Acryloyl terminated Poly (ethyleneoxide)macromonomers (PEO-A) with different PEO chain lengths have been prepared by deactivation of PEO alkoxide with acryloyl chloride. A new kind of amphiphilic polystyrene-g-poly (e...Acryloyl terminated Poly (ethyleneoxide)macromonomers (PEO-A) with different PEO chain lengths have been prepared by deactivation of PEO alkoxide with acryloyl chloride. A new kind of amphiphilic polystyrene-g-poly (ethylene oxide)graft copolymer containing both microphase separated and PEO side chain structures has been synthesized from radical copolymerization of PEO-A macromonomer with styrene. After careful purification by a newly-developed method called 'selective dissolution', the well-defined structure of the purified copolymers was confirmed by IR, ~1H-NMR and GPC. Various experimental parameters controlling the copolymerization were studied in detail. The results indicated that the feed ratio of styrene to macromonomer(S/M) was the most important determining factor for the composition of the copolymers. A detailed 'comb- model' was proposed to describe the molecular structure of the graft copolymers. Finally, this amphiphilic graft copolymers may readily form microphase separated structures as clearly indicated by transmission electron microscopy.展开更多
The structures and properties of benzoxazines were investigated by virtue of molecular modeling at a molecular level. By means of Cerius software(version 4.0) supplied by Molecular Simulations Inc., the molecular mech...The structures and properties of benzoxazines were investigated by virtue of molecular modeling at a molecular level. By means of Cerius software(version 4.0) supplied by Molecular Simulations Inc., the molecular mechanics and the molecular dynamics were performed under a PCFF force field. Five kinds of the polymeric chains of benzoxazines were created by using polymer builder and energy minimization. The relaxation process was conducted with both energy minimization and molecular dynamics.展开更多
Two polyethylene（PE） resins（samples A and B） are synthesized as high-speed extrusion coatings with similar minimum coating thickness and neck-in performance but different maximum coating speeds. Both samples are s...Two polyethylene（PE） resins（samples A and B） are synthesized as high-speed extrusion coatings with similar minimum coating thickness and neck-in performance but different maximum coating speeds. Both samples are separated into seven fractions using preparative temperature rising elution fractionation. The microstructures of the original samples and their fractions are studied by high-temperature gel permeation chromatography, Fourier transform infrared spectroscopy, 13 C nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and successive self-nucleation/annealing thermal fractionation. Compared with sample B, sample A has a broader MWD, more LCB contents, and less SCB contents. Moreover, sample A contains slightly more 30 ℃ and 50 ℃ fractions with lower molecular weights, and more fractions at 75 ℃ and 85 ℃ with higher molecular weight. The chain structure and its distribution in the two PE resins are studied in detail, and the relationship between the chain structure and resin properties is also discussed.展开更多
Ultra-high molecular weight polyethylene(UHMWPE)is widely utilized in low-dimensional materials due to its ultra-long chain imparted excellent strength and modulus.By employing gel-molding technology with a gradient t...Ultra-high molecular weight polyethylene(UHMWPE)is widely utilized in low-dimensional materials due to its ultra-long chain imparted excellent strength and modulus.By employing gel-molding technology with a gradient temperature control,this study successfully produced gel films with varying shish crystal contents of the UHMWPE with a molecular weight of 8.0 million.The structural evolution during film hotstretching was investigated by in-situ wide-angle X-ray diffraction(WAXD),small-angle X-ray scattering(SAXS),ultra-small-angle X-ray scattering(USAXS),and ex-situ methods of scanning electron microscopy(SEM)and differential scanning calorimetry(DSC).The ultra-long molecular chains delay stress transfer during stretching but provide more nucleation sites for shish-kebab crystallization to form well-ordered shish-kebab crystals under high strain.The reserved high-content shish facilitates structural evolution,inducing the formation of highly-ordered shish-kebab crystals that eventually transfer into shish crystals in the later stage of stretching.The samples with low shish content,although the structural evolution is facilitated during stretching,predominantly result in newly formed shish-kebab crystals through melt recrystallization.However,some unoriented lamellae persists in unreserved samples stretching progress,leading to less ordered shish-kebab structures.By comparing with previous work of UHMWPE with low molecular weights,we demonstrate that the ultra-long molecular chains also play a key role on enabling the construction of highly-ordered shish-kebab crystals with high shish content during hot-stretching of UHMWPE gel films,providing new insights into processing control and optimization for engineering applications.展开更多
The syntheses and structures of eleven novel polymeric transition metal complexes having one dimensional chain structures or three dimensional networks are summarized. They are prepared from the controlled assemblin...The syntheses and structures of eleven novel polymeric transition metal complexes having one dimensional chain structures or three dimensional networks are summarized. They are prepared from the controlled assembling reactions in organic solvents and characterized by X ray diffraction analyses. The spectroscopic or magnetic properties of some complexes are studied.展开更多
The mechanical behavior of polymer networks is intrinsically correlated with the local chain topology and chain connectivity.In this study,we delve into this relationship through the lens of coarse-grained molecular d...The mechanical behavior of polymer networks is intrinsically correlated with the local chain topology and chain connectivity.In this study,we delve into this relationship through the lens of coarse-grained molecular dynamics(CG-MD)simulations.Our aim is to illuminate the intricate interplay between local topology and stress distribution within polymer monomers,cross-linkers,and various components with distinct cross-link connections,thereby elucidating their collective impact on the mechanical properties of polymer networks.We mainly focus on how specific local structures contribute to the overall mechanical response of the network.In particular,we employ local stress analysis to unravel the mechanics of these structures.Our findings reveal the diverse responses of individual components,such as junctions,strands,cross-linkers between junctions,and dangling chain ends,when subjected to stretching.Notably,we observe that these components exhibit varying degrees of deformation tolerance,underscoring the significance of their roles in determining the mechanical characteristics of the network.Our investigations highlight junctions as primary contributors to stress accumulation,and particles with higher local stress showing a stronger correlation between stress and Voronoi volume.Moreover,our results indicate that both strands and cross-linkers between junctions exhibit heightened stress levels as strand lengths decrease.This study enhances our understanding of the multifaceted factors governing the mechanical attributes of cross-linked polymer systems at the microstructural level.展开更多
A new organo-directed titanium phosphate, [NH3CH2CH2NH3]·[TiO(HPO4)2], was synthesized by the solvothermal method and its structure was determined by single crystal X-ray diffraction. The structure consists of 1-...A new organo-directed titanium phosphate, [NH3CH2CH2NH3]·[TiO(HPO4)2], was synthesized by the solvothermal method and its structure was determined by single crystal X-ray diffraction. The structure consists of 1-D zigzag chains built up from trans-corner-sharing titanium oxo octahedra running along the b axis, with fused Ti2P three-membered rings being attached to the ( Ti ( O ( Ti ( O ( backbone.展开更多
A new one-dimensional（ID） fluoroaluminophosphate chain（C4H15N3）[AlPO4F2]（denoted AIPO-CJ28） was synthesized in the concentrated fluoride synthetic medium with a gel composition of 1.0Al（OPr^1）a：1.0H3PO4： 5.4...A new one-dimensional（ID） fluoroaluminophosphate chain（C4H15N3）[AlPO4F2]（denoted AIPO-CJ28） was synthesized in the concentrated fluoride synthetic medium with a gel composition of 1.0Al（OPr^1）a：1.0H3PO4： 5.4DETA：1.3HF：2.0H2O（DETA=diethylenetriamine）. The reagents were mixed directly without introducing additional water solvent. The 1D chain is constructed by alternating AlO2F2 arid doubly bridging PO4 tetrahedra to form the simplest serrate chain. AIPO-CJ28 can be transformed to another 1D aluminophosphate chain A1PO-CSC upon further crystallization at 230 ℃.展开更多
Through improvements on a fully commercial and automatic system measuring frequency andtemperature spectra of the complex elastic, dielectric, and piezoelectric constants of polymerfilms, the precision for measuring c...Through improvements on a fully commercial and automatic system measuring frequency andtemperature spectra of the complex elastic, dielectric, and piezoelectric constants of polymerfilms, the precision for measuring complex dielectric constants achieved 2‰ from original 1%.The complex dielectric constants of PVDF, VDF （95 ）/VF （5）, VDF （52）/TrFE （48） and VDF（47. 5）/TrFE（47. 5）/HeFP （5） over a range of-120-140℃, 10-2-10;Hz were measured bythe described system. The diminution of chain regularity due to 5mol% vinyl fluoride in the chainof PVDF led to disappearing of α-relaxation and increase in T;（3℃） of VDF （95）/VF （5）.Because of the spatial impediment of 5mol% HeFP in copolymer chain, the Curie point of VDF（52）/TrFE（48） decreased by 30℃ and T;by 3℃. The behavior of dielectric relaxation indicatedthat 5mol% vinyl fluoride and HeFP made the relaxation strength of noncrystalline regionreduced, the activation energy of local relaxation increased and the relaxation time prolonged respectively.展开更多
The chemical composition, molecular weight and its distribution, the bonding structure and the regulation of ultrahigh molecular weight polyacrylonitrile （UHMW-PAN） prepared by aqueous suspension polymerization were...The chemical composition, molecular weight and its distribution, the bonding structure and the regulation of ultrahigh molecular weight polyacrylonitrile （UHMW-PAN） prepared by aqueous suspension polymerization were determined by FIIR, viscometry, GPC, ^3H-NMR and ^13CNMR. The mechanical properties of the porous hollow fiber prepared by UHMW-PAN were discussed to provide a theoretical basis for the preparation of ideal precursors of the porous hollow oxidation fiber.展开更多
We consider an entangled Ising-XY Z diamond chain structure. Quantum correlations for this model are inves- tigated by using quantum discord and trace distance discord. Quantum correlations are obtained for different ...We consider an entangled Ising-XY Z diamond chain structure. Quantum correlations for this model are inves- tigated by using quantum discord and trace distance discord. Quantum correlations are obtained for different values of the anisotropy parameter, magnetic field and temperature. By comparison between quantum correlations, we show that the trace distance discord is always larger than quantum discord. Finally, some novel effects such as increasing the quantum correlations with temperature and constructive role of anisotropy parameter, which may play to the quantum correlations, are observed.展开更多
Ta_4(Te_2)_4Te_4I,Mr=2381.90,Monoclinic,C2/c,a=21.987(2),b=6.153(2),c= 19.936(3),β=122.42(14),V=2276.7 ~3,z=4,Dm=6.8(5)g/cm^3,Dc=6.95g/cm^3,λ(Mok)= 0.71073,μ=354.0cm^(-1),F(000)=3876,T=296(1)k,R=5.3%,Rw=6.8%,for 11...Ta_4(Te_2)_4Te_4I,Mr=2381.90,Monoclinic,C2/c,a=21.987(2),b=6.153(2),c= 19.936(3),β=122.42(14),V=2276.7 ~3,z=4,Dm=6.8(5)g/cm^3,Dc=6.95g/cm^3,λ(Mok)= 0.71073,μ=354.0cm^(-1),F(000)=3876,T=296(1)k,R=5.3%,Rw=6.8%,for 1118 unique observed reflections(1>3σ(Ⅰ)).The structure is composed of [Ta_4(Te_2)_4Te_4I]_∞~ chains,which are formed by the four-nuclear butterfly cluster units "Ta_4(Te_2)_4Te_4" with the Ⅰ atoms as the bridging atoms between different cluster units.展开更多
The crystal structure of[Cu(2-thienoyl-trifluoroacetone)(4,4—bipyridine)]_n was determined by X-ray diffraction analysis. The crystal belongs to monoclinie with the space group C2/c, Mr=440.91, a=9.640(5) A, b=24.97(...The crystal structure of[Cu(2-thienoyl-trifluoroacetone)(4,4—bipyridine)]_n was determined by X-ray diffraction analysis. The crystal belongs to monoclinie with the space group C2/c, Mr=440.91, a=9.640(5) A, b=24.97(1) A, c=16.032(7) A, β=106.76(3)°,V=3695(3) A^3, Z=8, Dc=1.58g/cm^3, F(000)=1776. Final R and Rw are 0.062 and 0.069, respectively. The local coordination geometry around Cu(I) ion is a distorted tetrahedron. Cu(TTA) are linked with 4,4-bipyridine, forming long chain in the crystal.展开更多
Two new crystals of chlorovanadates,Ba_8Cs_5V_8O_（24）Cl_（13）（1） and MgCsV_2O_6Cl（2）,were grown in the molten salt media. 1 crystallizes in tetragonal,space group P4/mmm（No. 123）,with a = 14.801（2）,c = 12....Two new crystals of chlorovanadates,Ba_8Cs_5V_8O_（24）Cl_（13）（1） and MgCsV_2O_6Cl（2）,were grown in the molten salt media. 1 crystallizes in tetragonal,space group P4/mmm（No. 123）,with a = 14.801（2）,c = 12.341（3） ？,V = 2703.5（8） ？~3,Z = 2,Mr = 3015.56,F（000） = 2640,μ = 11.044 mm-1,Dc = 3.704 g/cm3,the final R = 0.0380 and wR = 0.0937 for 1654 observed reflections with I 〉 2σ（I）. 2 crystallizes in a monoclinic space group C2/c（No. 15） with a = 11.128（2）,b = 10.540（2）,c = 6.9892（14） ？,β = 118.38（3）°,V = 721.2（2） ？~3,Z = 4,M_r = 390.55,F（000） = 712,μ = 7.997 mm-1,D_c = 3.597 g/cm^3,the final R = 0.0537 and w R = 0.1363 for 740 observed reflections with I 〉 2σ（I）. 1 exhibits a novel 8-membered-ring [V_8O_（24）] consisting of 8 corner-shared VO_4 tetrahetra,but in 2,an infinite ladder-like [VO_3]_∞ chain is formed by VO_5 square pyramids through sharing the edges.展开更多
A theoretical study on oligopeptide chains of glycine-alanine by density functional theory（DFT） is given in this paper. Raman spectra of the oligopeptide chains are examined. The geometric structures, frontier orbit...A theoretical study on oligopeptide chains of glycine-alanine by density functional theory（DFT） is given in this paper. Raman spectra of the oligopeptide chains are examined. The geometric structures, frontier orbital, energy gap, atomic charge distribution, density of states and chemical activity of the side chain are studied at the B3LYP/6-31G（d） level. Results show that, with the number of residues increasing, vibrations of typical functional groups present Raman frequency shift, and the energy gap is gradually reduced. The HOMO and LUMO focus on the amino and carboxyl at the ends of oligopeptides. It is helpful for oligopeptides to self-assemble into chains. In addition, different residues（glycine or alanine） at the ends of chains result in the even-odd effect of orbital energy in the growth process. The size effects of physical and chemical properties only exist when the oligopeptides are shorter, and the phenomenon disappeared as the chain continues to grow.展开更多
The article describes ethylene polymerization reactions with transition metal catalysts based on complexes of CoCl_(2) and FeCl_(2) with an N,N,N-tridentate ligand 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine. Th...The article describes ethylene polymerization reactions with transition metal catalysts based on complexes of CoCl_(2) and FeCl_(2) with an N,N,N-tridentate ligand 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine. The complexes are converted into polymerization catalysts by reacting them either with polymethylalumoxane (MAO) or with a combination of Al(C2H5)2Cl and Mg(C4H9)2 at an [Al]:[Mg] ratio of ~3. Both MAO-activated complexes readily polymerize ethylene at 35 ℃ with the formation of linear, low molecular weight polymers with a narrow molecular weight distribution. The same complexes, when activated with the Al(C2H5)2Cl-Mg(C4H9)2 combination, form multi-center catalysts and generate polyethylenes with a broad molecular weight distribution.展开更多
The linear-chain structure in which three alpha particles are arranged in a straight line was initially proposed by H.Morinaga[1]as the structure of the Hoyle state of carbon-12[2].This unique idea attracted much atte...The linear-chain structure in which three alpha particles are arranged in a straight line was initially proposed by H.Morinaga[1]as the structure of the Hoyle state of carbon-12[2].This unique idea attracted much attention,but it was rejected because it could not explain the lifetime of the Hoyle state.Half a century later,the concept of the linear chain structure was revived in the physics of unstable nuclei,and experimental and theoretical research have demonstrated that this structure exists in carbon-14 and 16.The authors have conducted internationally recognized experimental research on the linear-chain structure of carbon-14 and carbon-16.展开更多
Two novel silver（I） complexes {[Ag（OTf）（PPh3）（4,4＇-bipy）]}∞（1） and {[Ag2-（OTf）2（dppb）3]（CH3CN）4}∞（2）（OTf = trifluoromethanesulfonate, PPh3 = triphenylphophine, 4,4＇-bipy = 4,4＇-bipyridine, dppb...Two novel silver（I） complexes {[Ag（OTf）（PPh3）（4,4＇-bipy）]}∞（1） and {[Ag2-（OTf）2（dppb）3]（CH3CN）4}∞（2）（OTf = trifluoromethanesulfonate, PPh3 = triphenylphophine, 4,4＇-bipy = 4,4＇-bipyridine, dppb = bis（diphenylphosphino）butane） have been synthesized and characterized by IR, single-crystal X-ray diffraction, fluorescence spectrum and 1H NMR spectroscopy. Complex 1 crystallizes in orthorhombic, space group Pna21 with a = 19.259（2）, b = 9.85070（12）, c = 16.3827（17） A, V = 3108.0（5） A3, C29H23F3N2O3 PSAg, Mr = 675.39, Z = 4, Dc = 1.443 g/cm3, F（000） = 1360, μ = 0.816 mm-1, the final R = 0.0675 and w R = 0.1722 for 3662 observed reflections（I 〉 2σ（I））. Complex 2 crystallizes in triclinic, space group P1 with a = 12.9370（11）, b = 13.5261（13）, c = 16.4539（15） A, α = 106.7120（10）, β = 97.3830（10）, γ = 113.027（2）A, V = 2441.2（4）A3, C94H96F6N4O6P6S2Ag2, Mr = 1957.43, Z = 1, Dc = 1.331 g/cm3, F（000） = 1006, μ = 0.605 mm-1, the final R = 0.0717 and w R = 0.1795 for 5128 observed reflections（I 〉 2σ（I））. Complex 1 is of zigzag chain structure, in which each Ag atom is coordinated by one OTf- anion, two N atoms from two 4,4＇-bipy molecules and one P atom from PPh3 ligand. In 2, the central Ag atom is coordinated with one OTf- anion and three P atoms from three dppb ligands, which leads to the formation of a zigzag ring-bridge-ring chain with each ring consisting of two Ag atoms and two dppb ligands.展开更多
The compositional heterogeneity of two impact polypropylene copolymers（IPCs） was studied by a combinatory investigation of temperature rising elution fractionation（TREF） and solvent fractionation.The chain structu...The compositional heterogeneity of two impact polypropylene copolymers（IPCs） was studied by a combinatory investigation of temperature rising elution fractionation（TREF） and solvent fractionation.The chain structures and composition of fractions obtained from solvent fractionation were examined in detail.The TREF results shows that there are much more E-P segmented copolymer and more uniform distribution of ethylene sequence in IPC-1,which is responsible for its better comprehensive mechanical performance.The fractions from hexane and heptane are ethylene-propylene rubber phase and E-P block copolymers respectively.The result of solvent fractionation method also shows that custom hexane or heptane extractions can not extract the E-P copolymer completely.展开更多
Triggered by environmental concerns and the rising demands for metal-free polymers in e.g. bio-related and microelectronic applications, studies on organocatalytic polymerization have been launched and developed unpre...Triggered by environmental concerns and the rising demands for metal-free polymers in e.g. bio-related and microelectronic applications, studies on organocatalytic polymerization have been launched and developed unprecedentedly during the last 15 years. A wide range of organic molecules are now available in polymer chemists＇ toolbox to choose from as catalysts for polymerization of （hetero）cyclic and polar vinyl monomers. Apart from the intrinsic merits such as lower toxicity and better solubility compared with （transition） metal catalysts/initiators, organocatalysts have also shown, in many cases, excellence to achieve high polymerization rates and/or good control （selectivity）. In addition, particular natures and catalytic/activating mechanisms of organocatalysts have led to new opportunities for rational design and efficient synthesis of macromolecular architectures, i.e. chain structures, topological structures and functionalities. This mini-review is specially themed on pathways to construct copolymer chain structures by organocatalytic copolymerization of mixed type monomers （comonomers bearing different polymerizing moieties） and will be sectioned by different comonomer combinations, including cyclic monoesters of different sizes, cyclic monoesters and lactides, cyclic esters and cyclic carbonates or epoxides, heterocycles and vinyl monomers.展开更多
基金Supported by the National Natural Science Foundation of China and the State Education Committee of China
文摘Acryloyl terminated Poly (ethyleneoxide)macromonomers (PEO-A) with different PEO chain lengths have been prepared by deactivation of PEO alkoxide with acryloyl chloride. A new kind of amphiphilic polystyrene-g-poly (ethylene oxide)graft copolymer containing both microphase separated and PEO side chain structures has been synthesized from radical copolymerization of PEO-A macromonomer with styrene. After careful purification by a newly-developed method called 'selective dissolution', the well-defined structure of the purified copolymers was confirmed by IR, ~1H-NMR and GPC. Various experimental parameters controlling the copolymerization were studied in detail. The results indicated that the feed ratio of styrene to macromonomer(S/M) was the most important determining factor for the composition of the copolymers. A detailed 'comb- model' was proposed to describe the molecular structure of the graft copolymers. Finally, this amphiphilic graft copolymers may readily form microphase separated structures as clearly indicated by transmission electron microscopy.
基金Supported by the National Natural Science Foundation of China(No. 5 95 730 0 8) .
文摘The structures and properties of benzoxazines were investigated by virtue of molecular modeling at a molecular level. By means of Cerius software(version 4.0) supplied by Molecular Simulations Inc., the molecular mechanics and the molecular dynamics were performed under a PCFF force field. Five kinds of the polymeric chains of benzoxazines were created by using polymer builder and energy minimization. The relaxation process was conducted with both energy minimization and molecular dynamics.
基金financially supported by the National Basic Research Program of China(No.2005CB623806)the National Natural Science Foundation of China(Nos.20734006 and 50921062)
文摘Two polyethylene（PE） resins（samples A and B） are synthesized as high-speed extrusion coatings with similar minimum coating thickness and neck-in performance but different maximum coating speeds. Both samples are separated into seven fractions using preparative temperature rising elution fractionation. The microstructures of the original samples and their fractions are studied by high-temperature gel permeation chromatography, Fourier transform infrared spectroscopy, 13 C nuclear magnetic resonance spectroscopy, differential scanning calorimetry, and successive self-nucleation/annealing thermal fractionation. Compared with sample B, sample A has a broader MWD, more LCB contents, and less SCB contents. Moreover, sample A contains slightly more 30 ℃ and 50 ℃ fractions with lower molecular weights, and more fractions at 75 ℃ and 85 ℃ with higher molecular weight. The chain structure and its distribution in the two PE resins are studied in detail, and the relationship between the chain structure and resin properties is also discussed.
基金supported by the National Natural Science Foundation of China(Nos.52173021,52373038 and 52073149)S&T Innovation 2025 Major Special Programme of Ningbo(No.2023Z079)。
文摘Ultra-high molecular weight polyethylene(UHMWPE)is widely utilized in low-dimensional materials due to its ultra-long chain imparted excellent strength and modulus.By employing gel-molding technology with a gradient temperature control,this study successfully produced gel films with varying shish crystal contents of the UHMWPE with a molecular weight of 8.0 million.The structural evolution during film hotstretching was investigated by in-situ wide-angle X-ray diffraction(WAXD),small-angle X-ray scattering(SAXS),ultra-small-angle X-ray scattering(USAXS),and ex-situ methods of scanning electron microscopy(SEM)and differential scanning calorimetry(DSC).The ultra-long molecular chains delay stress transfer during stretching but provide more nucleation sites for shish-kebab crystallization to form well-ordered shish-kebab crystals under high strain.The reserved high-content shish facilitates structural evolution,inducing the formation of highly-ordered shish-kebab crystals that eventually transfer into shish crystals in the later stage of stretching.The samples with low shish content,although the structural evolution is facilitated during stretching,predominantly result in newly formed shish-kebab crystals through melt recrystallization.However,some unoriented lamellae persists in unreserved samples stretching progress,leading to less ordered shish-kebab structures.By comparing with previous work of UHMWPE with low molecular weights,we demonstrate that the ultra-long molecular chains also play a key role on enabling the construction of highly-ordered shish-kebab crystals with high shish content during hot-stretching of UHMWPE gel films,providing new insights into processing control and optimization for engineering applications.
文摘The syntheses and structures of eleven novel polymeric transition metal complexes having one dimensional chain structures or three dimensional networks are summarized. They are prepared from the controlled assembling reactions in organic solvents and characterized by X ray diffraction analyses. The spectroscopic or magnetic properties of some complexes are studied.
基金supported by the National Key R&D Program of China(No.2022YFB3707303)the National Natural Science Foundation of China(Nos.52293471 and 21833008).
文摘The mechanical behavior of polymer networks is intrinsically correlated with the local chain topology and chain connectivity.In this study,we delve into this relationship through the lens of coarse-grained molecular dynamics(CG-MD)simulations.Our aim is to illuminate the intricate interplay between local topology and stress distribution within polymer monomers,cross-linkers,and various components with distinct cross-link connections,thereby elucidating their collective impact on the mechanical properties of polymer networks.We mainly focus on how specific local structures contribute to the overall mechanical response of the network.In particular,we employ local stress analysis to unravel the mechanics of these structures.Our findings reveal the diverse responses of individual components,such as junctions,strands,cross-linkers between junctions,and dangling chain ends,when subjected to stretching.Notably,we observe that these components exhibit varying degrees of deformation tolerance,underscoring the significance of their roles in determining the mechanical characteristics of the network.Our investigations highlight junctions as primary contributors to stress accumulation,and particles with higher local stress showing a stronger correlation between stress and Voronoi volume.Moreover,our results indicate that both strands and cross-linkers between junctions exhibit heightened stress levels as strand lengths decrease.This study enhances our understanding of the multifaceted factors governing the mechanical attributes of cross-linked polymer systems at the microstructural level.
文摘A new organo-directed titanium phosphate, [NH3CH2CH2NH3]·[TiO(HPO4)2], was synthesized by the solvothermal method and its structure was determined by single crystal X-ray diffraction. The structure consists of 1-D zigzag chains built up from trans-corner-sharing titanium oxo octahedra running along the b axis, with fused Ti2P three-membered rings being attached to the ( Ti ( O ( Ti ( O ( backbone.
基金Supported by the National Natural Science Foundation of China(No.20871051)the Scientific and Technological Plan-ning Project of Jilin Province, China(No.20080504)
文摘A new one-dimensional（ID） fluoroaluminophosphate chain（C4H15N3）[AlPO4F2]（denoted AIPO-CJ28） was synthesized in the concentrated fluoride synthetic medium with a gel composition of 1.0Al（OPr^1）a：1.0H3PO4： 5.4DETA：1.3HF：2.0H2O（DETA=diethylenetriamine）. The reagents were mixed directly without introducing additional water solvent. The 1D chain is constructed by alternating AlO2F2 arid doubly bridging PO4 tetrahedra to form the simplest serrate chain. AIPO-CJ28 can be transformed to another 1D aluminophosphate chain A1PO-CSC upon further crystallization at 230 ℃.
文摘Through improvements on a fully commercial and automatic system measuring frequency andtemperature spectra of the complex elastic, dielectric, and piezoelectric constants of polymerfilms, the precision for measuring complex dielectric constants achieved 2‰ from original 1%.The complex dielectric constants of PVDF, VDF （95 ）/VF （5）, VDF （52）/TrFE （48） and VDF（47. 5）/TrFE（47. 5）/HeFP （5） over a range of-120-140℃, 10-2-10;Hz were measured bythe described system. The diminution of chain regularity due to 5mol% vinyl fluoride in the chainof PVDF led to disappearing of α-relaxation and increase in T;（3℃） of VDF （95）/VF （5）.Because of the spatial impediment of 5mol% HeFP in copolymer chain, the Curie point of VDF（52）/TrFE（48） decreased by 30℃ and T;by 3℃. The behavior of dielectric relaxation indicatedthat 5mol% vinyl fluoride and HeFP made the relaxation strength of noncrystalline regionreduced, the activation energy of local relaxation increased and the relaxation time prolonged respectively.
文摘The chemical composition, molecular weight and its distribution, the bonding structure and the regulation of ultrahigh molecular weight polyacrylonitrile （UHMW-PAN） prepared by aqueous suspension polymerization were determined by FIIR, viscometry, GPC, ^3H-NMR and ^13CNMR. The mechanical properties of the porous hollow fiber prepared by UHMW-PAN were discussed to provide a theoretical basis for the preparation of ideal precursors of the porous hollow oxidation fiber.
基金Supported by the Azerbaijan Shahid Madani University
文摘We consider an entangled Ising-XY Z diamond chain structure. Quantum correlations for this model are inves- tigated by using quantum discord and trace distance discord. Quantum correlations are obtained for different values of the anisotropy parameter, magnetic field and temperature. By comparison between quantum correlations, we show that the trace distance discord is always larger than quantum discord. Finally, some novel effects such as increasing the quantum correlations with temperature and constructive role of anisotropy parameter, which may play to the quantum correlations, are observed.
文摘Ta_4(Te_2)_4Te_4I,Mr=2381.90,Monoclinic,C2/c,a=21.987(2),b=6.153(2),c= 19.936(3),β=122.42(14),V=2276.7 ~3,z=4,Dm=6.8(5)g/cm^3,Dc=6.95g/cm^3,λ(Mok)= 0.71073,μ=354.0cm^(-1),F(000)=3876,T=296(1)k,R=5.3%,Rw=6.8%,for 1118 unique observed reflections(1>3σ(Ⅰ)).The structure is composed of [Ta_4(Te_2)_4Te_4I]_∞~ chains,which are formed by the four-nuclear butterfly cluster units "Ta_4(Te_2)_4Te_4" with the Ⅰ atoms as the bridging atoms between different cluster units.
文摘The crystal structure of[Cu(2-thienoyl-trifluoroacetone)(4,4—bipyridine)]_n was determined by X-ray diffraction analysis. The crystal belongs to monoclinie with the space group C2/c, Mr=440.91, a=9.640(5) A, b=24.97(1) A, c=16.032(7) A, β=106.76(3)°,V=3695(3) A^3, Z=8, Dc=1.58g/cm^3, F(000)=1776. Final R and Rw are 0.062 and 0.069, respectively. The local coordination geometry around Cu(I) ion is a distorted tetrahedron. Cu(TTA) are linked with 4,4-bipyridine, forming long chain in the crystal.
基金supported by the National Natural Science Foundation of China(No.21541009)
文摘Two new crystals of chlorovanadates,Ba_8Cs_5V_8O_（24）Cl_（13）（1） and MgCsV_2O_6Cl（2）,were grown in the molten salt media. 1 crystallizes in tetragonal,space group P4/mmm（No. 123）,with a = 14.801（2）,c = 12.341（3） ？,V = 2703.5（8） ？~3,Z = 2,Mr = 3015.56,F（000） = 2640,μ = 11.044 mm-1,Dc = 3.704 g/cm3,the final R = 0.0380 and wR = 0.0937 for 1654 observed reflections with I 〉 2σ（I）. 2 crystallizes in a monoclinic space group C2/c（No. 15） with a = 11.128（2）,b = 10.540（2）,c = 6.9892（14） ？,β = 118.38（3）°,V = 721.2（2） ？~3,Z = 4,M_r = 390.55,F（000） = 712,μ = 7.997 mm-1,D_c = 3.597 g/cm^3,the final R = 0.0537 and w R = 0.1363 for 740 observed reflections with I 〉 2σ（I）. 1 exhibits a novel 8-membered-ring [V_8O_（24）] consisting of 8 corner-shared VO_4 tetrahetra,but in 2,an infinite ladder-like [VO_3]_∞ chain is formed by VO_5 square pyramids through sharing the edges.
基金Supported by the National Natural Science Foundation of China(No.60878063)the Program from Traditional Chinese Medicine Bureau of Guangdong Province(No.2008233)
文摘A theoretical study on oligopeptide chains of glycine-alanine by density functional theory（DFT） is given in this paper. Raman spectra of the oligopeptide chains are examined. The geometric structures, frontier orbital, energy gap, atomic charge distribution, density of states and chemical activity of the side chain are studied at the B3LYP/6-31G（d） level. Results show that, with the number of residues increasing, vibrations of typical functional groups present Raman frequency shift, and the energy gap is gradually reduced. The HOMO and LUMO focus on the amino and carboxyl at the ends of oligopeptides. It is helpful for oligopeptides to self-assemble into chains. In addition, different residues（glycine or alanine） at the ends of chains result in the even-odd effect of orbital energy in the growth process. The size effects of physical and chemical properties only exist when the oligopeptides are shorter, and the phenomenon disappeared as the chain continues to grow.
基金carried out according to the program of Fundamental Scientific Research of the Russian Federation
文摘The article describes ethylene polymerization reactions with transition metal catalysts based on complexes of CoCl_(2) and FeCl_(2) with an N,N,N-tridentate ligand 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine. The complexes are converted into polymerization catalysts by reacting them either with polymethylalumoxane (MAO) or with a combination of Al(C2H5)2Cl and Mg(C4H9)2 at an [Al]:[Mg] ratio of ~3. Both MAO-activated complexes readily polymerize ethylene at 35 ℃ with the formation of linear, low molecular weight polymers with a narrow molecular weight distribution. The same complexes, when activated with the Al(C2H5)2Cl-Mg(C4H9)2 combination, form multi-center catalysts and generate polyethylenes with a broad molecular weight distribution.
文摘The linear-chain structure in which three alpha particles are arranged in a straight line was initially proposed by H.Morinaga[1]as the structure of the Hoyle state of carbon-12[2].This unique idea attracted much attention,but it was rejected because it could not explain the lifetime of the Hoyle state.Half a century later,the concept of the linear chain structure was revived in the physics of unstable nuclei,and experimental and theoretical research have demonstrated that this structure exists in carbon-14 and 16.The authors have conducted internationally recognized experimental research on the linear-chain structure of carbon-14 and carbon-16.
基金Supported by the National Natural Science Foundation of China(No.21171119)the National High Technology Research and Development Program 863 of China(No.2012AA063201)+3 种基金the Committee of Education of the Beijing Foundation of China(No.KM201210028020)Program for Excellent Talents of Beijing City(No.2010D005016000002)the Beijing Municipal Natural Science Foundation(No.7122015)Scientific Research Base Development Program of the Beijing Municipal Commission of Education
文摘Two novel silver（I） complexes {[Ag（OTf）（PPh3）（4,4＇-bipy）]}∞（1） and {[Ag2-（OTf）2（dppb）3]（CH3CN）4}∞（2）（OTf = trifluoromethanesulfonate, PPh3 = triphenylphophine, 4,4＇-bipy = 4,4＇-bipyridine, dppb = bis（diphenylphosphino）butane） have been synthesized and characterized by IR, single-crystal X-ray diffraction, fluorescence spectrum and 1H NMR spectroscopy. Complex 1 crystallizes in orthorhombic, space group Pna21 with a = 19.259（2）, b = 9.85070（12）, c = 16.3827（17） A, V = 3108.0（5） A3, C29H23F3N2O3 PSAg, Mr = 675.39, Z = 4, Dc = 1.443 g/cm3, F（000） = 1360, μ = 0.816 mm-1, the final R = 0.0675 and w R = 0.1722 for 3662 observed reflections（I 〉 2σ（I））. Complex 2 crystallizes in triclinic, space group P1 with a = 12.9370（11）, b = 13.5261（13）, c = 16.4539（15） A, α = 106.7120（10）, β = 97.3830（10）, γ = 113.027（2）A, V = 2441.2（4）A3, C94H96F6N4O6P6S2Ag2, Mr = 1957.43, Z = 1, Dc = 1.331 g/cm3, F（000） = 1006, μ = 0.605 mm-1, the final R = 0.0717 and w R = 0.1795 for 5128 observed reflections（I 〉 2σ（I））. Complex 1 is of zigzag chain structure, in which each Ag atom is coordinated by one OTf- anion, two N atoms from two 4,4＇-bipy molecules and one P atom from PPh3 ligand. In 2, the central Ag atom is coordinated with one OTf- anion and three P atoms from three dppb ligands, which leads to the formation of a zigzag ring-bridge-ring chain with each ring consisting of two Ag atoms and two dppb ligands.
基金financially supported by Science and Technology Project of PetroChina Refining&Chemicals Company (No.0904A07-19)Petrochemical Research Institute Innovation Project(No.09-YK-05-20)
文摘The compositional heterogeneity of two impact polypropylene copolymers（IPCs） was studied by a combinatory investigation of temperature rising elution fractionation（TREF） and solvent fractionation.The chain structures and composition of fractions obtained from solvent fractionation were examined in detail.The TREF results shows that there are much more E-P segmented copolymer and more uniform distribution of ethylene sequence in IPC-1,which is responsible for its better comprehensive mechanical performance.The fractions from hexane and heptane are ethylene-propylene rubber phase and E-P block copolymers respectively.The result of solvent fractionation method also shows that custom hexane or heptane extractions can not extract the E-P copolymer completely.
基金supported by the National Natural Science Foundation of China(Nos.21504024 and 21674038)Fundamental Research Funds for Central Universities
文摘Triggered by environmental concerns and the rising demands for metal-free polymers in e.g. bio-related and microelectronic applications, studies on organocatalytic polymerization have been launched and developed unprecedentedly during the last 15 years. A wide range of organic molecules are now available in polymer chemists＇ toolbox to choose from as catalysts for polymerization of （hetero）cyclic and polar vinyl monomers. Apart from the intrinsic merits such as lower toxicity and better solubility compared with （transition） metal catalysts/initiators, organocatalysts have also shown, in many cases, excellence to achieve high polymerization rates and/or good control （selectivity）. In addition, particular natures and catalytic/activating mechanisms of organocatalysts have led to new opportunities for rational design and efficient synthesis of macromolecular architectures, i.e. chain structures, topological structures and functionalities. This mini-review is specially themed on pathways to construct copolymer chain structures by organocatalytic copolymerization of mixed type monomers （comonomers bearing different polymerizing moieties） and will be sectioned by different comonomer combinations, including cyclic monoesters of different sizes, cyclic monoesters and lactides, cyclic esters and cyclic carbonates or epoxides, heterocycles and vinyl monomers.
