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
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
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
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 expansion of new structures in aggregation-induced emission/aggregation-induced emission enhancement(AIE/AIEE)systems has attracted persistent attention recently,from which more luminescent functional molecules wi...The expansion of new structures in aggregation-induced emission/aggregation-induced emission enhancement(AIE/AIEE)systems has attracted persistent attention recently,from which more luminescent functional molecules with characteristic skeletons are derived to satisfy specialized applications.In this study,a series of derivatives cored by tetraphenyl enamine with various terminal groups were designed and synthesized based on a novel p-πconjugate chain structure(–C=C–N–).Experimental and theoretical studies reveal that attaching modified groups to enamine core is decisive to achieve successful conversion from non-luminance to AIEE-activity.Moreover,due to different substituent effect on electronic structure,molecular conformation and molecular packing,diverse enamine compounds exhibited prominent substituent tunable emission properties,realizing regulated AIEE effect and multicolor emitting.These results not only offer a new method to design AIEgens/AIEEgens with p-πconjugate chain structures,but also provide in-depth knowledge for functional modifications of more novel AIE/AIEE units and materials.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
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
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
A new lead（Ⅱ） carboxylate-sulfonate has been hydrothermally synthesized and characterized by X-ray single-crystal and elemental analyses. It crystallizes in triclinic, space group Pi, with a = 8.1573（6）, b = 9.4...A new lead（Ⅱ） carboxylate-sulfonate has been hydrothermally synthesized and characterized by X-ray single-crystal and elemental analyses. It crystallizes in triclinic, space group Pi, with a = 8.1573（6）, b = 9.4663（7）, c = 12.7488（9）A, a = 89.2320（10）, β = 80.7380（10）, γ = 77.9760（10）°, Z = 2, V= 950.10（12） A^3, Mr= 599.57, Dc= 2.096 g/cm^3,μ = 9.032 mm^-1, F（000） = 572, the final R = 0.0412 and wR = 0.1035. It has a ID chain structure, and the Pb（Ⅱ） is six-coordinated. Two PbO6 polyhedra are interconnected via edge-sharing into a two-core unit. Such units are further interconnected by 3-sulfonato-benzoic acids into I D chains which are linked by hydrogen bonds into a layer structure. The 4,4＇-bipyridines are located at the interlayer space and link the layers into a supramolecular structure by π-π stacking interactions.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
The title compound, [Zn（Pybta）Cl2]n （Pybta = 1-（2-pyridylmethyl）benzontriazole）, has a zigzag chain structure. It crystallizes in the monoclinic system, space group P21/c with a = 9.0103（11）, b = 17.0276（18）...The title compound, [Zn（Pybta）Cl2]n （Pybta = 1-（2-pyridylmethyl）benzontriazole）, has a zigzag chain structure. It crystallizes in the monoclinic system, space group P21/c with a = 9.0103（11）, b = 17.0276（18）, c = 9.2288（11）A,β = 101.309（6）°, Mr= 346.51, V= 1388.4（3）A^3, Z= 4, De= 1.658 g/cm^3, F（000） = 696,/a = 2.143 mm^-1, the final R = 0.0492 and wR = 0.1236 for 2545 observed reflections with I 〉 2σ（I）. The Zn atom is four-coordinated by two N and two Cl atoms, forming a slightly distorted tetrahedral geometry. Each zigzag chain links its adjacent symmetryrelated equivalents via multiple π-π interactions, which are not frequently observed in the previously reported architectures.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
Thin wall samples of high density polyethylene （HDPE） were prepared via injection molding with different injection speeds ranging from 100 mm/s to 1200 mm/s. A significant decrease in the tensile strength and Young...Thin wall samples of high density polyethylene （HDPE） were prepared via injection molding with different injection speeds ranging from 100 mm/s to 1200 mm/s. A significant decrease in the tensile strength and Young＇s modulus was observed with increasing injection speed. In order to investigate the mechanism behind this decrease, the orientation, molecular weight, molecular weight distribution, melt flow rate, crystallinity and crystal morphology of HDPE were characterized using two-dimensional wide-angle X-ray diffraction （2D-WAXD）, gel permeation chromatography （GPC）, capillary rheometry and differential scanning calorimetry （DSC）, respectively. It is demonstrated that the orientation, molecular weight, molecular weight distribution, melt flow rate and crystallinity have no obvious change with increasing injection speed. Nevertheless, the content of extended chain crystals or large folded chain crystals was found to decrease with increasing injection speed. Therefore, it is concluded that the decrease in tensile properties is mainly contributed by the reduced content of extended chain crystals or large folded chain crystals. This study provides industry with valuable information for the application of high speed injection molding.展开更多
As the strict limitation of primary structure in traditional force method and displacement method in indeterminate analysis may lead to complicated high-order linear equations, a breakthrough of the limitation, i.e., ...As the strict limitation of primary structure in traditional force method and displacement method in indeterminate analysis may lead to complicated high-order linear equations, a breakthrough of the limitation, i.e., the application of irregular force method and irregular displacement method, would be introduced in this paper to ease the difficulty of hand computations. By using hyperstatic primary structures and partly chained primary structures, the primary structures of force method and displacement method are reformed, and the order of the system is decreased. The technique is explained through examples. The significance of the new method is summarized.展开更多
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.
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.
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.
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.
基金the National Natural Science Foundation of China(21574003)。
文摘The expansion of new structures in aggregation-induced emission/aggregation-induced emission enhancement(AIE/AIEE)systems has attracted persistent attention recently,from which more luminescent functional molecules with characteristic skeletons are derived to satisfy specialized applications.In this study,a series of derivatives cored by tetraphenyl enamine with various terminal groups were designed and synthesized based on a novel p-πconjugate chain structure(–C=C–N–).Experimental and theoretical studies reveal that attaching modified groups to enamine core is decisive to achieve successful conversion from non-luminance to AIEE-activity.Moreover,due to different substituent effect on electronic structure,molecular conformation and molecular packing,diverse enamine compounds exhibited prominent substituent tunable emission properties,realizing regulated AIEE effect and multicolor emitting.These results not only offer a new method to design AIEgens/AIEEgens with p-πconjugate chain structures,but also provide in-depth knowledge for functional modifications of more novel AIE/AIEE units and materials.
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.
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.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.
文摘A new lead（Ⅱ） carboxylate-sulfonate has been hydrothermally synthesized and characterized by X-ray single-crystal and elemental analyses. It crystallizes in triclinic, space group Pi, with a = 8.1573（6）, b = 9.4663（7）, c = 12.7488（9）A, a = 89.2320（10）, β = 80.7380（10）, γ = 77.9760（10）°, Z = 2, V= 950.10（12） A^3, Mr= 599.57, Dc= 2.096 g/cm^3,μ = 9.032 mm^-1, F（000） = 572, the final R = 0.0412 and wR = 0.1035. It has a ID chain structure, and the Pb（Ⅱ） is six-coordinated. Two PbO6 polyhedra are interconnected via edge-sharing into a two-core unit. Such units are further interconnected by 3-sulfonato-benzoic acids into I D chains which are linked by hydrogen bonds into a layer structure. The 4,4＇-bipyridines are located at the interlayer space and link the layers into a supramolecular structure by π-π stacking interactions.
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The project was supported by the Natural Science Foundation of Fujian Province (No. 2006J0272)
文摘The title compound, [Zn（Pybta）Cl2]n （Pybta = 1-（2-pyridylmethyl）benzontriazole）, has a zigzag chain structure. It crystallizes in the monoclinic system, space group P21/c with a = 9.0103（11）, b = 17.0276（18）, c = 9.2288（11）A,β = 101.309（6）°, Mr= 346.51, V= 1388.4（3）A^3, Z= 4, De= 1.658 g/cm^3, F（000） = 696,/a = 2.143 mm^-1, the final R = 0.0492 and wR = 0.1236 for 2545 observed reflections with I 〉 2σ（I）. The Zn atom is four-coordinated by two N and two Cl atoms, forming a slightly distorted tetrahedral geometry. Each zigzag chain links its adjacent symmetryrelated equivalents via multiple π-π interactions, which are not frequently observed in the previously reported architectures.
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.
基金supported by the National Natural Science Foundation of China(No.51073111)
文摘Thin wall samples of high density polyethylene （HDPE） were prepared via injection molding with different injection speeds ranging from 100 mm/s to 1200 mm/s. A significant decrease in the tensile strength and Young＇s modulus was observed with increasing injection speed. In order to investigate the mechanism behind this decrease, the orientation, molecular weight, molecular weight distribution, melt flow rate, crystallinity and crystal morphology of HDPE were characterized using two-dimensional wide-angle X-ray diffraction （2D-WAXD）, gel permeation chromatography （GPC）, capillary rheometry and differential scanning calorimetry （DSC）, respectively. It is demonstrated that the orientation, molecular weight, molecular weight distribution, melt flow rate and crystallinity have no obvious change with increasing injection speed. Nevertheless, the content of extended chain crystals or large folded chain crystals was found to decrease with increasing injection speed. Therefore, it is concluded that the decrease in tensile properties is mainly contributed by the reduced content of extended chain crystals or large folded chain crystals. This study provides industry with valuable information for the application of high speed injection molding.
文摘As the strict limitation of primary structure in traditional force method and displacement method in indeterminate analysis may lead to complicated high-order linear equations, a breakthrough of the limitation, i.e., the application of irregular force method and irregular displacement method, would be introduced in this paper to ease the difficulty of hand computations. By using hyperstatic primary structures and partly chained primary structures, the primary structures of force method and displacement method are reformed, and the order of the system is decreased. The technique is explained through examples. The significance of the new method is summarized.
