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）...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）.展开更多
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. T...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.展开更多
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 wav...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.展开更多
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 prepa...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.展开更多
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^...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).展开更多
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 struc...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.展开更多
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 sp...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.展开更多
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) ...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...展开更多
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-propenyl...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).展开更多
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 cyclocarbo...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.展开更多
基金This work was supported by the National Natural Science Fund of China (Nos. 50073001 and 90206014)Program for New Century Excellent Talents in University (NCET-04-0588)the Outstanding Youth Fund of Anhui Province (No. 04044060)the Award for High Level Intellectuals (No. 2004Z027) from Anhui Province
文摘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）.
文摘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.
文摘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.
基金supported by the National Natural Science Foundation of China(Grant No.50073001 and 90206014)Program for New Century Excellent Talents in University(NCET-04-0588)+1 种基金the Outstanding Youth Fund of Anhui Province(Grant No.04044060)the Award for High Level Intellectuals(Grant No.2004Z027)from Anhui Province.
文摘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.
文摘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).
基金Supported by the National Natural Science F oundation of China( No.198340 70)
文摘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.
文摘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.
基金supported by the"Program for New Century Excellent Talents in University"(NCET-08-0204)"The Project Sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry(China)"
文摘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...
基金the National Natural Sciences Foundation of China(21302194).
文摘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).
文摘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.
