 0.999.

Design, Synthesis, Antifungal Activities and SARs of （R）-2-Aryl-4,5-dihydrothiazole-4-carboxylic Acid Derivatives

Based on the structure of natural product 2-aryl-4,5-dihydrothiazole-4-carboxylic acid, a series of novel （R）-2-aryl-4,5-dihydrothiazole-4-carboxylic acid derivatives were designed and synthesized. Their structures were characterized by ^1H NMR, ^13C NMR and HRMS. The single crystal structure of compound 9b was determined by X-ray diffraction analysis. The antifungal activities were evaluated for the first time. The bioassay results indicated that most compounds exhibited moderate to good antifungal activities. The antifungal activities of compound 13a （against Cercospora arachidicola Hori）, 13d （against Alternaria solani）, and 16e （against Cercospora arachidieola Hori） were 61.9%, 67.3% and 61.9%, respectively, which are higher than those of the commercial fungicides chlorothalonil and carbendazim. Moreover, compound 13d exhibited excellent antifungal activities against 7 kinds of the fungi tested （66.7%, 77.3%, 63.0%, 87.9%, 70.0%, 70.0% and 80.0% at 50 μg/mL）. Therefore, 13d can be used as a new lead structure for the development of antifungal agents.

Hydrothermal Synthesis and Crystal Structure of One Novel 1-D Copper(Ⅱ)-organic Framework:{[Cu_2(PP)_2(CBPC)]_2·7H_2O}_n

One novel 1-D copper（Ⅱ）-organic compound,namely {[Cu2（PP）2（CBPC）]2·7H2O}n（1,H2CBPC=1-[（2＇-carboxybiphenyl-4-yl）methyl]-2-propylimidazole-4-carboxylic acid,HPP=3-（2-pyridyl）pyrazole）,was synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that the two Cu（Ⅱ） ions in the distorted dimer [Cu2（PP）2] of 1 are linked by the carboxylate oxygen atoms on the phenyl and imidazole rings,respectively,forming one interesting snake-like chain.Single-crystal X-ray analyses reveal that it crystallizes in monoclinic,space group C2/c with a=30.656（8）,b=12.715（3）,c=22.405（5）,β=122.758（3）°,V=7344（3）3,Z=4,Mr=1681.65,Dc=1.521 g/cm3,F（000）=3464,μ=1.221 mm-1,the final R=0.0453 and wR=0.1023 for 4617 observed reflections with Ⅰ 〉2σ（Ⅰ）.

Free fatty acids, glucose, and insulin in type 2 diabetes mellitus

Xu et al used the HOMA2 model to estimate theβ-cell function and insulin resistance levels in an individual from simultaneously measured fasting plasma glucose and fasting plasma insulin levels.This method is based on the assumption that the glucose-insulin axis is central for the metabolic activities,which led to type 2 diabetes.However,significant downregulation of both the NKX2-1 gene and the TPD52L3 gene force an increase in the release of free fatty acids(FFAs)into the blood circulation,which leads to a marked reduction in membrane flexibility.These data favor a FFA-glucose-insulin axis.The authors are invited to extend their study with the introduction of the saturation index(number of carbon-carbon double bonds per 100 fatty-acyl chains),as observed in erythrocytes.

Resolution of racemic R.S-α-arylethylamine by a new resolving agent (R)thiazolidine-2-thione-4-carboxylic acid

Racemic R.S-α-arylethylamine was resolved by R (-) thiazolidine-2-thione-4-carboxylic acid, a new resolving agent abbreviated as [R (-) TTCA], by which R (-) TTCA.S(-) arylethylamine salts2a-2e, [α] D 20 =-47.24° — 64.40° and optically active R(+)-a-arylethylamines3a – 3e, 74. 54%-94. 45% e, e., were obtained. Optically active S (-) -α-arylethylamines4a-4e, 72.84%-90.36% e.e., were obtained by the decomposition of2a-2e in basic solutions. The influence of substitutive group of the benzene ring on the basicity of the amino group was studied by semiempirical PM3 method. The structures of the R (-) TTCA.S (-) -α-phenylethylamine salt (2a(R-S) configuration) and R (-) TTCA-R(+)-a-phenylethylamine salt (2a(R-R) configuration) have been established by means of X-ray diffraction. They crystallize in a monoclinic system. Space group isP21. The cell constants of2a(R-S) configuration were obtained as follows: α = 1.387 8(2), b = 0.664 05(101,c = 1.580 O(2) nm; β = 90.844(10)° Z = 4; those obtained for2a(R-R) configuration were α = 1.080 6(2),b = 0.584 80(12),c = 1.2188(2) nm, β= 110.38(3)dg, V = 0.7220nm3,Z = 2. There are intermolecular hydrogen bonds in the crystals of the two kinds of configurations of the amine salt. The hydrogen bond number in the unit cell of R (-) TTCA.S (-)-α-phenylethylamine salt is twice as much as that of R (-) TTCA.R(+)-a-phenylethylamine salt.

A Facile Synthesis of 9,10-Dimethoxybenzo[6,7]- ox-epino[3,4-<i>b</i>]quinolin-13(6<i>H</i>)-one and Its Derivatives

A concise and efficient method for the synthesis of novel 9,10-imethoxybenzo[6,7]oxepino[3,4-b]quinolin13(6H)-one and its derivatives 7a-p has been developed via the intramolecular Friedel-Crafts acylation reactions of 6,7-dimethoxy-2-(phenoxymethyl)quinoline-3-carboxylic acids 6a-p with polyphosphoric acid (PPA) as catalyst and solvent under mild conditions. The key intermediates 6a-p were prepared through the in situ formation of ethyl 6,7-dimethoxy-2-(phenoxymethyl)quinoline-3-carboxylates 5a-p followed by hydrolysis with aqueous ethanolic sodium hydroxide solution. The novel synthetic method has the advantages of good yields, easy work-up, and environmentally friendly character, which may provide a novel highly efficient process for making quinoline and related azaheterocycle libraries.

The Influence of Aziridine on the Aging of Composite Solid Rocket Propellant

Aging of a solid composite propellant containing HTPB/AP/AL was performed in order to validate the conformance of the accelerated aging data to the Arrhenius law. The main objective of the work was to examine the influence of the aziridine bonding agents family on the propellant aging. Aging of the prepared propellant samples was conducted as follows: 1. Four samples, one free of bonding agents, and three containing aziridine based bonding agents MAPO,HX-752, MAT4 were aged at 65°C. 2. Another four samples based on HX-752, MAT4 with different curing agents were aged at 65°C. The measured mechanical properties of the free bonding agent propellant samples were very far from the specifications and this illustrates the importance of the bonding agents in both the preparation and the aging phases.The prepared bonding agent 'MAT4' gave remarkable improvements of the mechanical properties comparing with HX-752 and MAPO. The aziridine bonding agents family inhibited the rate of decomposition of the propellant during the aging periods and supported the propellant matrix against decomposition at the elevate temperatures. Using of HMDI as curing agent gave slight better mechanical properties to the IPDI.

百尾参化学成分的分离与鉴定

目的研究百尾参Disporum cantoniense的化学成分。方法利用各种色谱技术进行分离,运用现代光谱技术鉴定化合物结构。结果从百尾参中分离得到16个化合物,分别鉴定为马来酸酰亚胺-5-肟(1)、4-methylene-5-oxopyrrolidine-2-carboxylic acid(2)、胸腺嘧啶(3)、腺嘌呤核苷(4)、5′-deoxy-5′-methylamino-adenosine(5)、乙基-α-L-鼠李糖(6)、岩白菜素(7)、4-羟基-2-甲氧基苯基-6-脱氧-α-L-吡喃木糖苷(8)、(-)-表儿茶素(9)、(6R,9R)-roseoside(10)、3-(4-羟基-3,5-二甲氧基苯基)-丙烷-1,2-二醇(11)、3-羟基-5-(p-羟基苯基)-戊酸(12)、1-核糖醇基-2,3-二酮-1,2,3,4-四氢-6,7-二甲基-喹喔啉(13)、(6S,9R)-vomifoliol(14)、3,4-二羟基苯酰甲醇(15)和1,2-二羟基-1-(4-羟基-3,5-二甲基苯基)-乙烷(16)。结论化合物1、2、5~9、12~16为首次从该属植物中分离得到;化合物1、2、5~10、12~16为首次从该植物中分离得到。

Constituents from the Roots of Semiaquilegia adoxoides

In present literature search, some cyano-containing compounds, which are very rare in plants, from the traditional anticancer herb Tiankuizi were reported. To find more cyano-containing compounds in the important plant Semiaquilegia adoxoides （DC） Makino （Chinese name Tiankuizi）, the isolation of the chemical constituents was investigated for advancing the research. Two new compounds, a new alkaloid, 1,2,3,4-tetrahydro-6-hydroxy-1[（3,4-dihydroxyphenyl）methyl]-7-methoxy-2,2-dimethyl-isoquinolinium, named Semiaquilegine A （1）, and a new ester, 3-（4＇-hydroxyphenyl）-2-propenoic acid （4＂-carboxyl）-phenyl ester （2）, and four cyano-containing compounds, （Z）-6a-（β-D-glucosyloxy）-4a,5a-dihydroxy-2-cyclohexene-△^1,a-acetonitrile （3）, （L0-6α-（β-D-glucosyloxy）-4α-hydroxy-2-cyclohexene-△^1,α-acetonitrile （4）, lithospermoside （5）, ehretioside B （6）, as well as eleven known compounds, were isolated from the roots of Semiaquilegia adoxoides. The structures of new compounds 1 and 2 were elucidated mainly by 1D/2D-NMR techniques. Very unusual cyano-containing compounds 3 and 4 were first isolated from Ranunculaceae family. Hitherto, there were six cyano-containing compounds found in the herb.