Synthesis,Crystal Structure and Antitumor Activity of a Novel Zn(Ⅱ)Complex with 2-(Nicotinoyloxy)acetic Acid Ligand

A novel Zn（Ⅱ） complex, [ZnL2（H2O）4]·H2O（1, HL = 2-（nicotinoyloxy）acetic acid）, was synthesized using Zn（OAc）2·2H2O and 2-（nicotinoyloxy）acetic acid as raw materials. Its structure has been elucidated by elemental analysis, IR and single-crystal X-ray diffraction. The structural analysis revealed that complex 1 crystallizes in triclinic, space group P1 and the Zn（Ⅱ） atom is six-coordinated with two N atoms from two different 2-（nicotinoyloxy）acetate anion ligands and four O atoms from coordinated water molecules. Complex 1 forms a 3D network structure by O–H···O hydrogen bonds. The antitumor activities of 2-（nicotinoyloxy）acetic acid ligand and its Zn（Ⅱ） complex were evaluated against human lung adenocarcinoma A549 cells, human hepatoma SMMC-7721 cells and human colon carcinoma Wi Dr cells.

Synthesis,Structure,and Surface Photo-electric Properties of a New Zn(Ⅱ)Coordination Complex Constructed from 2-(1H-benzotriazol-1-yl)acetic Acid and 1,10-Phenanthroline Ligands

A new binuclear Zn^Ⅱ coordination complex,Zn2（bta）（phen）2（Cl）3（1,Hbta = 2-（1Hbenzotriazol-1-yl）acetic acid and phen = 1,10-phenanthroline）,has been synthesized and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental,and photoluminescent analysis.Complex 1 crystallizes in triclinic system,space group P1 with a = 9.3040（19）,b = 10.694（2）,c =16.841（3） A°,α = 101.18（3）,β = 105.77（3）,γ = 91.72（3）°,V= 1575.8（5） A°3,C（32）H（22）Zn2Cl3N7O2,Mr =773.66,Dc = 1.631 g/cm^3,Z = 2,F（000） = 780,μ = 1.820 mm^-1,the final R = 0.1238 and wR =0.1131.X-ray diffraction analyses indicate that 1 displays two crystallographic independent Zn^Ⅱmetal centers with a distorted tetragonal pyramidal（ZnN4O） and a tetrahedral（ZnNCl3） geometries,respectively.The phen serves as a common N,N＇-bidentate ligand,and the bta^- as a unique N,O-bridged ligand in 1.In the crystal,1 forms a stable 3D supramolecular architecture by trifurcated hydrogen bonding C-H…C1 interactions and C-H…π,π…π stacking.1 showed photo-electric conversion properties.

Synthesis of 2-(Benzodioxol-2-yl)acetic Acids as PPARδAgonists

A new series of compounds, 2-（benzodioxol-2-yl）acetic acids, have been synthesized. Their structures were confirmed by MS and 1H-NMR. The preliminary pharmacological screening showed that these compounds exhibited potent human PPARδ agonist activities.

Synthesis and Crystal Structure Analysis of 2-(3,5-Di-tert-butyl-2-hydroxyphenyl)-2-(3,4- dimethylphenyl) Acetic Acid Dimethylamine Salt

A new compound 2-（3,5-di-tert-butyl-2-hydroxyphenyl）-2-（3,4-dimethylphenyl） acetic acid dimethylamine salt （[NH2（CH3）2][C24H31O3]） was synthesized and structurally determined. It is of monoclinic system, space group P21/c with a = 14.731（2）, b = 10.1185（10）, c = 17.065（2） A^°, β = 98.293（10）° ,Z = 4, V = 2517.0（6）A^°^3, Dc = 1.091 g/cm^3, F（000） = 904 and Mr= 413.58. The dihedral angle defined by two benzene rings is 98.23°.

Synthesis and Molecular Structure of Acetic Acid-3,5-diacetoxy-2-acetoxymethyl-6-(4-quinoxalin-2-yl-phenoxy)-tetrahydro-pyran-4-yl-ester

The title compound, acetic acid-3,5-diacetoxy-2-acetoxymethyl-6-（4-quinoxalin- 2-yl-phenoxy）-tetrahydro-pyran-4-yl-ester 8 （C28H28N2O10, Mr = 552.54）, has been synthesized and its crystal structure was determined by X-ray diffraction analysis. It crystallizes in monoclinic, space group P21, a = 10.060（8）, b = 5.648（4）, c = 24.11（2）A, β = 91.078（10）°, Z = 2, V= 1369.9（19）A^3, Dc = 1.339 g/cm^3,μ（MoKa） = 1.03 cm^-1, F（000） = 580.00, T =. 193.1 Kx-9 θmax = 25.03, （△/σ）max = 0.0000, Flack = -0.0（24）, the final R = 0.0680 and wR = 0.140 （w = 1/[0.0016Fo^2 ＋ 1.00000（Fo^2）]/（4Fo^2）） for 3126 observed reflections （1 〉 20（/））. The pyranoid ring adopts chair conformation in the sugar moiety, and all of the acetyl groups are in the e bond of the pyranoid ring, so the sugar moiety is very stable.

Synthesis,Structure and DFT Calculations of a Novel Copper(Ⅱ)Complex Based on Tert-butyl 2-[N-(tert-butyloxycarbonylmethyl)-2-picolyamino]acetate

A novel copper（Ⅱ） complex with tert-butyl 2-[N-（tert-butyloxycarbonylmethyl）-2-picolyamino]acetate（ampy） was synthesized and structurally characterized by elemental analysis, FT-IR spectrum, electrospray ionization-mass spectrometry, UV-vis spectrum and single-crystal X-ray diffraction, respectively. A mononuclear copper（II） complex with ampy, [Cu（ampy）Cl2]（1）, was formed irrespective of the metal-to-ligand molar ratios（[Cu2＋]：[ampy] = 0.5：1, 1：1, and 2：1） as a single product. Complex 1 crystallizes in the orthorhombic system, space group Pbca with a = 12.343（2）, b = 18.928（3）, c = 20.058（4） A, V = 4686.1（14） A3, Z = 8, Dc = 1.3349（4） g/cm3, F（000） = 1920, S = 1.016, R = 0.0693 and w R = 0.1721 for 3151 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that the central copper（II） ion is bound by pyridyl N, tertiary amine N and carbonyl O atoms of the quadridentate ampy as well as two Cl anions, constructing a slightly distorted octahedral geometry. Complex 1 further constructs a stable 3D supramolecular architecture by intermolecular C–H…Cl hydrogen bonds. In addition, the molecular geometry was calculated by density functional theory（DFT/B3LYP） method with the basis sets（6-31＋G（d,p） for H, C, N, O and Cl atoms, and LANL2 DZ for Cu atom, respectively）. The calculated results show that the optimized geometrical parameters are in good agreement with the experimental data. Natural bond orbital（NBO） analysis and frontier molecular orbitals（FMOs） analysis were investigated at the same level.

Synthesis, Structure and Quantum Mechanical Calculations of Methyl 2-(5-((Quinolin-8-yloxy)-methyl)-1,3,4-oxadiazol-2-ylthio)-acetate

The title compound was synthesized by the base catalyzed reaction of 5-（（quinolin- 8-yloxy）methyl）-1,3,4-oxadiazole-2（3H）-thione with methyl chloroacetate. The structure was supported by the spectroscopic data and unambiguously confirmed by single-crystal X-ray diffraction studies. It crystallizes from a methanol solution in the triclinic space group Pi with unit cell dimensions a = 7.4509（9）, b = 10.2389（12）, c = 12.2299（15）A, a = 74.771（2）, β = 77.956（2）, 7 = 69.263（2）°, V = 834.98（17） A3 and Z = 2. In order to gain some valuable insights into the molecular structure, the quantum mechanical calculations were performed using both HF and time-dependent density functional theory at the B3LYP/6-31G（d,p） level. The molecular geometry from X-ray determination of the title compound in the ground state has been compared using the Hartree-Fock （HF） and density functional theory （DFT） with the 6-31G（d） basis set. The calculated results show that the DFT and HF can well reproduce the structure of the title compound. The energetic behavior of the title compound was examined using the B3LYP method with the 6-31G（d） basis set. The harmonic vibrational frequencies calculated have been compared with the experimental FTIR and FT-Raman spectra. The restricted Hartree-Fock and density functional theory-based nuclear magnetic resonance （NMR） calculation procedure was also performed, and it was used for assigning the 13C and 1H NMR chemical shifts of the title compound. Moreover, molecular electrostatic potential and thermodynamic parameters of the title compound were investigated by theoretical calculations.

Synthesis,Characterization,X-ray Crystal Structure and Safener Activity of Chiral 2-(3-Methyl-2,3-dihydrobenzo[b][1,4]oxazin-4-yl)-2-oxoethyl Acetate

The new title compound, chiral 2-（3-methyl-2,3-dihydrobenzo[b][1,4]oxazin-4-yl）- 2-oxoethyl acetate, has been synthesized via reduction, cyclization and acylation reaction. The structure of the product has been confirmed by IR, 1H NMR, 13C NMR, LC-MS （ESI） and single-crystal X-ray diffraction. （R）-2-（3-methyl-2,3-dihydrobenzo[b][1,4]oxazin-4-yl）-2-oxoethyl acetate crystallizes in monoclinic, space group P21/c with a = 11.867（2）, b = 8.4087（2）, c = 14.325（6） A^°, β = 117.59（2）°, Z = 4, V = 1266.9（6） A^°3, Dc = 1.307 g/cm^3, F（000） = 528, μ（MoKα） = 0.097 mm-1, R = 0.0453 and wR = 0.1237; （S）-2-（3-methyl-2,3-dihydrobenzo[b][1,4]oxazin-4-yl）-2-oxoethyl acetate belongs to the triclinic system, space group P with a = 8.2647（17）, b = 8.7034（17）, c = 9.5479（19） A^°, α = 105.33（3）, β = 100.95（3）, γ = 105.14（3）°, Z = 2, V = 614.1（2） A^°3, Dc = 1.348 g/cm^3, F（000） = 264, μ（MoKα） = 0.10 mm-1, R = 0.0613 and wR = 0.1037. Both of the molecules prefer to form crystal packing through C–H…O hydrogen bonds.

Synthesis of 3-(1-Cyclohexenyl)-2-butanone via Environmentally Friendly Catalysts

We substituted several environmentally friendly catalysts which included HY and H- β zeolites, various cation-exchanged β zeolites, and solid-supported ferric chloride for conventional catalysts for the synthesis of 3-(1-cyclohexenyl)-2-butanone from the reaction of ethylidenecyclohexane with acetic anhydride at room temperature. HY zeolite was found to be the most effective for this reaction, and gave the acylated product in a 72% yield under the conditions of n (ethylidenecyclohexane)/ n (acetic anhydride)/ m (HY zeolite)=1 mmol/10 mmol/0 100 g, reaction temperature 25 ℃ and reaction time 2 h. The used HY zeolite can be recovered, regenerated and gave almost the same yield as the fresh one. The lifetime of the HY zeolite is over 80 h. The effect of different factors on the reaction has also been investigated.

The Expression of Cyclooxygenase-2 in Cervical Cancers and Hela Cells Was Regulated by Estrogen/Progestogen

To investigate the relationship between the expression of cyclooxygenase-2 （COX-2） and menstrual cycle, the regulatory effects of 17-β-estradiol （E2） and medroxyprogesterone acetate （MPA） on the expression of COX-2 in cervical cancer Hela cells were examined. Cervical cancer specimens were obtained from 47 pre-menopausal patients. The phase of menstrual cycle was determined by case history and HE staining of uterine endometrium. COX-2 was immunohistochemically stained by SABC staining and the staining intensity was determined with computerized image analysis system. Hela cells were incubated with alcohol, E2, E2＋MPA, MPA for 12, 24 and 48 h respectively. The expression of COX-2 in Hela cells was detected by Western blotting and reverse transcriptase-polymerase chain reaction （RT-PCR）. Our results showed that the expression of COX-2 was significantly higher during proliferative phase than secretory phase （P〈0.05）, but there was no difference in the positive rate between proliferative phase and secretory phase （P〉0.05）. Incubation with E2 could significantly enhance the expression of COX-2 continually. On the contrary, E2＋MPA and MPA alone could decrease the expression of COX-2 as compared with the control and E2 group （P〈0.05 and P〈0.01 respectively）. It is concluded that the expression of COX-2 in cervical cancer of pre-menopausal patients and Hela cells was regulated by estrogen/progestogen.

A Sensitive HPLC-MS/MS Analysis of Dencichine in Rat Plasma and Its Application to Pharmacokinetics

In order to quantitate dencichine in biological samples, a selective and sensitive method for the determination of dencichine in rat plasma based on high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed and validated. (l)-2-amino-3-(carboxymethylthio)propionic acid was used as the internal standard (I.S.). After a protein precipitation extraction with acetonitrile, dencichine and the I.S. were chromatographed on an Xterra MS-C18 column. The mobile phase was consisted of 20mmol/L ammonium acetate solution-acetonitrile (35:65, V/V) at a flow rate of 0.2 mL/min. The detection was performed on a triple quadrupole mass via electrospray ionization (ESI) source in the positive mode. The intra- and inter-day precision (relative standard deviation, R.S.D.) values of dencichine were below 6.7%. The extraction recoveries were up 85%. The lower limit of quantification was 20 ng/ml, which was sensitive enough to detect the analyte. The HPLC-MS/MS method was successfully applied to the pharmacokinetic study after an intravenous administration of dencichine in Sprague-Dawley (SD) rat.

Synthesis, Crystal Structure and Thermal Behavior of 4,5-Diacetoxyl-2-（dinitromethylene）-imidazolidine

A new energetic material, 4,5-diacetoxyl-2-（dinitromethylene）-imidazolidine （DADNI）, was synthesized by the reaction of 4,5-dihydroxyl-2-（dinitromethylene）-imidazolidine （DDNI） and acetic anhydride, and characterized by single crystal X-ray diffraction. Crystal data for DADNI are monoclinic, space group C2/c, a= 15.9167（3）A, b= 8.6816（4）A, c=8.5209（3） A, t= 103.294（9）°, V= 1145.9（3） A3, Z=4,A=0.150 mm 1, F（000）=600, Dc= 1.682 gocm-3, R] =0.0565 and wR2=0.1649. Thermal decomposition behavior of DADNI was studied and an intensely exothermic process was observed. The kinetic equation of the decomposition reaction is：exp（-1.582 ×10^5/RT）. The critical temperature of thermal explosion is 163.76℃. The specific heat capacity of DADNI was studied with micro-DSC method and theoretical calculation method. The molar heat capacity is 343.30 J·mol^-1·K^-1 at 298.15 K. The adiabatic time-to-explosion of DADNI was calculated to be 87.7 s.

花蓟马雄虫释放的聚集信息素的分离和鉴定

明确花蓟马Frankliniella intonsa雄虫释放的聚集信息素对于花蓟马生物防治具有重要意义。但目前除了西花蓟马F. occidentalis,关于其他蓟马雄虫释放的聚集信息素及其成分鉴定的研究未有报道。本研究采用Y型嗅觉仪测定花蓟马雌雄成虫和西花蓟马雌雄成虫对花蓟马雄虫和西花蓟马雄虫气味源的嗅觉反应;用固相微萃取(solid-phase microextraction,SPME)方法提取花蓟马雄虫挥发物,利用含有BGB-176SE或CP-chirasil-DexCB2种不同手性柱的气-质联用仪(gas chromatography-mass spectrometry,GC-MS)对挥发物进行分离和鉴定。行为学试验结果表明:花蓟马雄虫气味源对其雄性及雌性成虫均具有明显的吸引作用。经GC-MS分析,花蓟马雄虫挥发物中含有2种主要的化合物,分别为(R)-lavandulyl acetate和neryl(S)-2-methylbutanoate,其与已报道的西花蓟马雄虫释放的聚集信息素成分相同。但定量分析结果表明,(R)-lavandulyl acetate与neryl(S)-2-methylbutanoate在花蓟马和西花蓟马雄虫中释放的比例不同;行为学试验进一步证明,2种组分比例的不同在花蓟马和西花蓟马种间识别过程中发挥重要作用。本研究推测花蓟马属的昆虫释放的聚集信息素组分可能是相同的。

注射相关因素对11C标记正电子显像剂注入有效活度的影响

由于用11C核素标记的正电子显像剂11C-胆碱(11C-choline)、11C-蛋氨酸(11C-methylmethionine,11C-MET)、11C-乙酸盐(11C-sodium acetate,11C-ACE)、11C-甲基-N-2β-甲基酯-3β-(4-F-苯基)托烷[11C-methy-N-2β-carbomethoxy-3β-(4-fluoropheny)tropane,11C-βCFT]等进行PET/CT检查,在蛋白质合成、脂肪酸代谢、受体及配体和神经递质显像等方面具有明显优势,与已广泛应用的18F-2-氟-2-脱氧-D-葡萄糖(18F-2-fluoro-2-deoxy-D-glucose,18F-FDG)正电子发射计算机断层显像(PET/CT)在肿瘤的诊断和鉴别诊断等方面起到互补或相互印证的作用,因此近年来应用逐渐普及,但与18F标记的显像剂相比,11C半衰期很短,仅有20.34 min,其放射性活度的变化速率较快,因此研究注射前放射性活度的测量时机和静脉注射方法对实际注入的有效活度的影响有重要意义。