SOLID-STATE BATTERY WITH POLYACETYLENE ELECTRODE

The Li/Lil/(CHIy)x battery was fabricated by using fast ionic conductor-LiI as the solid electrolyte has not been reported. The battery exhibited an open circuit voltage of 3.1v and an initial short circuit of 7ma/cm^2. (CHIy)x can be used in the Li/l2 battery as the rote of charge transfer complex. Experimental enerny density of 110Wh/kg was obtained based on the weight of (CH)x film (weight of (CH)x electrode:ca. 4mg, doping level:y=0.11).

Electronic Structure of Doped Trans-Polyacetylene

The behavior of electronic structures of doped trans-polyacetylene is revealed by a simple method. (C24H26)+n is used to simulate p-type doped trans-polyacetylene at various doping concentrations. The electronic structure is calculated, by CNDO/2 method. These calculations show that at low doping level, the decrease of electronic energy compensates the increase of elastic energy, thus the bond alternation exists, and the charge carriers are solitons. When doping level is high, the increase of elastic energy is larger than the decrease, of electronic energy, the bond alternation disappears, solitons no longer exist, and polyacetylene is in a metalic state.

A new polyacetylene glycoside from the rhizomes of Atractylodes lancea

A new polyacetylene glycoside,（1,3Z,11E）-tridecatriene-7,9-diyne-5-hydroxyl-6-O-β-D-glucopyranoside,was isolated from the rhizomes of Atractylodes lancea（Thunb.） DC.Its structure was elucidated on the basis of spectral analysis.

SYNTHESIS AND PROPERTIES OF POLYACETYLENES CONTAINING CARBAZOLE AND AMINO ACID MOIETIES

Novel 9-proparylcarbazole monomers containing amino acid moieties,2-N(tert-butoxycarbonyl)-L-alanine- 9-proparylcarbazole ester(1),2-N-(tert-butoxycarbonyl)-L-O-cyclohexyl-L-glutamic acid-9-proparylcarbazole ester(2) and 2-N-(tert-butoxycarbonyl)-L-phenylalanine-9-proparylcarbazole ester(3) were synthesized and polymerized with (nbd)Rh^+[η~6-C_6H_5B^-(C_6H_5)_3]to give the corresponding polymers with number-average molecular weights ranging from 7050 to 10500 in 70%-86%yields.The polymers were completely so...

A Viscidane Diterpene and Polyacetylenes from Cultures of Hypsizygus marmoreus

Investigation on the cultures of Hypsizygus marmoreus resulted in the isolation of a new viscidane diterpene,8-oxoviscida-3,11(18)-diene-13,14,15,19-tetraol(1)and two new polyacetylenes,(E)-10-(1,1-dimethyl-2-propenyloxy)-2-decene-4,6,8-triyn-1-ol(2)and 10-(1,1-dimethyl-2-propenyloxy)deca-4,6,8-triyn-1-ol(3),together with two known polyacetylenes,(E)-2-decen-4,6,8-triyn-1-ol(4)and 4,6,8-decatriyn-1-ol(5).Their structures were elucidated on the basis of extensive spectroscopic studies.Compound 1 is the first finding of viscidane diterpene in mushrooms.Compounds 1,3 and 5 were tested for cytotoxicity against human tumor cell lines HL-60,SMMC-7721,A-549,MCF-7 and SW-480.None of the compounds showed cytotoxic activity(IC50[40 lM).

Accurate theoretical evaluation of strain energy of all-carboatomic ring(cyclo[2n]carbon),boron nitride ring,and cyclic polyacetylene

Cyclocarbon fully consists of sp-hybridized carbon atoms,which shows quite unusual electronic and geometric structures compared to common molecules.In this work,we systematically studied strain energy(SE)of cyclocarbons of different sizes using regression analysis method based on electronic energies evaluated at the very accurate DLPNO-CCSD(T)/ccp VTZ theoretical level.In addition,ring strain of two systems closely related to cyclocarbon,boron nitride(BN)ring,and cyclic polyacetylene(c-PA),is also explored.Very ideal relationships between SE and number of repeat units(n)are built for cyclo[2n]carbon,B_(n)N_(n),and[2n]c-PA as SE=555.0·n^(-1),145.1·n^(-1),and 629.8·n^(-1)kcal·mol^(-1),respectively,and the underlying reasons of the difference and similarity in their SEs are discussed from electronic structure perspective.In addition,force constant of harmonic potential of C-C-C angles in cyclocarbon is derived based on SE values,the result is found to be 56.23 kcal·mol^(-1)·rad^(-2).The possibility of constructing homodesmotic reactions to calculate SEs of cyclocarbons is also explored in this work,although this method is far less rigorous than the regression analysis method,its result is qualitatively correct and has the advantage of much lower computational cost.In addition,comparisons show thatωB97XD/def2-TZVP is a good inexpensive alternative to the DLPNO-CCSD(T)/cc-p VTZ for evaluating energies used in deriving SE,while the popular and very cheap B3LYP/6-31G(d)level should be used with caution for systems with global electron conjugation such as c-PA.

STUDY ON THE CHEMICAL CONSTITUENTS OF BIDENS BIPINNATA A NEW POLYACETYLENE GLYCOSIDE

A new naturally occurring compound 1-polyacetylene glycoside has been isolated form the n- butanol soluble fraction of the leaves of Bidens bipinnata. The chemical structure of 1 was shown to be 3E, 11E—Diethenylene 5. 7. 9—triacetylene, 1, 13—tridecanglycol-2-O-β-D-glycoside named bipinnatpolyacetyloside according to spectral analyses of UV. IR. FDMS, ~1H-NMR, ~H-~H COSY, ^(13)C-NMR and DEPT.

INFLUENCE OF BACKBONE RIGIDITY ON THE LIQUID CRYSTALLINITY OF MESOGEN-CONTAINING POLYACETYLENES

Two acetylene polymers containing cyanobiphenyl-based mesogens, poly{10-[((4'-cyano-4-biphenylyl)oxy)carbonyl]-1-decyne} (PA8CN), which has a relatively flexible polyalkyne backbone, and poly {[4-(((12-((4'-cyano-4-biphenylyl)oxy)dodecyl)oxy) carbonyl) phenyl]-acetylene} (PB12CN), which has a fairly rigid poly(phenylacetylene) backbone, were synthesized using respectively WCl6 and [Rh(nbd)Cl](2) as the catalysts. PA8CN exhibits enantiotropic interdigitated smectic A phase (S-Ad) over a temperature range as wide as ca. 100 degrees C, whereas PB12CN is non-mesomorphic, demonstrating that the backbone rigidity plays an important role in determining the liquid crystallinity of the polyacetylenes.

POLYMER DIODES MADE OF ION IMPLANTED POLYACETYLENE FILMS

Polyacetylene films were doped with FeCl3 and implanted with 30 k’eV K+ ions. Physical changes to the films were examined by a series of measurements, which include the four-probe test, infrared ray absorption and 2 MeV He+ particle elastic recoil dettection and Rutherford backscattering. The chemical dopants (Fe+++ and Cl-) were redistributed after the implantation and the different species (K+. Fe+++ and Cl-ions) formed p - n junctions at the implantation depths. The implanted films exhibited desirable Ⅰ-Ⅴ characteristics, with current densities as high as 600 mA/cm- at 3V and back - to - forward ratio of current over 300. The polymer diodes kept their behavior for over 60 days. Discussions on the results were given in detail.

PREPARATION OF SOLUBLE SUBSTITUTED POLYACETYLENE OPTICAL LIMITING MATERIAL

Two novel polyacetylenes bearing nonlinear optical chromophoric group poly（3-（4-[4-（n-butyloxy） phenylazophenyl]carbonyl）oxy-1-propyne） （poly（1a）） and poly（3-（4-[4-（n-heptyloxy）phenylazophenyl]carbonyl）-oxy-l- propyne） （poly（lb）） were synthesized with [Rh（nbd）Cl]2-EtaN as catalysts. These polyacetylenes are soluble by using an alkyl spacer and an alkyloxyl group as a substituent. They were characterized by FTIR, NMR, GPC and UV-Vis and their optical limiting and nonlinear optical properties were investigated using 8 ns pulse at 532 nm wavenumber. The results show that these soluble functional polyacetylenes possess optical limiting properties and large nonlinear optical properties and poly（1b） possesses better optical limiting and nonlinear optical properties than poly（ 1 a）.

Calculation of the transfer integrals in Wannier representation for a planar trans-polyacetylene chain

In this paper, the electronic transfer integrals, the energy gap, and the bandwidth of a planar trans polyacetylene chain are calculated in Wannier representation, in which a combination of the wave function of hydrogen like atoms is used to stand for the Wannier function. When the effective nuclear charge number Z = 2.125 and the distortion amplitude of the carbon sites u =0.0038 nm, the nearest, next, and third neighbor hopping energies obtained are -3.224 78 eV, -2.388 61 eV, 0.148 14 eV, 0.006 65 eV, and 0.006 50 eV, respectively. The energy bandwidth and gap corresponding to these values are W d =11.19 eV and E g =1.70 eV, respectively. These results coincide with the experimental values.

Preparation and property of a novel soluble oxadiazole-containing functional polyacetylene

A novel high molecular weight functional polyacetylene bearing oxadiazole group as a pendant, poly{4-[2-（4-octoxyphenyl）-1,3,4-oxadiazolyl]-benzenyloxypropynylene}, was synthesized by [Rh（nbd）Cl]2-Et3N catalyst. The polymer was soluble in common organic solvents such as CHCl3 and THE The structures and properties of monomer and polymer were characterized and evaluated with FTIR, NMR, UV, TGA, GPC, and CV, respectively. The results show that the polymer possesses high thermal stability and well electron-injection property.

Effects of Various Dopants on Solitons in Polyacetylene

The effects of various dopants on solitons in polyacetylene were studied by using CNDO/2 level semiempirical quantum chemical method. The width of solitons is reduced when dopant is present, and the charge density wave(CDW) is further gathered on the carbon atom in soliton center. The effects of p-type of dopants are greater than those of n-type of ones. The charge transfer in doped polyacetylene can be achieved by the propagation of CDW along the chain. The conductivity of doped polyacetylene is proportional to the quantity of charge transfer between dopant and polyacetylene chain.

PHOTOCONDUCTIVITY STUDY OF NEW POLYACETYLENE DERIVATIVES WITH DIFFERENT SUBSTITUENTS

The photoconductivities of a series of novel polyacetylene derivatives （PAs） serving as charge generation materials in the single-layered photoreceptors were investigated using photoinduced xerographic discharge technique. It was found that the substitution can improve the photosensitivity of PAs by increasing the conjugation of π electrons. When the substituent is itself photoconductive, the photoconductivity becomes even higher. It can be concluded from cyclic voltammetry that when the HOMO level of the polymer is closer to that of the charge transport material, the photoconduction performance will be better.

Preparation and Nonlinear Optical Property of Azobenzene Substituted Polyacetylene

Two new functional polyacetylenes bearing different azobenzene group, -{ HC=C[azo-N （CH3）CH2CH2OH] } n-, [poly（EHAB）; azo = 4,4＇-azobenzene] and - { HC=C[azo-N（CH3）CH2CH2O COC3H7]},-, [poly（EEAB）]} were prepared by [Rh（nbd）Cl]2-Et3N catalysts. Poly（EHAB） has poor solubility while poly（EEAB） can be dissolved in common solvent. The polymers were characterized by FHR, ^1H NMR, UV and GPC. The nonlinear optical property of the soluble poly（EEAB） was investigated with 8 ns width pulse at 532 nm by Z-scan technique. The results show that poly（EEAB） is endowed with the larger third-order nonlinear optical property.

MECHANICAL PERTURBATION INDUCED MOLECULAR ALIGNMENTS IN A SIDE-CHAIN LIQUID CRYSTALLINE POLYACETYLENE, POLY{10-[4-(4'-METHOXYPHENOXY-CARBOML)PHENOXYCARBONYL]-1-DECYNE}

A new liquid crystalline polyacetylene containing a phenyl benzoate mesogen (5) is synthesized,whose mesomorphic properties are found to be easily 'tunab1e' by simple mechanical perturbation. Thepolymerization of 10- [ 4 - (4' -methoxyphenoxycarbonyl )phenoxycarbonyl] - 1 -decyne (4 ) in itiated by theWCl_6-Ph_4Sn/dioxane complex yields polymer 5 with a M_w of 28400. The molecular structure of 5 ischaracterized by NMR, IR, and UV spectroscopy and its liquid crystalline behavior is investigated by DSC,POM, and XRD analysis. Upon mechanical perturbation, 5 exhibits unusual agitation-induced high-strengthdisclinations, shear-induced inversion walls, and solidification-induced banded textures. Such phenomenahave been observed in the main-chain liquid crystalline polymers with rigid backbones, but have seldom beenreported for the side-chain liquid crystalline polymers with flexible backbones, suggesting that the rigidpolyacetylene backbone of 5 plays a constructive role in inducing the novel molecular alignments.

Antidiabetic Properties of Bidens pilosa and Its Polyacetylenic Compounds for Management of Diabetes: Systematic Review

Bidens pilosa is a member of the Asteraceae family that is widely distributed across the tropics. It has been utilized by different communities both as food and medicinal herb. This plant and its polyacetylenic compounds hold potential as a natural antidiabetic intervention that can be used to combat this global public health problem. Bioactive compounds found in this plant constitute promising interventions for combating obesity which is a major risk factor for the development of type 2 diabetes. These phytocompounds can work independently or synergistically to modulate appetite, lipase activity, adipogenesis and adipocyte apoptosis. However, the efficacy, mode of action and scope of management of diabetes by these compounds remains elusive. The current review aims to summarize data on efficacy in the management of diabetes, an antidiabetic candidate polyacetylenic compound and possible biological activities as an antidiabetic agent from the available literature. Much emphasis has been directed to cytopiloyne as a representative of polyacetylenic compounds extracted from Bidens pilosa and its activity on diabetic animal models. The majority of the studies conducted on animal models described antidiabetic mechanisms that range from hypoglycemic to secretagogue activity of cytopiloyne in a dose-dependent manner. A clinical trial pilot indicated improved glycemic control of Bidens pilosa formulation among diabetic patients in the study. Bidens pilosa and its compounds are highly potent antidiabetic agent(s) that should be graduated to an intervention for management of diabetes through pre-clinical and clinical trials to elucidate its efficacy and safety.

怀菊花茎叶中聚炔类化合物对ox-LDL诱导的HUVECs细胞损伤的保护作用

研究怀菊花茎叶中分离得到的聚炔类化合物对氧化低密度脂蛋白(oxidized low density lipoprotein,ox-LDL)诱导的人脐静脉内皮细胞(human umbilical vein endothelial cells,HUVECs)损伤的保护作用及初步探讨作用机制。采用ox-LDL(200μg/mL)处理HUVECs细胞建立内皮细胞损伤模型,同时给予聚炔类化合物1~10(100μg/mL)干预;通过CCK-8法检测细胞生存率,筛选出有细胞保护作用的目标化合物;采用目标化合物5和9(12.5、25、50、100μg/mL)干预细胞24 h,CCK-8检测细胞生存率,采用流式细胞术检测细胞凋亡率和活性氧(reactive oxygen species,ROS)生成率,酶联免疫(ELISA)检测细胞上清液中白介素-1β(interleukin-1β,IL-1β)、白介素-6(interleukin-6,IL-6)及肿瘤坏死因子-α(tumor necrosis factor-α,TNF-α)含量;细胞免疫印迹法(In-Cell Western)检测细胞中核转录因子-κB(nuclear transcription factor-κB,NF-κB)2p100/p52与NF-κBp65蛋白的相对表达水平。结果显示:与正常对照组(Con)相比,模型组(ox-LDL)中的细胞生存率明显下降,细胞凋亡率、ROS生成,炎性因子IL-1β、IL-6及TNF-α明显升高(P<0.01);与ox-LDL组相比,聚炔类化合物5和9可以明显提高HUVECs细胞的生存率、降低细胞凋亡率、ROS生成率,炎性因子IL-1β、IL-6及TNF-α的分泌(P<0.05或P<0.01),下调NF-κB2 p100/p52、NF-κB p65蛋白的表达(P<0.05或P<0.01)。综上所述,怀菊花茎叶中聚炔苷类成分可以改善ox-LDL诱导的HUVECs细胞损伤与功能障碍,其作用机制可能与NF-κB信号通路相关。

楤木属FAD2基因家族的鉴定及生物信息学分析

聚炔类化合物(PAs)是一类主要由桔梗类植物产生、具生物活性的植物特异性防御物质。其上游合成步骤由脂肪酸去饱和酶2(FAD2)催化。本文以PA的主要来源植物之一,桔梗类的五加科楤木属(Aralia)为研究对象,对楤木(A.elata(Miq.)Seem.)和龙眼独活(A.fargesii Franch.)的FAD2基因家族进行鉴定,并对其保守基序、结构域、染色体分布、基因共线性、进化关系、分子演化速率以及表达情况进行分析。结果显示,楤木属的FAD2基因家族经历了广泛扩张,这可能是通过全基因组加倍/片段重复实现的;不同功能的FAD2保守基序完全一致,但楤木属不同生活型(草本vs.木本)代表物种FAD2的保守基序却产生了分化;楤木中可能有4个不同功能的FAD2基因,其在不同组织中的表达情况不同。本研究可为后续楤木属的物种鉴定、聚炔类物质合成新基因的挖掘以及桔梗类植物具高度多样化PAs分子机制的揭示提供参考。

导电高分子材料制备及应用进展

导电高分子材料是一类具有导电性能的聚合物材料,通常是由一些有机单体聚合而成,由于其含有共轭的π-电子体系组成,使得电子能够在材料中进行自由移动,从而具有良好的导电性能。导电高分子材料在传感器技术、能源存储和转换、生物医学、电磁屏蔽材料、涂料和涂层等领域得到广泛的应用,主要综述了近几年来导电高分子材料最新研究进展,以及其在相关领域的应用。