Synthesis and Crystal Structure of N-[(3aR,4R,4aR,5aS,6S,6aS)-1,3-Dioxooctahydro-4,6-ethenocyclopropa[f]isoindol-2(1H)-yl]-3-(trifluoromethyl)phenylmethanimine

The crystal structure of the title compound（C19H15F3N2O2,Mr = 360.33） was determined by single-crystal X-ray diffraction.The crystal belongs to triclinic,space group P1,with a = 6.5604（7）,b = 13.9614（16）,c = 18.1790（18） ,α = 102.749（7）,β = 97.542（6）,γ = 94.355（4）°,V = 1600.5（3） 3,Z = 4,Dc = 1.495 g/cm3,λ（MoKα） = 0.71070,F（000） = 744,μ（MoKα） = 0.122 mm-1,R = 0.0434 and wR = 0.1051.A total of 7590 unique reflections were collected,of which 5429 with ｜F｜2 ≥ 2σ｜F｜2 were observed.The two cyclohexene rings in the molecule adopt boat-boat conformations with the deviations of ring atoms C（9） and C10 from the C（5）/C（6）/C（7）/C（8） plane（Ⅰ） by 1.1204（0.0023） and 1.1132（0.0023） ,respectively,whereas from the C（2）/C（3）/C（5）/C（8） plane（Ⅱ） by 1.1627（0.0022） and 1.1818（0.0021） ,respectively.In the cyclopropane and lactam rings,atoms C（11） and N（1） point towards the double bond of C（9）-C（10） and the dihedral angle between the ring plane（Ⅲ） containing C（1）,C（2）,C（3） and C（4） and plane（IV） consisting of C（6）,C（7） and C（11） is 55.76（0.07）°.The dihedral angles between planes Ⅳ and Ⅰ and Ⅱ and Ⅲare 63.58（0.07）° and 58.10（0.06）°,respectively.The dihedral angle between the benzene ring C（13）～ C（18） and plane Ⅳ is 42.41（0.06）°.

Synthesis and Crystal Structure of a Novel Ethyl 5-(4-(2-Phenylacetamido)phenyl)-1H-pyrazole-3-carboxylate as an Acrosin Inhibitor

The title compound （ethyl5-（4-（2-phenylacetamido）phenyl）-lH-pyrazole-3-carboxylate, C20H19N3O3） was synthesized by the reaction of Claisen condensation, cyclization, reduction and acylation. The structure was characterized by X-ray diffraction, MS, NMR and IR. It belongs to the monoclinic system, space group C2/c with a = 22.723（9）, b = 9.324（4）, c = 18.890（8） A, β = 114.259（6）°, V = 3649（3） A^3, Dc = 1.272 Mg·m^3, Z = 8, Mr = 349.38, p = 0.087 mm^-1, F（000） = 1472, the final R = 0.0615 and wR = 0.1643. The biological test shows that the title compound has a moderate acrosin inhibition activity.

Synthesis Hexadecyl 3-{4-[2-Hydroxy-3(isopropylamino)propoxy] phenyl}propionate as Potential Ligand for Liposome Targeting to Ischemic Myocardium

Novel hexadecyl 3-{4-[2-hydroxy-3(isopropylamino)propoxy]phenyl}propionate(HPP)was synthesized and its effect on delivery of liposomes into cultured cardiomyocytes was examined.The structure of HPP was characterized by IH NMR,1R and MS.The amount of cardiomyocytes uptake of HPP-liposome was 3.9-fold higher than plain-liposome,and the increase was 6.2-fold when hypoxia happens.It indicated that HPP was a potential ligand for liposome targeting to ischemic myocardium.

Synthesis and Crystal Structure of (Z)-Methyl-3-methoxy-2-{2-[(4-(E-3-p-tolylacryloyl)phenoxy)methyl]phenyl}acrylate

The title compound,(Z)-methyl-3-methoxy-2-{2-[(4-(E-3-p-tolylacryloyl)phenoxy)-methyl]phenyl}acrylate,was synthesized and determined by X-ray single-crystal diffraction.The crystal belongs to the triclinic system,space group P1 with a=8.0157(8),b=12.5748(13),c=13.3768(14)Å,α=64.770(2),β=75.720(2),γ=89.784(2)°,μ=0.085 mm^(-1),Mr=442.49,V=1174.1(2)Å3,Z=2,Dc=1.252 g/cm^(3),F(000)=468,T=294(2)K,R=0.0603 and wR=0.1498 for 2644 observed reflections with I〉2σ(I).X-ray diffraction analysis reveals that the single crystal contains strong non-classical hydrogen bonds.The preliminary bioassay showed that the title compound exhibits inhibitory activity against the Pseudoperoniospora cubensis and Rhizoctonia solani at the test concentration of 200 mg/L.

Synthesis and Crystal Structure of(E)-Ethyl 2-(4-(2,4-dimethoxybenzylideneamino)-5-(3,4,5-trimethoxyphenyl)-4H-1,2,4-triazol-3-ylthio)acetate

The crystal structure of the title compound(E)-ethyl 2-(4-(2,4-dimethoxy benzylide-neamino)-5-(3,4,5-trimethoxyphenyl)-4H-1,2,4-triazol-3-ylthio)acetate(4,C_(24)H_(28)N_(4)O_(7)S,Mr=516.17)was synthesized and determined by X-ray single-crystal diffraction.The crystal belongs to the monoclinic system,space group P2_(1)/n with a=13.162(2),b=8.4506(13),c=22.602(4)Å,β=99.888(3)°,μ=0.183 mm^(-1),V=2476.5(7)Å^(3),Z=4,D_(c)=1.385 g/cm^(3),F(000)=1088,T=110(2)K,R=0.0426 and wR=0.1216 for 3859 observed reflections with I 2σ(Ⅰ).

Formation of Hybrid Ring Structure of Cyanurate/Isocyanurate in the Reaction be-tween 2,4,6-Tris(4-Phenyl-Phenoxy)-1, 3,5-Triazine and Phenyl Glycidyl Ether

Reaction products of 2,4,6-tris(4-phenyl-phenoxy)-1,3,5-triazine derived from 4-phenylphenol cyanate ester and phenyl glycidyl ether were analyzed. In addition to an isocyanurate compound and an oxazolidone compound which were well known as reaction products of cyanate esters and epoxy resins, compounds with hybrid ring structure of cyanurate/isocyanurate were determined. Gibbs free energies of the compound having hybrid ring structure of cyanurate/isocyanurate with two isocyanurate moiety were found to be lower than that of the compound with cyanurate ring structure through calculations. Calculation data supported the existence of hybrid ring structure of cy-anurate/isocyanurate. It was revealed that isomerization from cyanurate to isocyanurate occurs via hybrid ring structure of cyanurate/isocyanurate in the reaction of aryl cyanurate and epoxy.

Synthesis and Crystal Structure of a Two-hydroxyphenyl Adamantane-type Epoxy Resin

A two-hydroxyphenyl adamantane-type epoxy resin oligomer,namely 1,3-bis（4-（2,3-epoxpropyloxy）phenyl） adamantine （BEPAD）,has been synthesized and structurally characterized by single-crystal X-ray diffraction.The unit cell of C28H32O4：Mr =432.5,monoclinic,space group P21/n,with a =10.510（6）,b =16.972（9）,c =13.374（7） （A）,β =109.356（6）°,V=2251（2） （A）3,Z =4,Dc =1.277 Mg·m^-3 and μ（MoKa） =0.084 mm^-1.In BEPAD,the methylene and epoxide rings on two ends are statistically disordered.The intermolecular interactions are also discussed,suggesting that the intermolecular interactions in BEPAD are stronger than that in the crystals of similar compounds due to the large adamantine group between the two benzene rings.

Synthesis and Herbicidal Activity of Novel N-（2-Fluoro-5（3- methyl-2,6-dioxo-4-（trifluoromethyl）-2,3-dihydro-pyrimidin- l（6H）-yl）phenyl）-2-phenoxyacetamide Derivatives

Thirteen novel N-（2-fluoro-5-（3-methyl-2,6-dioxo-4-（trifluoromethy）-2,3-dihydropyrimidin-1（6H）-yl）phenyl）- 2-phenoxy）acetamides were designed and synthesized utilizing 4-fluoro-aniline and ethyl 3-amino-4,4,4-trifluoro-but-2-enoate as starting materials. The chemical structures of all compounds were confirmed by IH NMR, IR, mass spectrum and elemental analyses. Subsequently, the herbicidal activities of the as-prepared compounds were evalu-ated in the greenhouse. Bioassay results indicated that most of compounds had better herbicidal activities against dicotyledonous weeds. Among all the tested compounds, compounds 4a--4i showed good herbicidal activities at both pre-emergence and post-emergence treatment against two or three kinds of dicotyledonous weeds, such as Abutilon theophrasti Medic, Amaranthus ascendens L, and Chenopodium album L at the dosage of 75 g ai/ha.

AAZ2 induces mitochondrial-dependent apoptosis by targeting PDK1 in gastric cancer

Drastic surges in intracellular reactive oxygen species(ROS)induce cell apoptosis,while most chemotherapy drugs lead to the accumulation of ROS.Here,we constructed an organic compound,arsenical N-(4-(1,3,2-dithiarsinan-2-yl)phenyl)acrylamide(AAZ2),which could prompt the ROS to trigger mitochondrial-dependent apoptosis in gastric cancer(GC).Mechanistically,by targeting pyruvate dehydrogenase kinase 1(PDK1),AAZ2 caused metabolism alteration and the imbalance of redox homeostasis,followed by the inhibition of phosphoinositide-3-kinase(PI3K)/protein kinase B(AKT)/mammalian target of rapamycin(mTOR)pathway and leading to the activation of B-cell lymphoma 2(Bcl2)/Bcl2-associated X(Bax)/caspase-9(Cas9)/Cas3 cascades.Importantly,our in vivo data demonstrated that AAZ2 could inhibit the growth of GC xenograft.Overall,our data suggested that AAZ2 could contribute to metabolic abnormalities,leading to mitochondrial-dependent apoptosis by targeting PDK1 in GC.

两种红光铱配合物的合成和电致发光性能研究

以二（二苯基磷酰）胺fHtpip）作为辅助配体，与主配体2-（2，4-二氟苯基）异喹啉和2-（4-三氟甲基苯基）异喹啉合成了红光铱磷光配合物Ir（dfpiq）2tpip和Ir（tfmpiq）2tpip并得到了晶体结构。在CH2Cl2中发射光谱主要是MLCT发射，峰位置分别为622和600nm．量子效率分别为15％和17％，而HOMO／LUMO能级分别是-4．80／-2．58和-4．73／-2．57eV。在1150-1300（V·cm-1）1/2电场范围．Ir（dfpiq）2tpip的电子迁移率为6．61-8．49×10^-6cm2·V-1·s-1，Ir（tfmpiq）2tpip的电子迁移率为6．08～6．61×10^-6cm2·V-1·s-1。ITO／TAPC（60nm）／Ir-complex（l5wt％）：CBP（50nm）／TPBi（60nm）/LiF（1nm）／Al（100nm）中基于Ir（dfpiq）2tpip的器件最大安培效率和功率效率分别为4．71cd．A-1和1．82lm．W-1，12．0V时达到的最大亮度为18195cd·m-2。基于Ir（tfmpiq）2tpip的器件最大安培效率和功率效率分别为3．47cd．A-1和1．51lm·W-1，12．4V时达到的最大亮度为14676cd·m-2。

吡唑化合物pyr3干预对压力负荷诱导的大鼠左心室肥厚的影响

目的：探讨瞬时受体电位通道C亚族3亚型（TRPC3）的选择性阻滞剂吡唑化合物Ethyl-1-（4-f2，3，3一trichloroacrylamide）phenyl）-5-（trifluoromethyl）-1H—pyrazole-4-carboxylate（pyr3）的体内干预对压力负荷大鼠左心室肥厚（LvH）程度的影响。方法：采用腹主动脉缩窄手术建立左心压力负荷模型。30只200—240g雄性SD大鼠随机分为五组（n=6）：假手术对照组、手术对照组、假手术后全程给药组、手术后后期给药组，手术后全程给药组。6周后，计算各组大鼠左心室质量指数、左心室心肌细胞横径，逆转录多聚酶连反应（RT—PCR）、免疫组织化学和蛋白免疫印迹检测TRPC3和钙调神经磷酸酶A13信使核糖核酸（mRNA）和蛋白的表达水平。结果：与假手术对照组相比，手术对照组左心室肥厚相关指标（左心室质量指数和左心室心肌细胞横径）及TRPC3、钙调神经磷酸酶AB蛋白和mRNA的表达显著升高；假手术后全程给药组左心室肥厚相关指标无显著变化，而TRPC3和钙调神经磷酸酶AB蛋白及mRNA的表达量显著升高，差异均有统计学意义（P均〈0．05）。与手术对照组比较，手术后全程给药组左心室肥厚相关指标、TRPC3及钙调神经磷酸酶A13蛋白和mRNA表达均明显降低（P均〈0．05）；手术后后期给药组左心室肥厚相关指标及钙调神经磷酸酶AB蛋白和mRNA的表达下降，差异均有统计学意义（P均〈0．05），而TRPC3的蛋白和mRNA表达未见显著降低。结论：pyr3体内干预能够一定程度上阻止压力负荷导致的大鼠左心室肥厚，降低压力负荷大鼠左心室TRPC3和钙调神经磷酸酶AB表达的上调。

A New Chromone Derivative from Stellera chamaejasme L

A new chromone derivative, 3-[1- (2, 4, 6-trihydroxyphenyl) 3-di-(4-hydroxyphenyl) 1-propanone-2-yl] 5,7-dihydroxy-8-di(4-hydroxyphenyl)methyl-4H-1-benzopyran-4-one, named as isomohsenone was isolated from the roots of Stellera chamaejasme L. together with known chamaechromone. Its structure was determined by the analysis of MS and NMR data, especially 2D NMR spectra.

A new prenylated arylbenzofuran derivative from Morus alba L.

2-[3,5-Di-O-β-D-glucosyl-4-(3-methylbut-2-enyl)phenyl]benzofuran-6-ol,a new prenylated arylbenzofuran derivative was isolated from Morus alba L.Its structure was elucidated by various spectroscopic methods including MS,~1H NMR,^(13)C NMR,DEPT,~1H-~1HCOSY,HMQC and HMBC.

Improved stability of blue TADF organic electroluminescent diodes via OXD-7 based mixed host

Thermally activated delayed fluorescence(TADF)organic light-emitting diodes(OLEDs)have been demonstrated in applications such as displays and solid-state lightings.However,weak stability and ineffi-cient emission of blue TADF OLEDs are two key bottlenecks limiting the development of solution processable displays and white light sources.This work presents a solution-processed OLED using a blue-emitting TADF small molecule bis[4-(9,9-dimethyl-9,10-dihydroacridine)phenyl]sulfone(DMAC-DPS)as an emitter.We comparatively investigated the effects of single host poly(Nvinylcarbazole)(PVK)and a co-host of 60%PVK and 30%2,2′-(1,3-phenylene)-bis[5-(4-tert-butylphenyl)-1,3,4-oxadiazole](OXD-7)on the device performance(the last 10%is emitter DMAC-DPS).The co-host device shows lower turn-on voltage,similar maximum luminance,and much slower external quantum efficiency(EQE)rolloff.In other words,device stability improved by doping OXD-7 into PVK,and the device impedance simultaneously and significantly reduced from 8.6103 to 4.2103 W at 1000 Hz.Finally,the electroluminescent stability of the co-host device was significantly enhanced by adjusting the annealing temperature.

Design, Synthesis and Biological Evaluation of Novel α-Acyloxycarboxamide-Based Derivatives as c-Met Inhibitors

Dysregulated HGF/c-Met signalling has been associated with many human cancers,poor clinical outcomes,and even resistance acquisition to some approved targeted therapies.As such,c-Met kinase has emerged as an attractive target for anticancer drug discovery.

Isolation and structural elucidation of cytotoxic compounds from the root bark of Diospyros quercina (Baill.) endemic to Madagascar

Objective:To isolate and characterize the cytotoxic compounds from Diospyros quercina(Baill.)G.E.Schatz&Lowry(Ebenaceae).Methods:An ethno-botanical survey was conducted in the south of Madagascar from July to August 2010.Bio-guided fractionation assay was carried out on the root bark of Diospyros quercina,using cytotoxicity bioassay on murine P388 leukemia cell lines as model.The structures of the cytotoxic compounds were elucidated by 1D and 2D NMR spectroscopy and mass spectrometry.Results:Biological experiments resulted in the isolation of three bioactive pure compounds(named TR-21,TR-22,and TR-23)which exhibited very good in vitro cytotoxic activities with the IC_(50)values of(0.017 5±0.0060)μg/mL,(0.089±0.005)μg/mL and(1.027±0.070)μg/mL respectively.Thus,they support the claims of traditional healers and suggest the possible correlation between the chemical composition of this plant and its wide use in Malagasy folk medicine to treat cancer.Conclusions:The ability of isolated compounds in this study to inhibit cell growth may represent a rational explanation for the use of Diospyros quercina root bark in treating cancer by Malagasy traditional healers.Further studies are,therefore,necessary to evaluate the in vivo antineoplastic activity of these cytotoxic compounds as effective anticancer drugs.

Curing Behaviors and Thermal Properties of Dimer Fatty Acid （DFA） Modified Multifunctional Epoxy Resin

In order to improve the toughness of the cured aromatic tetrafunctional epoxy resins, a dlmer rarboxylic acid named dlmer fatty acid （DFA） was used to modify an aromatic tetrafunctional epoxy, N, N, N＇, N＇-tetraglycidyl-2,2-bis [ 4-（ 4-aminophcuoxy ） phenyl ] propane （TGBAPP）. The curing behaviors of DFA- TGBAPP/MNA （ methyl nadic anhydride） systems were studied by differential scanning calorimetry （DSC） method. And the thermal properties of the cured epoxy resin were investigated with the thermo-gravimetric analysis （TGA） and dynamic mechanical analysis （DMA）. Besides, the toughness was characterized with the impact strength tested by charpy impact testing. The results indicated that the modification would improve the curing reactions, and the curing temperatures were decreased with the increasing content of DFA. The thermal properties were not influenced obviously, and the toughness could be improved when the epoxy resin was modified with DFA.

New Phloroglucinol Glycosides from Hypericum japonicum

Two new phloroglucinol glycosides, 2,6-dihydroxy-3,5-dimethyl-1-isobutyrylbenzene-4-O-beta-D-glucoside and 2,6-dihydroxy-3,5-dimethyl-1-(2-methylbutyryl) benzene-4-O-beta-D-glucoside were isolated from Hypericum japonicum. Their structures were determined by spectroscopic and chemical methods.

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.

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.