A novel brideed bis(β-cvclodextrin), 4, 4'-diaminodiphenyl ether-bfiged-bis (6-aimino-6-deoxv-β-cyclodextrin) 3, has been synthesized and its inclusion complexation behavior with three linear'guest dyes (AR, ...A novel brideed bis(β-cvclodextrin), 4, 4'-diaminodiphenyl ether-bfiged-bis (6-aimino-6-deoxv-β-cyclodextrin) 3, has been synthesized and its inclusion complexation behavior with three linear'guest dyes (AR, NR and MB ) has been investigated by. means of fluorescence spectrometry. The-result obtained demonstrated that the novel bridged bis(β-cyclodextnn) showed much higher affinities towards guest dyes than native β-cyclodextrin.展开更多
A novel organotin complex of μ-pentaoxygen bridged penta(bis-benzyltin) bissalicylate has been synthesized by the reaction of bis-benzyltin oxide and salicylic acid and its structure has been determined by X-ray di...A novel organotin complex of μ-pentaoxygen bridged penta(bis-benzyltin) bissalicylate has been synthesized by the reaction of bis-benzyltin oxide and salicylic acid and its structure has been determined by X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 1.7206(5), b = 2.1401(6), c = 2.1488(6)nm, β= 93.325(5)°, V = 7.899(4) nm^3, Z = 4, Dc = 1.564 g/cm^3,μ(MoKα) = 16.17cm^-1, Mr = 1859.94, F(000) = 3692, R1= 0.0755 and wR2= 0.1557. According to structural analysis, the coordination geometry of tin is a distorted trigonal bipyramid, and the ladder-like structure is shaped by four Sn2O2 planar four-membered rings.展开更多
The heterobinuclear complex of formula Cu (oxap )Gd(phen)2 (CIO4 )3 has been synthesized, where oxap denotes the N, N'-bis (2-aminopropyl )oxamido dianion and phen represents 1,10-phenanthroline. The complex was c...The heterobinuclear complex of formula Cu (oxap )Gd(phen)2 (CIO4 )3 has been synthesized, where oxap denotes the N, N'-bis (2-aminopropyl )oxamido dianion and phen represents 1,10-phenanthroline. The complex was characterized with ESR and variable temperature magnetic susceptibility (4- 300K). The least-squares fit of the experimental sosceptibilities yielded J=2. 25cm-1. The observed Gd (Ⅲ)-Cu (Ⅱ) coupling is ferromagnetic.One Plausible mechanism that can cause a ferromagnetic coupling between Gd(Ⅱ) and Cu (Ⅱ) is discussed in terms of spin-polarization.展开更多
Bis-silicon-bridged stilbene derivatives were synthesized in a modified procedure that combined the preparation of bis[2- (silyl)phenyl]acetylene and its intramolecular reductive cyclization in one pot. The results ...Bis-silicon-bridged stilbene derivatives were synthesized in a modified procedure that combined the preparation of bis[2- (silyl)phenyl]acetylene and its intramolecular reductive cyclization in one pot. The results indicated that the one pot approach produced target products in a comparable yield to that of the two-step method reported previously.展开更多
μ_2-O-and μ_2-dimethylglyoximato-bridged μ_3-O-tris[di(m-fluorobenzyl)tin] bis(dimethylglyoximate)(1) has been synthesized by the reaction of di(m-fluorobenzyl)tin dichloride with dimethylglyoxime. Complex ...μ_2-O-and μ_2-dimethylglyoximato-bridged μ_3-O-tris[di(m-fluorobenzyl)tin] bis(dimethylglyoximate)(1) has been synthesized by the reaction of di(m-fluorobenzyl)tin dichloride with dimethylglyoxime. Complex 1 was characterized by means of IR,~1H NMR,elemental analysis and X-ray diffraction. It crystallizes in orthorhombic system,space group Pna21 with a = 2.22172(12),b = 1.05566(6),c = 2.15577(12) nm,V = 5.0561(5) nm^3,Z = 4,C_(50)H_(50)F_6N_4O_6Sn_3,Mr = 1273.01,Dc = 1. 6721 g/cm3,μ_(MoΚα) = 15.44 cm^(-1),F(000) = 2520,R = 0.0281 and wR = 0.0683. The stabilities,orbital energies and composition characteristics of some frontier molecular orbitals of 1 have been investigated with the quantum chemistry calculation. The properties of thermogravimetric and vitro anticancer activities of the compound have been discussed.展开更多
A new bridging reagent, N,N ′\|bis(chloroacetyl)propylenediamine was used to explore the relative activity and bridging pattern of p \|tert\|buty lcalix\arene, p \|tert\|buty lcalix\arene and butyl...A new bridging reagent, N,N ′\|bis(chloroacetyl)propylenediamine was used to explore the relative activity and bridging pattern of p \|tert\|buty lcalix\arene, p \|tert\|buty lcalix\arene and butylcalix\arene. It was found that the bridging reaction is selectively, at least, preferably at 1,3\|position for p \|tert\|butylcalix\arene and p \|tert\|b utylcalix\arene, 1,5\|position for p \|tert \|butylcalix\arene. Taking the yield of bridged calixarene as a comparsion standard, the activity decreases with the increasing of the number of phenolic units in calixarene.展开更多
为快速构建并准确预测温度作用引起的斜拉桥主梁应变用于结构状态评估,基于某大跨度斜拉桥主梁超过1年的温度和应变监测数据,提出了一种基于迁移学习和双向长短时记忆(bi-directional long short-term memory,Bi-LSTM)神经网络的斜拉桥...为快速构建并准确预测温度作用引起的斜拉桥主梁应变用于结构状态评估,基于某大跨度斜拉桥主梁超过1年的温度和应变监测数据,提出了一种基于迁移学习和双向长短时记忆(bi-directional long short-term memory,Bi-LSTM)神经网络的斜拉桥温度-应变映射模型建立方法。首先,利用解析模态分解(analytical mode decomposition,AMD)去噪应变数据,得到仅由温度引起的应变响应;其次,选择温度和某一测点应变数据构成数据集,采用Bi-LSTM神经网络训练该数据集,并通过网络结构和超参数优化建立温度-应变Bi-LSTM基准模型;最后,利用迁移学习方法,将已训练好的基准模型中部分参数迁移到其他温度-应变数据集,建立相应的温度-应变映射被迁移模型,并与未采用迁移学习的神经网络训练方法进行对比。研究结果表明,相比直接建立的温度-应变Bi-LSTM神经网络映射模型,采用迁移学习方法建立的被迁移模型,其拟合精度均高于所用的基准模型,且训练时间短,预测误差小。展开更多
The synthesis of mono- and bis-1,3-diazabicyclo[3.1.0]hex-3-ene derivatives with indole ring and p-phenylene spacer, which behave as photochromic materials, is reported. The structure-photochromic behavior relationsh...The synthesis of mono- and bis-1,3-diazabicyclo[3.1.0]hex-3-ene derivatives with indole ring and p-phenylene spacer, which behave as photochromic materials, is reported. The structure-photochromic behavior relationship (SPBR) of the synthesized compounds has been analyzed.展开更多
By 1,4-bridging of p-tert-butylcalix [6] arene with 2,6-bis (bromomethyl)-4-methyl- anisole, a new type of bis-calix [5] arene analogue was obtained in high yield..
The synthesis and characterization of aluminum alkoxide and alkyl complexes stabilized by piperazidine- bridged bis(phenolate) ligands are described. Treatment of ligand precursors Hz[ONNO]^1 {Hz[ONNO]^1= 1,4-bis(2...The synthesis and characterization of aluminum alkoxide and alkyl complexes stabilized by piperazidine- bridged bis(phenolate) ligands are described. Treatment of ligand precursors Hz[ONNO]^1 {Hz[ONNO]^1= 1,4-bis(2-hydroxy-3-tert-butyl-5-methylbenzyl)piperazidine} and Hz[ONNO]2 {H2[ONNO]2=1,4-bis(2-hydroxy3,5-di-tert-butylbenzyl)piperazidine} with A1Et2(OCH2Ph) and A1Etz(OPr-i), which were generated in situ by the reactions of AIEt3 with equivalent of the corresponding alcohols, in a 1: 1 molar ratio in THF gave the corresponding aluminum alkoxide complexes [ONNO]IAI(OCH2Ph) (1) and [ONNO]2Al(OPr-i) (2), respectively. The reaction of H2[ONNO]^1 with A1Etz(OCHzPh) in a 1 : 2 molar ratio in THF afforded a mixture of monometallic aluminum ethyl complex [ONNO] 1A1Et (3) and complex 1, which can be isolated by stepwise crystallization. Similarly, Hz[ONNO]2 reacted with A1Etz(OPr-0 in a 1: 2 molar ratio in THF to give a mixture of aluminum ethyl complex [ONNO]2AlEt (4) and complex 2. Complexes 1 and 2 were also available via treatment of complexes 3 and 4 with 1 equiv, of benzyl alcohol and isopropyl alcohol, respectively. All of these complexes were fully characterized including X-ray structural determination. It was found that complexes 1 to 4 can initiate the ring-opening polymerization of e-caprolactone, and complexes 1 and 2 showed higher catalytic activity in comparison with com- plexes 3 and 4.展开更多
Polyoxometalates(POMs) with Cd-coordination complexes acting as supporting units are rarely reported. The linkage of the supporting units with inorganic building block(polyanion) is generally established on termin...Polyoxometalates(POMs) with Cd-coordination complexes acting as supporting units are rarely reported. The linkage of the supporting units with inorganic building block(polyanion) is generally established on terminal O-atoms, but scarcely via bridging O-atoms. By introducing liquid small organic molecule(pyridine, C5NH5) as assistant "structure-directing agent", we obtained a novel organic-inorganic hybrid polytungstate,(Hpy)4[Cd(phen)2(P2W18O62)]·nH2O(1, n ≈ 3, py = pyridine, phen = 1,10-phenanthroline), under hydrothermal conditions. The single-crystal X-ray diffraction analysis shows that 1 is the first compound containing an asymmetric heteropolyanion, [Cd(phen)2(P2W18O62)]4–, a Wells-Dawson-type polyanion monosupported by Cd-coordination complex via di-bridging O-atoms.展开更多
A Novel β-cyclodextrin dimer,2,2′-o-phenylenediseleno-bridgedbis(β-cyclodextrin)(2),has been synthesized by reaction ofmono-[2-O-(p-tolylsulfonyl)]-β-cyclodextrin and poly(o-phenylenediselenide).The comple...A Novel β-cyclodextrin dimer,2,2′-o-phenylenediseleno-bridgedbis(β-cyclodextrin)(2),has been synthesized by reaction ofmono-[2-O-(p-tolylsulfonyl)]-β-cyclodextrin and poly(o-phenylenediselenide).The complexation stability constants(Ks)and Gibbs free energy changes(-ΔG°)of dimer 2 with fourfluorescence dyes,that is,ammonium 8-anilino-1-naphthalene-sulfonate(ANS),sodium 6-(p-toluidino)-2-naphthalenesul-fonate(TNS),Acridine Red(AR)and Rhodamine B(RhB)have been determined in aqueous phosphate buffer solution(pH=7.2,0.1 mol·L-1at 25℃ by means of fluorescence spec-展开更多
A series of bimetallic lanthanide bis(amido) complexes stabilized by bridged bis(guanidinate) ligands {[(Me3Si)2N]2Ln[(RN)2-CN(CH2)2]}2 [R=iPr, Ln=Sm(1), Yb(2), Y(3); R=cyclohexyl(Cy), Ln=Sm(4), and Yb(5)] were synthe...A series of bimetallic lanthanide bis(amido) complexes stabilized by bridged bis(guanidinate) ligands {[(Me3Si)2N]2Ln[(RN)2-CN(CH2)2]}2 [R=iPr, Ln=Sm(1), Yb(2), Y(3); R=cyclohexyl(Cy), Ln=Sm(4), and Yb(5)] were synthesized through the metathesis reactions of {Ln(μ-Cl)[N(Si Me3)2]2(THF)}2(Ln=Sm, Yb, Y) with lithium guanidinate {Li[(RN)2CN(CH2)2]}2(R=iPr, Cy), the latter of which was generated in situ by the reaction of carbodiimides with lithium amides. Complexes 1–5 were well characterized by elemental analyses, IR spectra, and(for Complex 3) NMR spectroscopy. The solid-state molecular structures of all of the complexes were determined by single-crystal X-ray analyses with the exception of Complex 3, which showed similar unsolvated centrosymmetric dinuclear structures. Each of the lanthanide centers is four-coordinated with two nitrogen atoms from a guanidinate ligand and two nitrogen atoms from two amido groups. The piperazidine rings adopt chair conformations in all cases. These organolanthanide complexes were found to be efficient catalysts for the hydrophosphonylation reaction of various aldehydes and unactivated ketones and to afford ?-hydroxyphosphonates in high yields under low catalyst loading(0.1 mol%) in a short reaction time.展开更多
基金supported by the Yunnan Province Natural Science Foundation (Nos. 2003C009M and 2003B0014Q)
文摘A novel brideed bis(β-cvclodextrin), 4, 4'-diaminodiphenyl ether-bfiged-bis (6-aimino-6-deoxv-β-cyclodextrin) 3, has been synthesized and its inclusion complexation behavior with three linear'guest dyes (AR, NR and MB ) has been investigated by. means of fluorescence spectrometry. The-result obtained demonstrated that the novel bridged bis(β-cyclodextnn) showed much higher affinities towards guest dyes than native β-cyclodextrin.
基金This work was supported by the Natural Science Foundation (05JJ40015) and Basic Research(03JZY3036) of the Hunan Province ,Key Foundation of Education Committee of HuNan Province(03A009) and Sustentation Fund of HenYang Science& Technology bureau (2004-25, 2005KG01-09)
文摘A novel organotin complex of μ-pentaoxygen bridged penta(bis-benzyltin) bissalicylate has been synthesized by the reaction of bis-benzyltin oxide and salicylic acid and its structure has been determined by X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 1.7206(5), b = 2.1401(6), c = 2.1488(6)nm, β= 93.325(5)°, V = 7.899(4) nm^3, Z = 4, Dc = 1.564 g/cm^3,μ(MoKα) = 16.17cm^-1, Mr = 1859.94, F(000) = 3692, R1= 0.0755 and wR2= 0.1557. According to structural analysis, the coordination geometry of tin is a distorted trigonal bipyramid, and the ladder-like structure is shaped by four Sn2O2 planar four-membered rings.
文摘The heterobinuclear complex of formula Cu (oxap )Gd(phen)2 (CIO4 )3 has been synthesized, where oxap denotes the N, N'-bis (2-aminopropyl )oxamido dianion and phen represents 1,10-phenanthroline. The complex was characterized with ESR and variable temperature magnetic susceptibility (4- 300K). The least-squares fit of the experimental sosceptibilities yielded J=2. 25cm-1. The observed Gd (Ⅲ)-Cu (Ⅱ) coupling is ferromagnetic.One Plausible mechanism that can cause a ferromagnetic coupling between Gd(Ⅱ) and Cu (Ⅱ) is discussed in terms of spin-polarization.
文摘Bis-silicon-bridged stilbene derivatives were synthesized in a modified procedure that combined the preparation of bis[2- (silyl)phenyl]acetylene and its intramolecular reductive cyclization in one pot. The results indicated that the one pot approach produced target products in a comparable yield to that of the two-step method reported previously.
基金Supported by the Open Fund Project of Key Laboratory of Functional Organometallic Materials of Hengyang Normal University(15K017,14K014,13K105)Natural Science Foundation of Hunan Province(No.13JJ3112)+1 种基金Scientific&Technological Projects of Hunan Province(No.2014NK3086)Aid programs for Science and Technology Innovative Research Team in Higher Educational Institutions of Hunan Province,the Key Discipline of Hunan Province,Project funding for research and innovation experiment of university students in Hunan Province,and the Scientific Research Fund of Hunan Provincial Education Department of China(No.14C0171,14C0168,15C0199,15C0200)
文摘μ_2-O-and μ_2-dimethylglyoximato-bridged μ_3-O-tris[di(m-fluorobenzyl)tin] bis(dimethylglyoximate)(1) has been synthesized by the reaction of di(m-fluorobenzyl)tin dichloride with dimethylglyoxime. Complex 1 was characterized by means of IR,~1H NMR,elemental analysis and X-ray diffraction. It crystallizes in orthorhombic system,space group Pna21 with a = 2.22172(12),b = 1.05566(6),c = 2.15577(12) nm,V = 5.0561(5) nm^3,Z = 4,C_(50)H_(50)F_6N_4O_6Sn_3,Mr = 1273.01,Dc = 1. 6721 g/cm3,μ_(MoΚα) = 15.44 cm^(-1),F(000) = 2520,R = 0.0281 and wR = 0.0683. The stabilities,orbital energies and composition characteristics of some frontier molecular orbitals of 1 have been investigated with the quantum chemistry calculation. The properties of thermogravimetric and vitro anticancer activities of the compound have been discussed.
基金Projects(52078487,U1934207,52178180)supported by the National Natural Science Foundations of ChinaProjects(2022YFB2302603,2022YFC3004304)supported by the National Key Research and Development Program of China+2 种基金Project(2022TJ-Y10)supported by the Hunan Province Science and Technology Talent Lifting,ChinaProject(SKL-IOTSC(UM)-2021-2023)supported by the Science and Technology Development Fund,ChinaProject(SKL-IoTSC(UM)-2024-2026/ORP/GA08/2023)supported by the State Key Laboratory of Internet of Things for Smart City(University of Macao),China。
文摘A new bridging reagent, N,N ′\|bis(chloroacetyl)propylenediamine was used to explore the relative activity and bridging pattern of p \|tert\|buty lcalix\arene, p \|tert\|buty lcalix\arene and butylcalix\arene. It was found that the bridging reaction is selectively, at least, preferably at 1,3\|position for p \|tert\|butylcalix\arene and p \|tert\|b utylcalix\arene, 1,5\|position for p \|tert \|butylcalix\arene. Taking the yield of bridged calixarene as a comparsion standard, the activity decreases with the increasing of the number of phenolic units in calixarene.
文摘The synthesis of mono- and bis-1,3-diazabicyclo[3.1.0]hex-3-ene derivatives with indole ring and p-phenylene spacer, which behave as photochromic materials, is reported. The structure-photochromic behavior relationship (SPBR) of the synthesized compounds has been analyzed.
基金Financial supports from the National Natural Science Foundation of China and Hubei province are gratefully acknowledged.
文摘By 1,4-bridging of p-tert-butylcalix [6] arene with 2,6-bis (bromomethyl)-4-methyl- anisole, a new type of bis-calix [5] arene analogue was obtained in high yield..
文摘The synthesis and characterization of aluminum alkoxide and alkyl complexes stabilized by piperazidine- bridged bis(phenolate) ligands are described. Treatment of ligand precursors Hz[ONNO]^1 {Hz[ONNO]^1= 1,4-bis(2-hydroxy-3-tert-butyl-5-methylbenzyl)piperazidine} and Hz[ONNO]2 {H2[ONNO]2=1,4-bis(2-hydroxy3,5-di-tert-butylbenzyl)piperazidine} with A1Et2(OCH2Ph) and A1Etz(OPr-i), which were generated in situ by the reactions of AIEt3 with equivalent of the corresponding alcohols, in a 1: 1 molar ratio in THF gave the corresponding aluminum alkoxide complexes [ONNO]IAI(OCH2Ph) (1) and [ONNO]2Al(OPr-i) (2), respectively. The reaction of H2[ONNO]^1 with A1Etz(OCHzPh) in a 1 : 2 molar ratio in THF afforded a mixture of monometallic aluminum ethyl complex [ONNO] 1A1Et (3) and complex 1, which can be isolated by stepwise crystallization. Similarly, Hz[ONNO]2 reacted with A1Etz(OPr-0 in a 1: 2 molar ratio in THF to give a mixture of aluminum ethyl complex [ONNO]2AlEt (4) and complex 2. Complexes 1 and 2 were also available via treatment of complexes 3 and 4 with 1 equiv, of benzyl alcohol and isopropyl alcohol, respectively. All of these complexes were fully characterized including X-ray structural determination. It was found that complexes 1 to 4 can initiate the ring-opening polymerization of e-caprolactone, and complexes 1 and 2 showed higher catalytic activity in comparison with com- plexes 3 and 4.
基金supported by the Foundation of Education Department of Fujian Province(Nos.JB12199 and JA11245)the National Natural Science Foundation of China(Nos.21233004 and 40972035)
文摘Polyoxometalates(POMs) with Cd-coordination complexes acting as supporting units are rarely reported. The linkage of the supporting units with inorganic building block(polyanion) is generally established on terminal O-atoms, but scarcely via bridging O-atoms. By introducing liquid small organic molecule(pyridine, C5NH5) as assistant "structure-directing agent", we obtained a novel organic-inorganic hybrid polytungstate,(Hpy)4[Cd(phen)2(P2W18O62)]·nH2O(1, n ≈ 3, py = pyridine, phen = 1,10-phenanthroline), under hydrothermal conditions. The single-crystal X-ray diffraction analysis shows that 1 is the first compound containing an asymmetric heteropolyanion, [Cd(phen)2(P2W18O62)]4–, a Wells-Dawson-type polyanion monosupported by Cd-coordination complex via di-bridging O-atoms.
基金Project supported by the National Natural Science Foundation of China(Nos.29992590-8 and 20272028),the Natural Science Fund of Tianjin(No.013613511)and Special Fund for Doctoral Program from the Ministry of Education of China(No.20010055001).
文摘A Novel β-cyclodextrin dimer,2,2′-o-phenylenediseleno-bridgedbis(β-cyclodextrin)(2),has been synthesized by reaction ofmono-[2-O-(p-tolylsulfonyl)]-β-cyclodextrin and poly(o-phenylenediselenide).The complexation stability constants(Ks)and Gibbs free energy changes(-ΔG°)of dimer 2 with fourfluorescence dyes,that is,ammonium 8-anilino-1-naphthalene-sulfonate(ANS),sodium 6-(p-toluidino)-2-naphthalenesul-fonate(TNS),Acridine Red(AR)and Rhodamine B(RhB)have been determined in aqueous phosphate buffer solution(pH=7.2,0.1 mol·L-1at 25℃ by means of fluorescence spec-
基金supported by the National Natural Science Foundation of China(21132002,21372172,21402138)the Major Research Project of the Natural Science Foundation of the Jiangsu Higher Education Institutions(14KJA150007)the Qing Lan Project
文摘A series of bimetallic lanthanide bis(amido) complexes stabilized by bridged bis(guanidinate) ligands {[(Me3Si)2N]2Ln[(RN)2-CN(CH2)2]}2 [R=iPr, Ln=Sm(1), Yb(2), Y(3); R=cyclohexyl(Cy), Ln=Sm(4), and Yb(5)] were synthesized through the metathesis reactions of {Ln(μ-Cl)[N(Si Me3)2]2(THF)}2(Ln=Sm, Yb, Y) with lithium guanidinate {Li[(RN)2CN(CH2)2]}2(R=iPr, Cy), the latter of which was generated in situ by the reaction of carbodiimides with lithium amides. Complexes 1–5 were well characterized by elemental analyses, IR spectra, and(for Complex 3) NMR spectroscopy. The solid-state molecular structures of all of the complexes were determined by single-crystal X-ray analyses with the exception of Complex 3, which showed similar unsolvated centrosymmetric dinuclear structures. Each of the lanthanide centers is four-coordinated with two nitrogen atoms from a guanidinate ligand and two nitrogen atoms from two amido groups. The piperazidine rings adopt chair conformations in all cases. These organolanthanide complexes were found to be efficient catalysts for the hydrophosphonylation reaction of various aldehydes and unactivated ketones and to afford ?-hydroxyphosphonates in high yields under low catalyst loading(0.1 mol%) in a short reaction time.