Synthesis and Crystal Structure of 2-Ethoxy-spiro[2H-1, 4,2-benzoxazaphosphorine-3(4H), 1'-Cycloheptane] 2-Oxide

The title compound 2-ethoxy-spiro[2H-1,4,2-benzoxazaphosphorine-3（4H）,1＇-cycloheptane] 2-oxide （C15H22NO3P） was synthesized by the Mannich-type reaction of ο-amino-phenol with ethyl dichlorophosphinite and cycloheptanone, and structurally characterized by single-crystal X-ray diffraction analysis. It crystallizes in orthorhombic, space group P212121 with a = 8.9840（12）, b = 9.2978（12）, c = 37.205（5） A, V= 3107.8（7） ,A^3, Z= 8, Mr = 295.31, Dc = 1.262 g/cm^3, F（000） = 1264, μ = 0.184 mm^-1, S = 1.026, the final R = 0.0502 and wR = 0.1017 for 3849 observed reflections with Ⅰ 〉 2σ（Ⅰ） and 378 variable parameters. The structure exhibits that the six-membered phosphorus heterocycle is in the envelope conformation.

SYNTHESIS OF 3,4-DIPHENYL-1.3,4-DIAZAPHOSPHOLID1N-2-ONE-4-OXIDE BY MANNICH-TYPE REACTION

Phenylurea reacted with dichlorophenylphosphine and aldehydes or ketones by Mannich-type reaction in anhydrous benzene to give five-mem- bered phosphorous heterocyclic compounds.However.derivatives of α-ureidoalkylphosphonic acids were obtained as the reaction performed in glacial acetic acid.

Synthesis, Crystal Structure and Flame Retardance of 2-(3-Silatranylpropylamino)-4-phenyl-5,5-dimethyl-1,3,2-dioxaphosphorinane-2-oxide

The title compound, 2-（3-silatranylpropylamino）-4-dichlorophenyl-5,5-dimethyl- 1,3,2-dioxaphosphorinane-2-oxide （2（C20H33N2O6Psi）？C2H6O？CH4O, Mr = 991.20）, has been synthe- sized by the nucleophilic substitution reaction of 2-chloro-4-phenyl-5,5-dimethyl-1,3,2-dioxa- phosphorinane-2-oxide with γ-aminopropylsilatrane, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P with a = 10.3783（15）, b = 11.2402（17）, c = 12.1675（18） ？, ？ = 70.653（4）, ？ = 82.908（4）, ？ = 85.690（4）？, V = 1328.1（3） ？3, Z = 1, Dc = 1.239 g/cm3, μ = 0.19 mm？1, F（000） = 532, the final R = 0.0640 and wR = 0.2090 for 3615 observed reflections with I 〉 2？（I）. The cyclic dioxaphosphorinane ring in the molecule adopts a thermodynamically stable cis conformation, while the silatrane fragment forms a cage-like structure in which there exists an intramolecular Si？N donor-acceptor bond. In the crystal structure, centrosymmetrically related molecules are linked by pairs of N–H？？？O hydrogen bonds into dimers, generating rings with graph-set motif R22（8）. Furthermore, a couple of O（7）–H（10）？？？O（3） hydrogen bonds were formed by O atom of P=O and H atom from hydroxyl in the solvent ethanol. Thermal property of the compound was also studied by means of thermogravimetry （TGA）. The thermal analysis and preliminary fireproofing test show that the title compound has good flame retardance.

THE SYNTHESIS AND CHARACTERIZATION OF THE COORDINATION COMPOUNDS OF Pt(Ⅱ)AND Ir(Ⅲ)WITH 2-MERCAPTOPYRIDINE-1-OXIDE AND ITS METHYL DERIVATIVES

Six coordination compounds of Pt(Ⅱ)L_2 and Ir(Ⅲ)L_3 type(where L is PT^-, 3Me-PT^-or 4Me-PT^-)are reported here.Four coordination compounds of the latter two ligands have never been reported before,while PT^-'s were synthesized with H_2PtCl_6 and(NH_4)_3IrCl_6 respectively,which were different from the methods of Davidson et al.~1 and Sterinbrech^2.They were characterized by elemental analysis, UV,IR,~1HNMR and molar conductance.Their structural formulas have been determined,and the mechanism of synthetic reaction has been discussed.

THE SYNTHESIS AND CHARACTERISTICS OF THE COORDINATION COMPOUNDS OF 2-MERCAPTOPYRIDINE-1-OXIDE WITH THE FIPST TRANSITION SERIES METALS

The stability of the coordination compounds of the first transition series metal ions(Mn(Ⅱ),Co(Ⅱ),Ni(Ⅱ),Cu(Ⅱ)and Zn(Ⅱ))with 2-mercaptopyridine-1- oxide is reported.A coordination compound CoL_2 is synthesized and characterized for the first time.

尿酸对大鼠血管平滑肌细胞赖氨酰氧化酶和基质金属蛋白酶-2表达的影响

目的:研究尿酸对大鼠血管平滑肌细胞赖安酰氧化酶(LOX)和基质金属蛋白酶-2(MMP-2)表达的影响。方法:人工传代培养大鼠血管平滑肌细胞,分为对照组、尿酸组(20、40、60 mg/L尿酸干预48 h;40 mg/L尿酸干预24、48、72 h)、β氨基丙腈组(40 mg/L尿酸干预48 h后加入LOX的特异性抑制剂β氨基丙腈10 mg/ml孵育24 h)。用激光共聚焦显微镜观察细胞内活性氧情况。提取大鼠血管平滑肌细胞RNA和蛋白,用逆转录聚合酶链式反应和免疫印迹法测定LOX及MMP-2信使核糖核酸(mRNA)和蛋白的表达水平。结果:尿酸组大鼠血管平滑肌细胞增殖量、细胞内活性氧、LOX及MMP-2的m RNA和蛋白水平均明显高于对照组;与尿酸组相比,β氨基丙腈组大鼠血管平滑肌细胞LOX及MMP-2 mRNA和蛋白表达均明显下调,差异均有统计学意义(P均<0.01)。结论:尿酸可上调大鼠血管平滑肌细胞LOX及MMP-2表达。

阿托伐他汀经LOX-p38-MMP-2信号轴逆转糖尿病心肌病大鼠心肌组织纤维化的研究

目的观察阿托伐他汀逆转糖尿病心肌病大鼠心肌组织纤维化与LOX-p38-MMP-2信号轴的关系。方法选取8周、52~58g、SPF级健康雄性SD大鼠40只,随机分为DCM组15只、治疗组15只、对照组10只。DCM组及治疗组单次腹腔注射链脲佐菌素(STZ)65mg/kg制作糖尿病动物模型。治疗组采用阿托伐他汀2mg·kg-1·d-1灌胃,DCM组采用等量0.9%氯化钠注射液灌胃。第8周末处死大鼠,采用HE及Masson染色方法观察心肌组织形态及纤维化程度。从心肌组织中提取RNA和蛋白质,通过实时荧光定量PCR检测赖氨酰氧化酶(LOX)和基质金属蛋白酶-2(MMP-2)mRNA。Western blot方法检测LOX,MMP-2,p38和磷酸化p38的表达。结果 DCM组大鼠心功能明显受损、心肌组织纤维化。与对照组比较,DCM组大鼠心肌组织中LOX、MMP-2、磷酸化p38蛋白水平[(0.79±0.06)、(0.71±0.03)、(0.71±0.03)]显著升高,差异均有统计学意义(均P<0.01)。与DCM组比较,治疗组大鼠心肌组织纤维化明显减轻,心肌组织中LOX、MMP-2、磷酸化p38明显下调[(0.56±0.04)、(0.49±0.04)、(0.49±0.04)],差异均有统计学意义(均P<0.01)。各组p38蛋白表达差异无统计学意义(均P>0.05)。结论阿托伐他汀逆转糖尿病心肌病大鼠心肌组织纤维化与LOX-p38-MMP-2信号轴有关。

阿托伐他汀对急性心肌梗死小鼠心肌组织赖安酰氧化酶表达的影响

目的研究阿托伐他汀对急性心肌梗死小鼠心肌组织赖安酰氧化酶表达的影响及机制。方法随机抽取8周龄健康清洁雄性C57BL/6小鼠30只,结扎冠状动脉前降支制作急性心肌梗死模型,随机分成两组,每组15只:(1)急性心肌梗死组(MI组:等量生理盐水灌胃);(2)治疗组(阿托伐他汀2 mg.kg^(-1).d^(-1)灌胃);另取15只健康清洁雄性C57BL/6小鼠设为对照组。第4周末处死小鼠,TUNEL染色检测细胞凋亡。提取左心室心肌组织RNA及蛋白质,实时荧光定量PCR法及Western Blot测定心肌组织LOX和MMP-2 mRNA和蛋白表达。结果TUNEL染色显示MI组小鼠心肌梗死周边细胞凋亡数增加,而治疗组小鼠心肌梗死周边细胞凋亡数减少。与对照组比较,MI组小鼠心肌组织LOX、MMP-2 mRNA和蛋白明显增加,差异有统计学意义(P<0.01);与MI组比较,治疗组小鼠心肌组织LOX、MMP-2 mRNA和蛋白明显下调,差异有统计学意义(P<0.01)。结论阿托伐他汀可下调急性心肌梗死小鼠心肌组织LOX表达,进而调控MMP-2表达。

Studies on Interaction between 4-（4-Hydroxybut-2-ynyloxy）-3-（phenylsulfonyl）-1,2,5- oxadiazole-2-oxide and Bovine Serum Albumin by Spectroscopic Method

The interaction between 4-（4-hydroxybut-2-ynyloxy）-3-（phenylsulfonyl）-1,2,5-oxadiazole-2-oxide （FB） and bovine serum albumin （BSA） was studied by spectroscopic methods including fluorescence and UV-Vis absorption spectroscopy. The quenching mechanism of fluorescence of BSA by FB was considered to be a dynamic quenching procedure. The number of binding sites n and apparent binding constant K were measured by fluorescence quenching method. The results indicate that there is FB molecular binding with BSA, and forming 1 ： 1 complex. The thermodynamic parameters such as △H, △G and △S, etc., were calculated, The results indicate that the binding reaction is mainly entropy-driven and hydrophobic forces play major role in the binding reaction, The distance r between donor （BSA） and acceptor （FB） was obtained according to Forster theory of non-radioactive energy transfer.

Syntheses and properties of 2-[bis-(2-chloroethyl)amino]-6-alkoxylmethyl-tetrahydro-2H-1, 3, 2-oxazapho-sphorine-2-oxide

<正> The syntheses of a series of 2-[bis-(2-chloroethyl)amino]-6-alkoxylmethyl-tetrahydro-2H-1, 3, 2-oxazaphosphonne-2-oxide are described The structures of all target compounds have been determined by 1H NMR, MS and elementary analysis, and their configurations and conformations have been studied by 31P NMR and X-ray diffraction analysis. The properties of NMR and MS of these compounds are discussed

阿托伐他汀对糖尿病心肌病大鼠心肌组织赖氨酰氧化酶的影响

目的探讨阿托伐他汀对糖尿病心肌病(DCM)大鼠心肌组织赖氨酰氧化酶(LOX)表达的影响及机制。方法将30只DCM大鼠分为DCM组、治疗组(阿托伐他汀2mg·kg-1·d-1灌胃)、β氨基丙腈(BAPN)组(BAPN 80mg·kg^(-1)·d^(-1)灌胃),每组10只;另选10只SD大鼠为空白对照组。第8周末处死大鼠。提取心肌组织RNA及蛋白质,RT-PCR和Western blot测定心肌组织LOX、基质金属蛋白酶2(MMP-2)及核因子-κB(NF-κB)mRNA和蛋白表达。结果 DCM组LOX、MMP-2及NF-κB mRNA和蛋白表达明显高于对照组(P<0.01);与DCM组比较,治疗组及BAPN组LOX、MMP-2及NF-κB mRNA和蛋白表达明显下调(P<0.01)。结论阿托伐他汀可逆转DCM大鼠心肌组织LOX表达,进而调控MMP-2及NF-κB表达。