Synthesis,Crystal Structure and Bioactivity of a Pd(Ⅱ) Complex with Demethylcantharate and 2,2′-Bipyridine

A novel crystal with the molecular formula [Pd(DCA)(bipy)]2 [Pd(bipy)Cl2 ]·6.75H2O was formed by PdCl2 with disodium demethylcantharate (Na2 (DCA),DCA2= 7-oxa-bicyclo[2.2.1]heptane-2,3-bicarboxylate) and 2,2-bipyidine (bipy) through the hydrothermal method.The complex was characterized by elemental analysis and infrared spectroscopy.The structure of the complex was determined by single-crystal X-ray diffraction,which is of triclinic system,space group P1 with a=13.6818(7),b=14.8426(8),c=15.0043(8),α=97.319(3),β=92.521(3),γ=105.776(2)°,V=2898.4(3) 3,Dc=1.545 g·cm-3,Z=1,F(000)=1420,S=0.852,the final R=0.0525 and wR=0.1777 for 13634 observer reflections (I>2σ(I)).The binding reaction of the complex with ct-DNA and bovine serum albumin (BSA) was studied by fluorescence spectroscopy.The results indicated that the complex binds to ct-DNA via the partial intercalation.The binding constant K A of the complex interaction with BSA was 3.98×10 5 L·mol-1 and one binding site would be formed.The antiproliferative activity of the complex against human hepatoma cells (SMMC7721) in vitro is much higher than that of Na 2 (DCA).     

Synthesis,Structure and Fluorescence Study of 3-Bromo-7-methyloxy-4-methylcoumarin

Coumarin derivative 3-bromo-7-methyloxy-4-methylcoumarin(C11H9BrO3) was synthesized and characterized by FT-IR,1H NMR spectra,and thermal analysis.The crystal structure was determined by X-ray single-crystal diffraction.The title compound crystallizes in the mono-clinic system,space group P21/n,with a = 7.770(16),b = 12.501(3),c = 10.627(2),β = 98.46(3)°,Mr = 269.09,V = 1021.0(4) 3,Z = 4,Dc = 1.751 g/cm3,μ = 4.008 mm-1,F(000) = 536,R = 0.0650 and wR = 0.1463.The optimization of the title compound was obtained by quantum chemical method at the SVWN5/6-31G** level.In the structure,the measured angles of the crystal structure are similar to those calculated,while the measured bond lengths are shorter than the calculated values due to the crystal field which functions to the molecule.The title compound also shows good fluorescent behaviors and good linear relationship with the equal concentration gradient in methanol.     

Synthesis and Structural Features of 3,5-Dihydroxy N′-(3-nitrobenzylidene) Benzohydrazide and Its Effect on the Intestinal Smooth Muscle

A new compound,3,5-dihydroxy-N-(3-nitrobenzylidene)benzohydrazide (DNBB) methanol solvate,was synthesized and characterized by single-crystal X-ray diffraction.DNBB crystallizes in a monoclinic system,space group P2 1/c with a=8.387(4),b=23.237(10),c=9.133(3),β=122.10(3)o,Z=4,V=1507.8(12) 3,D c=1.464 g/cm 3,F(000)=696.0,μ=0.116 mm-1,the final R=0.0480 and wR=0.1294.DNBB exhibited low toxicity on Caco-2 cell culture and produced significant inhibitory effect on the contraction of rat jejunal longitudinal smooth muscle (JLSM).The mechanism of DNBB on JLSM was correlated to the stimulation of α and β adrenergic receptors since α receptor antagonist phentolamine and β receptor antagonist propranolol abolished the inhibitory effects of DNBB on the contraction of JLSM,respectively.     

Theoretical Studies on the Binding of Cd~（2＋） to Uracil and Its Thio-derivatives

The interaction of Cd2+ with uracil,2-thiouracil,4-thiouracil and 2,4-dithiouracil have been investigated by the density functional theory(DFT) calculations.For uracil and 2,4-dithiouracil,where the two basic sites are the same,Cd2+ attachment to the heteroatom at position 4 is preferred.However,for the systems where both types of basic centers,a carbonyl and a thiocarbonyl groups,are present,Cd2+ association with sulfur is favorable.The enhanced stability of these enolic and thiol forms comes from Cd2+ interaction with two basic sites simultaneously,which thereby triggers a significant aromatization of the ring.More significantly,the Cd2+ binding energy with uracil and its thio-derivatives is larger than the tautomerization barriers connecting the diketo-like forms with the corresponding enolic-like tautomers.Consequently,when associated with Cd2+,all tautomers are energetically accessible and should be observed in the gas phase.     

DFT Investigation on the Insertion Reaction of an Isocyanide into the（Silyl）（silylene）molybdenum Si-C Bond

The chemistry of silylene-transition-metal complexes LnM(=SiR2)SiR3 is one of the attractive synthetic targets in organometallic chemistry for such complexes are key intermediates in many transition metal-catalyzed systems.In the present work,the novel insertion reactions of an isocyanide into the Cp*Mo(CO)2(=SiMe2)(SiMe3) Si-C bond were investigated extensively by using the DFT method.The effective core potentials(ECP) with a double-ζ valence basis set(LanL2DZ) were employed for Mo and Si and the standard 6-31G basis set for all other atoms.Polarization functions[22] were added for Si(ζd = 0.262),C(ζd = 0.8) and N(ζd = 0.8).The effect of solvent was evaluated with the standard PCM model.Our calculations show that the two-step channel is energetically favorable,and the solvation mode has minor influence on the relative energies.     

Synthesis and Characterization of Two Chiral Cadmium Coordination Compounds Constructed from (1S,1′S)-1,1′-(4-amino-4H-1,2,4-triazole-3,5-diyl)diethanol

Two chiral cadmium coordination compounds,(S)-[Cd(deoatrz)2 Cl2](1)and(S)[Cd(deoatrz)2 (NO3)2](2)(deoatrz=(1S,1 S)-1,1-(4-amino-4H-1,2,4-triazole-3,5-diyl)diethanol),are reported.Both 1 and 2 are mononuclear,crystallizing in tetragonal P41212 chiral space group with Z=2.For1,a=11.520(3),b=11.520(3),c=15.175(1),V=2013.6(1)3,Mr=527.7,Dc =1.741 g/cm 3,μ=1.386mm-1,F(000)=1064,the final GOF=1.05,R=0.0147 and wR=0.0433 for1932 observed reflections with I>2σ(I).For 2,a=12.201(3),b=12.201(3),c=15.027(4),V=2237.1(1)3,Mr=580.8,Dc=1.725 g/cm 3,μ=1.047mm-1,F(000)=1176,the final GOF=1.00,R=0.0201 and wR=0.0415 for 2408 observed reflections with I>2σ(I).Compounds 1 and 2 are connected into three-dimensional supramolecular networks through hydrogen bonding interactions.     

高效液相色谱法测定硫酸氢氯吡格雷中的有关物质

建立高效液相色谱法测定硫酸氢氯吡格雷中的有关物质的方法。其分解产物的检测,采用SinoChrom ODS-BP（200mm×4.6mm,5μm）色谱柱,以1%（V/V）三乙胺（pH=4.0）-乙腈（25∶75）为流动相,检测波长225nm,流速1.0mL/min。硫酸氢氯吡格雷在0.48—0.72μg范围内线性关系良好（r=0.9999）,定量下限为3ng,检出限为0.6ng,各种破坏性样品的分离度符合规定。其光学纯度的测定采用ULTRON ES-OVM（Analytical）手性柱（150mm×4.6mm,5μm）,色谱填料为L57。以磷酸盐缓冲液（pH=4.67）-乙腈（75∶25）为流动相,检测波长为220nm。硫酸氢氯吡格雷相关物质B分离度均大于2.5,符合要求。本方法简便,灵敏,准确,专属性强,能够满足硫酸氢氯吡格雷对有关物质测定的要求。     

Synthesis,Crystal Structure and Biological Activity of N-（2,6-Difluorobenzoyl）-N＇-[5-（4-trifluoromethyl-phenyl）-1,3,4-thiadiazol-2-yl]ure

The title compound N-(2,6-difluorobenzoyl)-N'-[5-(4-trifluoromethylphenyl)-1,3,4-thiadiazol-2-yl]urea(C17H9F5N4O2S,Mr = 428.34) has been synthesized by the reaction of 2-amino-5-(4-trifluoromethylphenyl)-1,3,4-thiadiazole with 2,6-difluorobenzoyl isocyanate,and its crystal structure was determined by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21/n with a = 10.7316(13),b = 10.5617(13),c = 16.037(2) ,β = 106.408(2)°,V = 1743.6(4) 3,Z = 4,Dc = 1.632 g/cm3,μ = 0.260 mm-1,F(000) = 864,the final R = 0.0599 and wR = 0.1420 for 3467 observed reflections with I > 2σ(I).The urea group,which adopts a planar configuration mediated by the intramolecular N-H...O hydrogen bond,is nearly coplanar with the thiadiazole and 4-trifluoromethylbenzene rings.The title compound was found to exhibit good fungicidal activity against Rhizoctonia solani and Botrytis cinerea.