In order to promote development of linear/branched block polyethylenes based on new catalytic systems,we synthesized a novel a.dimine nickel(Ⅱ)complex with isopropyl substituents on ortho-N-aryl and hydroxymethyl phe...In order to promote development of linear/branched block polyethylenes based on new catalytic systems,we synthesized a novel a.dimine nickel(Ⅱ)complex with isopropyl substituents on ortho-N-aryl and hydroxymethyl phenyl substituents on para-Naryl structures.The activity of a-dimine nickl(Ⅱ)catalyst was 3.02x10^(6)g-mol_(ni)^(-1)·h^(-1) at 70℃,and resultant polyethylene possessed 135/1000C branches.The linear/branched block polyethylenes were synthesized from ethylene polymerization catalyzed by the a-dimine nicke(Ⅱ)complex/bis(phenoxy-imine)zirconium in the presence of diethyI zinc.With the addition of ZnEtz(from 0 to 400),the melting peak of resultant polyethylene changed from a single melting peak to bimodal melting peaks.The molecular weights of resultant polyethylene ranging from 26.8 kg/mol to 17.1 kg/mol and PDI values varying gradually from 24.4 to 15.2 were obtained vla adjusting ZnEt;equiv.and molar ratio of two catalysts.In addition,the branching degree of the polyethylene increased from 13/1000C to 56/1000 with the increase of the proportion of a dimine nickel(Ⅱ)catalyst.Using this binary catalyst system,the reaction temperature of chain shutting polymerization can be carried out at 70℃,which is more conducive to industrial application.展开更多
The female inflorescence,or ear,of maize develops no branch meristem(BM),which differs from the male inforescence,or tassel.While the mutations of some well documented genes,such as fea2/3/4 and ramosa1/2/3,can cause ...The female inflorescence,or ear,of maize develops no branch meristem(BM),which differs from the male inforescence,or tassel.While the mutations of some well documented genes,such as fea2/3/4 and ramosa1/2/3,can cause the branched architecture of ears in maize,such mutations also change the normal phenotypic performance of the tassels.In the present study,a natural maize mutant with branched ears,named branched ear1(be1),was characterized.be1 shows several branched ears at the base of the central ear with unchanged architecture of the tassels.Besides,both the branched and central ears of be1 possess regularly arranged kerels.The phenotypic characteristics of be1 differ completely from those reported mutants of fasciated ears or RAMOSA-like ears in maize.An SEM survey at the very early development stage showed that meristems with three protrusions,similar to the BM in tassels,were present during the development of the branched ears in be1.Gene mapping and sequence alignment suggested that TEOSINTE BRANCHED1(TB1)was the candidate gene of BE1.Further verification showed that a be1-specific 31 bp deletion at the downstream of BE1 led to statistically reduced expression of this gene in the immature ear,which serves as the potential causal reason for the branched ears of be1.CRISPR/Cas9-based gene editing downstream of TB1 complemented the phenotypic architecture of branched ears,suggesting that TB1 was the target of BE1,and it was named as Zm TB1be1.The results of the present study implied a novel function of TB1 in female inforescence development,rather than shaping the plant architecture in maize.Meanwhile,further functional dissection of ZmTB1be1might shed new light on TB1,the most famous domestication related gene in maize.展开更多
Mechanochromic polyolefins represent a novel class of functionalized polyolefins,which still remains significant challenges.Pd(II)-catalyzed coordination-insertion copolymerization is a feasible method for achieving t...Mechanochromic polyolefins represent a novel class of functionalized polyolefins,which still remains significant challenges.Pd(II)-catalyzed coordination-insertion copolymerization is a feasible method for achieving this kind of polymers,yet with linear microstructures.Ringopening metathesis polymerization(ROMP)offers another promising avenue for affording functionalized polyolefins.This method exhibits high polar group tolerance and the ability to precisely regulate polymer branches.In this study,we report the method for producing mechanochromic branched polyethylenes via ROMP.By employing the terpolymerization of a well-designed monomer containing the mechanochromic group,NB-ABF,with cyclooctene(COE)and long-chain 5-hexylcyclooctene(COE-C6),following by hydrogenation process,we synthesized a range of functionalized branched polyethylenes characterized by varied branching density and polar monomer incorporation.These polymers bear a structural resemblance to functionalized ethylene-octene copolymers.After crosslinking,mechanochromophores are generated,and mechanochromism is achieved in uniaxial tensile testing.A comprehensive assessment reveals that both the incorporation of polar monomers and variations in branching density significantly influence their mechanical properties.Notably,upon stretching,these materials display pronounced visible color change,confirming the successful development of mechanochromic branched polyethylenes.展开更多
Cutting-edge research has primarily focused on flow synthesis of linear block copolymers,lacking the ability for manipulating chain architectures for more extensive applications.Herein,we develop a flow chemistry plat...Cutting-edge research has primarily focused on flow synthesis of linear block copolymers,lacking the ability for manipulating chain architectures for more extensive applications.Herein,we develop a flow chemistry platform for the continuous microflow synthesis of bottlebrush block copolymers(BBCPs)using a grafting-through method.This involves performing ring-opening metathesis polymerization(ROMP)of two different macromonomers within two microfluidic reactors connected in series.The microflow environment allows for complete monomer conversion within a few tens of seconds,benefiting from the superior mixing efficiency achieved in Z-shaped channels as indicated by both theoretical simulations and experimental results.Consequently,a library of well-defined BBCPs of up to 528 distinct samples can be produced within one day through automation of the continuous procedure,while keeping precise control on degree of polymerization(DP<4)and polydispersity indices(PDI<1.2).The synthetic method is generally applicable to different macromonomers with different compositions and contour lengths,yielding libraries of branched block copolymers with great diversity in physiochemical properties and chain architectures.This work presents a powerful platform for high-throughput production of branched copolymers,significantly lowering the costs of the materials for real applications.展开更多
Athletes often use branched-chain amino acid (BCAAs) supplements with a ratio of 2:1:1 (leucine:isoleucine:valine) for their impact on muscle building. Research suggests that by altering the ratio, an improvement in g...Athletes often use branched-chain amino acid (BCAAs) supplements with a ratio of 2:1:1 (leucine:isoleucine:valine) for their impact on muscle building. Research suggests that by altering the ratio, an improvement in glucose metabolism might be possible. The purpose of this study was to examine how isoleucine would influence glucose tolerance. We recruited healthy male (n = 13) and female (n = 5) participants who were asked to fast for 12 hours before coming to the laboratory. A fasting blood sample was collected, followed by the subjects consuming a breakfast containing 113 g carbohydrates, 8 g protein, 1.5 g fat, and BCAA powder in the 2:1:1 ratio (Control) or BCAA powder enriched with Isoleucine (2:6:1), both added to orange juice. The opposite meal was consumed on a second visit one week apart. Blood was collected at 30, 60, 90, and 120 minutes post-meal. No differences were observed between the Control and Isoleucine for changes in serum glucose or insulin response when examining all subjects together. However, when comparing between genders, males tended to have a significantly lower serum glucose response compared to females when consuming the Isoleucine, with no difference between the genders when consuming the Control. Also, males had significantly lower serum glucose responses when consuming the Isoleucine compared to when they consumed the Control, while females had significantly higher serum glucose responses when consuming the Isoleucine compared to when they consumed the Control. In general, males tended to have a lower serum insulin response than females when consuming both the Control and the Isoleucine. Our study indicates a significant difference in the way genders respond to BCAA supplementation, where isoleucine may improve glucose tolerance and insulin response in males but not females.展开更多
In this study,non-linear thermal-mechanical stability and vibration analyses of different end-shaped single-walled carbon nanotube conveying viscous nano-magnetic fluid embedded in non-linear visco-elastic foundation ...In this study,non-linear thermal-mechanical stability and vibration analyses of different end-shaped single-walled carbon nanotube conveying viscous nano-magnetic fluid embedded in non-linear visco-elastic foundation under the influence of magnetic fields are presented.The development of the equation of motion was based on Euler-Bernoulli theory,Hamilton principle and nonlocal elasticity theory.The results of the analytical solutions using Galerkin decomposition differential transform method(GDDTM)were validated with existing experimental results.From the parametric studies,it was shown that decreasing the temperature difference as well as increasing the downstream angle decreased the system's stability for pre-bifurcation analysis but increased stability of the system for post bifurcation analysis.Also,the results obtained from the dynamic behaviour of the system indicated that the magnetic effect had an attenuating impact of about 45%on the system's response at any mode and for any boundary condition considered.It is hoped that this work will enhance the design and optimization of nano-devices with I,V,Y,L,K and T-shaped junctions under the influence of thermal-magneto-mechanical flow induced vibration.展开更多
Branched chain amino acids(BCAAs)have been shown to affect gene expression,protein metabolism,apoptosis and regeneration of hepatocytes,and insulin resistance.They have also been shown to inhibit the proliferation of ...Branched chain amino acids(BCAAs)have been shown to affect gene expression,protein metabolism,apoptosis and regeneration of hepatocytes,and insulin resistance.They have also been shown to inhibit the proliferation of liver cancer cells in vitro,and are essential for lymphocyte proliferation and dendritic cell maturation.In patients with advanced chronic liver disease,BCAA concentrations are low,whereas the concentrations of aromatic amino acids such as phenylalanine and tyrosine are high,conditions that may be closely associated with hepatic encephalopathy and the prognosis of these patients.Based on these basic observations,patients with advanced chronic liver disease have been treated clinically with BCAA-rich medicines,with positive effects.展开更多
By making use of Thiele-type bivariate branched continued fractions and Sumelson inverse,we construct a few kinds of bivariate vector valued rational interpolonts (BVRIs) over rectangular grids and find out certain re...By making use of Thiele-type bivariate branched continued fractions and Sumelson inverse,we construct a few kinds of bivariate vector valued rational interpolonts (BVRIs) over rectangular grids and find out certain relations among these BVRIs such as boundary identity and duality.展开更多
Korean larch(Larix olgensis)is one of the main tree species for aff orestation and timber production in northeast China.However,its timber quality and growth ability are largely infl uenced by crown size,structure and...Korean larch(Larix olgensis)is one of the main tree species for aff orestation and timber production in northeast China.However,its timber quality and growth ability are largely infl uenced by crown size,structure and shape.The majority of crown models are static models based on tree size and stand characteristics from temporary sample plots,but crown dynamic models has seldom been constructed.Therefore,this study aimed to develop height to crown base(HCB)and crown length(CL)dynamic models using the branch mortality technique for a Korean larch plantation.The nonlinear mixed-eff ects model with random eff ects,variance functions and correlation structures,was used to build HCB and CL dynamic models.The data were obtained from 95 sample trees of 19 plots in Meng JiaGang forest farm in Northeast China.The results showed that HCB progressively increases as tree age,tree height growth(HT growth)and diameter at breast height growth(DBH growth).The CL was increased with tree age in 20 years ago,and subsequently stabilized.HT growth,DBH growth stand basal area(BAS)and crown competition factor(CCF)signifi cantly infl uenced HCB and CL.The HCB was positively correlated with BAS,HT growth and DBH growth,but negatively correlated with CCF.The CL was positively correlated with BAS and CCF,but negatively correlated with DBH growth.Model fi tting and validation confi rmed that the mixed-eff ects model considering the stand and tree level random eff ects was accurate and reliable for predicting the HCB and CL dynamics.However,the models involving adding variance functions and time series correlation structure could not completely remove heterogeneity and autocorrelation,and the fi tting precision of the models was reduced.Therefore,from the point of view of application,we should take care to avoid setting up over-complex models.The HCB and CL dynamic models in our study may also be incorporated into stand growth and yield model systems in China.展开更多
Lithium-ion batteries(LIBs) are considered new generation of large-scale energy-storage devices.However,LIBs suffer from a lack of desirable anode materials with excellent specific capacity and cycling stability.In th...Lithium-ion batteries(LIBs) are considered new generation of large-scale energy-storage devices.However,LIBs suffer from a lack of desirable anode materials with excellent specific capacity and cycling stability.In this work,we design a novel hierarchical structure constructed by encapsulating cobalt sulfide nanowires within nitrogen-doped porous branched carbon nanotubes(NBNTs)for LIBs.The unique hierarchical Co9S8@NBNT electrode displayed a reversible specific capacity of 1310 mAhg-1 at a current density of 0.1 Ag-1,and was able to maintain a stable reversible discharge capacity of 1109 mAhg-1 at a current density of 0.5 Ag-1 with coulombic efficiency reaching almost 100% for 200 cycles.The excellent rate and cycling capabilities can be ascribed to the hierarchical porosity of the one-dimensional Co9S8@NBNT internetworks,the incorporation of nitrogen doping,and the carbon nanotube confinement of the active cobalt sulfide nanowires offering a proximate electron pathway for the isolated nanoparticles and shielding of the cobalt sulfide nanowires from pulverization over long cycling periods.展开更多
The rheological behavior, thermal properties and foam morphology of linear polypropylene and long chain branching polypropylene prepared through UV irradiation reactive extrusion were studied by rheological test, melt...The rheological behavior, thermal properties and foam morphology of linear polypropylene and long chain branching polypropylene prepared through UV irradiation reactive extrusion were studied by rheological test, melt index test, DSC and supercritical carbon dioxide foaming technology. Rheological test and melt index test confirmed that under UV irradiation and extrusion, adding photo-initiator and cross- linking agent could achieve the purpose of branching, thus improved the melt strength of polypropylene effectively. The DSC results revealed that with the introducing of long chain branching, the melting range of the polypropylene broadened and the crystallization temperature increased. Owing to the introduction of long chain branches, polypropylene exhibited higher melt strength and strain hardening behavior. Compared with linear polypropylene, the foam morphologies of long chain branching polypropylene were more uniform.展开更多
A series of hyperbranched polyurethane-benzyltetrazoles （H-PBTZs） with different linkage structures were synthesized via the polycondensation of hexamethylenediisocyanate as an A2 type monomer with （4-（1H-tetrazol...A series of hyperbranched polyurethane-benzyltetrazoles （H-PBTZs） with different linkage structures were synthesized via the polycondensation of hexamethylenediisocyanate as an A2 type monomer with （4-（1H-tetrazol-5- yl）benzyl）-diethanolamine （TBDEA） as a BB＇2 type monomer in the absence of catalyst at different temperatures. The FTIR, and 13C and 1H-NMR spectroscopy were used to characterize the molecular structures of TBDEA and H-PBTZs as well as the counterpart linear polyurethane-benzyltetrazole （L-PBTZ）. The molecular composition was determined by the reaction selectivity that the isocyanate group reacted with the hydroxyl group in diethanolamine segment or the active hydrogen atom on tetrazole ring. Raising reaction temperature was propitious to the reaction of isocyanate group with the active hydrogen atom on tetrazole ring. The degrees of branching （DB） for H-PBTZs obtained from the 1H-NMR spectra increased with raising reaction temperature. The wider molecular weight distribution of 1.7-2.9 for H-PBTZs was obtained via GPC analysis. TGA results showed that H-PBTZs had high thermal stability compared with L-PBTZ.展开更多
A vertical (laterally averaged) two-dimensional hydrodynamic model is developed for tides, tidal current, and salinity in a branched estuarine system. The governing equations are solved with the hydrostatic pressure d...A vertical (laterally averaged) two-dimensional hydrodynamic model is developed for tides, tidal current, and salinity in a branched estuarine system. The governing equations are solved with the hydrostatic pressure distribution assumption and the Boussinesq approximation. An explicit scheme is employed to solve the continuity equations. The momentum and mass balance equations are solved implicitly in the Cartesian coordinate system. The tributaries are governed by the same dynamic equations. A control volume at the junctions is designed to conserve mass and volume transport in the finite difference schemes, based on the physical principle of continuum medium of fluid. Predictions by the developed model are compared with the analytic solutions of steady wind-driven circulatory flow and tidal flow. The model results for the velocities and water surface elevations coincide with analytic results. The model is then applied to the Tanshui River estuarine system. Detailed model calibration and verification have been conducted with measured water surface elevations, tidal current, and salinity distributions. The overall performance of the model is in qualitative agreement with the available field data. The calibrated and verified numerical model has been used to quantify the tidal prism and flushing rate in the Tanshui River-Tahan Stream, Hsintien Stream, and Keelung River.展开更多
Perfluorooctanoic acid(PFOA) or perfluorooctane sulphonate(PFOS) was one of the most prominent fluorosurfactants and applied widely in firefighting and daily chemical, etc. However, these surfactants have recently bee...Perfluorooctanoic acid(PFOA) or perfluorooctane sulphonate(PFOS) was one of the most prominent fluorosurfactants and applied widely in firefighting and daily chemical, etc. However, these surfactants have recently been identified as toxic and undegradability in the environment. Developing an efficient approach to environment-friendly fluorosurfactants is essential. A fluorocarbon branched chain strategy was adopted to develop/PFOS substitutes. A series of intermediates of novel branched fluorinated surfactants with CF_3 CF_2CF_2C(CF3)_2 group were synthesized from perfluoro-2-methyl-2-pentene. All the steps were mild, easy-handled and cheap. It is expected to be a very significant direction for the development of non-bioaccumulable alternatives of PFOA or PFOS.展开更多
Although it is common to eliminate the singularity of parallel mechanism by adding the branched chain with actuation redundancy, there is no theory and method for the configuration synthesis of the branched chain with...Although it is common to eliminate the singularity of parallel mechanism by adding the branched chain with actuation redundancy, there is no theory and method for the configuration synthesis of the branched chain with actuation redundancy in parallel mechanism. Branched chains with actuation redundancy are synthesized for eliminating interior singularity of 3-translational and 1-rotational（3T1R） parallel mechanisms. Guided by the discriminance method of hybrid screw group according to Grassmann line geometry, all the possibilities are listed for the occurrence of interior singularities in 3T1R parallel mechanism. Based on the linear relevance of screw system and the principles of eliminating parallel mechanism singularity with actuation redundancy, different types of branched chains with actuation redundancy are synthesized systematically to indicate the layout and the number of the branched chainsinterior with actuation redundancy. A general method is proposed for the configuration synthesis of the branched chains with actuation redundancy of the redundant parallel mechanism, and it builds a solid foundation for the subsequent performance optimization of the redundant actuation parallel mechanism.展开更多
A series of branched poly（butylene succinate）（PBS） were synthesized with several branching agents namely trimethylol propane（TMP）, malic acid, trimesic acid, citric acid and glycerol propoxylate. The structure o...A series of branched poly（butylene succinate）（PBS） were synthesized with several branching agents namely trimethylol propane（TMP）, malic acid, trimesic acid, citric acid and glycerol propoxylate. The structure of the branched polymers was analyzed by SEC and ~1H-NMR. The effect of branching agent structure on crystallization was also investigated and played a significant role. Isothermal studies showed that glycerol propoxylate could act as a nucleating agent. By contrast high content of TMP disturbed the regularity of the chain and hindered the crystallization of PBS. From the non-isothermal kinetic study, it was found that glycerol propoxylate increased noticeably the crystallization rate due to the flexible structure of the branching agent. A secondary nucleation was observed with glycerol propoxylate attributed to the crystallization of amorphous fraction included between crystallites formed at the primary crystallization. Chain topology was obtained through rheological investigations and the synthesized polymers showed a typical behavior of a mixture of linear and randomly branched PBS. The incorporation of branches improved the processability of PBS for film blowing application and the modulus and the stress at break of the resulting film were significantly increased.展开更多
The structure-property characteristics of a series of newly synthesized intramolecular charge- transfer （ICT） compounds, single-branch monomer with triphenylmethane as electron donor and 2,1,3-benzothiadiazole as ac...The structure-property characteristics of a series of newly synthesized intramolecular charge- transfer （ICT） compounds, single-branch monomer with triphenylmethane as electron donor and 2,1,3-benzothiadiazole as acceptor, the corresponding two-branch dimer and three- branch trimer, have been investigated by means of steady-state and femtosecond time- resolved stimulated emission fluorescence depletion （FS TR-SEP FD） techniques in different polar solvents. The TD-DFT calculations are further performed to explain the observed ICT properties. The interpretation of the experimental results is based on the comparative studies of the series of compounds which have increased amount of identical branch moiety. The similarity of the absorption and fluorescence spectra as well as strong solvent-dependence of the spectral properties for the three compounds reveal that the excited state of the dimer and trimer are nearly the same with that of the monomer, which may localize on one branch. It is found that polar excited state emerged through multidimensional intramolecular charge transfer from the donating moiety to the acceptor upon excitation, and quickly relaxed to one branch before emission. Even so, the red-shift in the absorption and emission spectra and decreased fluorescence radiative lifetime with respect to their monomer counterpart still suggest some extent delocalization of excited state in the dimer and trimer upon excitation. The similar behavior of their excited ICT state is demonstrated by FS TR-SEP FD measurements, and shows that the trimer has the largest charge-separate extent in all studied three samples. Finally, steady-state excitation anisotropy measurements has further been carried out to estimate the nature of the optical excitation and the mechanism of energy redistribution among the branches, where no plateau through the ICT band suggests the intramolecular excitation transfer process between the branches in dimer and trimer.展开更多
A series of N-phosphoryl branched peptides were synthesized by coupling of various N-phosphoryl amino acids to L-Lysine methyl ester, and their structures were confirmed by 31P NMR, 1H NMR, MS and elemental analysis....A series of N-phosphoryl branched peptides were synthesized by coupling of various N-phosphoryl amino acids to L-Lysine methyl ester, and their structures were confirmed by 31P NMR, 1H NMR, MS and elemental analysis. The results of cell biological tests indicated that compound 1d and 1e obviously inhibited the growth of both K562 and A2780 cells.展开更多
基金by the National Natural Science Foundation of China(Nos.21004017 and 21004043)the Natural Science Foundation of Hebei Provinee(No.B2015202049).
文摘In order to promote development of linear/branched block polyethylenes based on new catalytic systems,we synthesized a novel a.dimine nickel(Ⅱ)complex with isopropyl substituents on ortho-N-aryl and hydroxymethyl phenyl substituents on para-Naryl structures.The activity of a-dimine nickl(Ⅱ)catalyst was 3.02x10^(6)g-mol_(ni)^(-1)·h^(-1) at 70℃,and resultant polyethylene possessed 135/1000C branches.The linear/branched block polyethylenes were synthesized from ethylene polymerization catalyzed by the a-dimine nicke(Ⅱ)complex/bis(phenoxy-imine)zirconium in the presence of diethyI zinc.With the addition of ZnEtz(from 0 to 400),the melting peak of resultant polyethylene changed from a single melting peak to bimodal melting peaks.The molecular weights of resultant polyethylene ranging from 26.8 kg/mol to 17.1 kg/mol and PDI values varying gradually from 24.4 to 15.2 were obtained vla adjusting ZnEt;equiv.and molar ratio of two catalysts.In addition,the branching degree of the polyethylene increased from 13/1000C to 56/1000 with the increase of the proportion of a dimine nickel(Ⅱ)catalyst.Using this binary catalyst system,the reaction temperature of chain shutting polymerization can be carried out at 70℃,which is more conducive to industrial application.
基金supported by the Special Key Project for Technological Innovation and Application Development in Chongqing,China(CSTB2022TIAD-KPX0011)the Special Fund for Youth Team of the Southwest Universities,China(SWU-XJPY202306)+1 种基金the Natural Science Foundation of Chongqing,China(cstc2021jcyj-msxmX0583)the Fundamental Research Funds for the Central Universities of Southwest University,China(S202210635326)。
文摘The female inflorescence,or ear,of maize develops no branch meristem(BM),which differs from the male inforescence,or tassel.While the mutations of some well documented genes,such as fea2/3/4 and ramosa1/2/3,can cause the branched architecture of ears in maize,such mutations also change the normal phenotypic performance of the tassels.In the present study,a natural maize mutant with branched ears,named branched ear1(be1),was characterized.be1 shows several branched ears at the base of the central ear with unchanged architecture of the tassels.Besides,both the branched and central ears of be1 possess regularly arranged kerels.The phenotypic characteristics of be1 differ completely from those reported mutants of fasciated ears or RAMOSA-like ears in maize.An SEM survey at the very early development stage showed that meristems with three protrusions,similar to the BM in tassels,were present during the development of the branched ears in be1.Gene mapping and sequence alignment suggested that TEOSINTE BRANCHED1(TB1)was the candidate gene of BE1.Further verification showed that a be1-specific 31 bp deletion at the downstream of BE1 led to statistically reduced expression of this gene in the immature ear,which serves as the potential causal reason for the branched ears of be1.CRISPR/Cas9-based gene editing downstream of TB1 complemented the phenotypic architecture of branched ears,suggesting that TB1 was the target of BE1,and it was named as Zm TB1be1.The results of the present study implied a novel function of TB1 in female inforescence development,rather than shaping the plant architecture in maize.Meanwhile,further functional dissection of ZmTB1be1might shed new light on TB1,the most famous domestication related gene in maize.
基金supported by the National Natural Science Foundation of China(No.U23B6011)the Jilin Provincial Science and Technology Department Program(No.20230101347JC)。
文摘Mechanochromic polyolefins represent a novel class of functionalized polyolefins,which still remains significant challenges.Pd(II)-catalyzed coordination-insertion copolymerization is a feasible method for achieving this kind of polymers,yet with linear microstructures.Ringopening metathesis polymerization(ROMP)offers another promising avenue for affording functionalized polyolefins.This method exhibits high polar group tolerance and the ability to precisely regulate polymer branches.In this study,we report the method for producing mechanochromic branched polyethylenes via ROMP.By employing the terpolymerization of a well-designed monomer containing the mechanochromic group,NB-ABF,with cyclooctene(COE)and long-chain 5-hexylcyclooctene(COE-C6),following by hydrogenation process,we synthesized a range of functionalized branched polyethylenes characterized by varied branching density and polar monomer incorporation.These polymers bear a structural resemblance to functionalized ethylene-octene copolymers.After crosslinking,mechanochromophores are generated,and mechanochromism is achieved in uniaxial tensile testing.A comprehensive assessment reveals that both the incorporation of polar monomers and variations in branching density significantly influence their mechanical properties.Notably,upon stretching,these materials display pronounced visible color change,confirming the successful development of mechanochromic branched polyethylenes.
基金financially supported by the National Natural Science Foundation of China(No.22071176)。
文摘Cutting-edge research has primarily focused on flow synthesis of linear block copolymers,lacking the ability for manipulating chain architectures for more extensive applications.Herein,we develop a flow chemistry platform for the continuous microflow synthesis of bottlebrush block copolymers(BBCPs)using a grafting-through method.This involves performing ring-opening metathesis polymerization(ROMP)of two different macromonomers within two microfluidic reactors connected in series.The microflow environment allows for complete monomer conversion within a few tens of seconds,benefiting from the superior mixing efficiency achieved in Z-shaped channels as indicated by both theoretical simulations and experimental results.Consequently,a library of well-defined BBCPs of up to 528 distinct samples can be produced within one day through automation of the continuous procedure,while keeping precise control on degree of polymerization(DP<4)and polydispersity indices(PDI<1.2).The synthetic method is generally applicable to different macromonomers with different compositions and contour lengths,yielding libraries of branched block copolymers with great diversity in physiochemical properties and chain architectures.This work presents a powerful platform for high-throughput production of branched copolymers,significantly lowering the costs of the materials for real applications.
文摘Athletes often use branched-chain amino acid (BCAAs) supplements with a ratio of 2:1:1 (leucine:isoleucine:valine) for their impact on muscle building. Research suggests that by altering the ratio, an improvement in glucose metabolism might be possible. The purpose of this study was to examine how isoleucine would influence glucose tolerance. We recruited healthy male (n = 13) and female (n = 5) participants who were asked to fast for 12 hours before coming to the laboratory. A fasting blood sample was collected, followed by the subjects consuming a breakfast containing 113 g carbohydrates, 8 g protein, 1.5 g fat, and BCAA powder in the 2:1:1 ratio (Control) or BCAA powder enriched with Isoleucine (2:6:1), both added to orange juice. The opposite meal was consumed on a second visit one week apart. Blood was collected at 30, 60, 90, and 120 minutes post-meal. No differences were observed between the Control and Isoleucine for changes in serum glucose or insulin response when examining all subjects together. However, when comparing between genders, males tended to have a significantly lower serum glucose response compared to females when consuming the Isoleucine, with no difference between the genders when consuming the Control. Also, males had significantly lower serum glucose responses when consuming the Isoleucine compared to when they consumed the Control, while females had significantly higher serum glucose responses when consuming the Isoleucine compared to when they consumed the Control. In general, males tended to have a lower serum insulin response than females when consuming both the Control and the Isoleucine. Our study indicates a significant difference in the way genders respond to BCAA supplementation, where isoleucine may improve glucose tolerance and insulin response in males but not females.
文摘In this study,non-linear thermal-mechanical stability and vibration analyses of different end-shaped single-walled carbon nanotube conveying viscous nano-magnetic fluid embedded in non-linear visco-elastic foundation under the influence of magnetic fields are presented.The development of the equation of motion was based on Euler-Bernoulli theory,Hamilton principle and nonlocal elasticity theory.The results of the analytical solutions using Galerkin decomposition differential transform method(GDDTM)were validated with existing experimental results.From the parametric studies,it was shown that decreasing the temperature difference as well as increasing the downstream angle decreased the system's stability for pre-bifurcation analysis but increased stability of the system for post bifurcation analysis.Also,the results obtained from the dynamic behaviour of the system indicated that the magnetic effect had an attenuating impact of about 45%on the system's response at any mode and for any boundary condition considered.It is hoped that this work will enhance the design and optimization of nano-devices with I,V,Y,L,K and T-shaped junctions under the influence of thermal-magneto-mechanical flow induced vibration.
文摘Branched chain amino acids(BCAAs)have been shown to affect gene expression,protein metabolism,apoptosis and regeneration of hepatocytes,and insulin resistance.They have also been shown to inhibit the proliferation of liver cancer cells in vitro,and are essential for lymphocyte proliferation and dendritic cell maturation.In patients with advanced chronic liver disease,BCAA concentrations are low,whereas the concentrations of aromatic amino acids such as phenylalanine and tyrosine are high,conditions that may be closely associated with hepatic encephalopathy and the prognosis of these patients.Based on these basic observations,patients with advanced chronic liver disease have been treated clinically with BCAA-rich medicines,with positive effects.
基金Supported by the National Natural Science Foundation of China.
文摘By making use of Thiele-type bivariate branched continued fractions and Sumelson inverse,we construct a few kinds of bivariate vector valued rational interpolonts (BVRIs) over rectangular grids and find out certain relations among these BVRIs such as boundary identity and duality.
基金supported by the National Key Research and Development Program of China(2017YFD0600401)the Fundamental Research Funds for the Central Universities(2572019CP08)
文摘Korean larch(Larix olgensis)is one of the main tree species for aff orestation and timber production in northeast China.However,its timber quality and growth ability are largely infl uenced by crown size,structure and shape.The majority of crown models are static models based on tree size and stand characteristics from temporary sample plots,but crown dynamic models has seldom been constructed.Therefore,this study aimed to develop height to crown base(HCB)and crown length(CL)dynamic models using the branch mortality technique for a Korean larch plantation.The nonlinear mixed-eff ects model with random eff ects,variance functions and correlation structures,was used to build HCB and CL dynamic models.The data were obtained from 95 sample trees of 19 plots in Meng JiaGang forest farm in Northeast China.The results showed that HCB progressively increases as tree age,tree height growth(HT growth)and diameter at breast height growth(DBH growth).The CL was increased with tree age in 20 years ago,and subsequently stabilized.HT growth,DBH growth stand basal area(BAS)and crown competition factor(CCF)signifi cantly infl uenced HCB and CL.The HCB was positively correlated with BAS,HT growth and DBH growth,but negatively correlated with CCF.The CL was positively correlated with BAS and CCF,but negatively correlated with DBH growth.Model fi tting and validation confi rmed that the mixed-eff ects model considering the stand and tree level random eff ects was accurate and reliable for predicting the HCB and CL dynamics.However,the models involving adding variance functions and time series correlation structure could not completely remove heterogeneity and autocorrelation,and the fi tting precision of the models was reduced.Therefore,from the point of view of application,we should take care to avoid setting up over-complex models.The HCB and CL dynamic models in our study may also be incorporated into stand growth and yield model systems in China.
基金financially supported by the Natural Science Foundation of Anhui Province(KJ2018A0534)the research fund of Anhui Science and Technology University(ZRC2014402)+1 种基金Materials Science and Engineering Key Discipline Foundation(AKZDXK2015A01)the Deanship of Scientific Research at King Saud University for its funding of this research through the Research Group Project No.Prolific Research Group No.1436-011
文摘Lithium-ion batteries(LIBs) are considered new generation of large-scale energy-storage devices.However,LIBs suffer from a lack of desirable anode materials with excellent specific capacity and cycling stability.In this work,we design a novel hierarchical structure constructed by encapsulating cobalt sulfide nanowires within nitrogen-doped porous branched carbon nanotubes(NBNTs)for LIBs.The unique hierarchical Co9S8@NBNT electrode displayed a reversible specific capacity of 1310 mAhg-1 at a current density of 0.1 Ag-1,and was able to maintain a stable reversible discharge capacity of 1109 mAhg-1 at a current density of 0.5 Ag-1 with coulombic efficiency reaching almost 100% for 200 cycles.The excellent rate and cycling capabilities can be ascribed to the hierarchical porosity of the one-dimensional Co9S8@NBNT internetworks,the incorporation of nitrogen doping,and the carbon nanotube confinement of the active cobalt sulfide nanowires offering a proximate electron pathway for the isolated nanoparticles and shielding of the cobalt sulfide nanowires from pulverization over long cycling periods.
基金Funded by the National Natural Science Foundation of China(No.51103091)Scientific Research Foundation for the Returned Overseas Chinese Scholars State Education Ministry(No.20101174-4-3)the Opening Project of the Key Laboratory of Polymer Processing Engineering,Ministry of Education,China and the Fundamental Research Funds for the Central Universities(No.2012ZM0074)
文摘The rheological behavior, thermal properties and foam morphology of linear polypropylene and long chain branching polypropylene prepared through UV irradiation reactive extrusion were studied by rheological test, melt index test, DSC and supercritical carbon dioxide foaming technology. Rheological test and melt index test confirmed that under UV irradiation and extrusion, adding photo-initiator and cross- linking agent could achieve the purpose of branching, thus improved the melt strength of polypropylene effectively. The DSC results revealed that with the introducing of long chain branching, the melting range of the polypropylene broadened and the crystallization temperature increased. Owing to the introduction of long chain branches, polypropylene exhibited higher melt strength and strain hardening behavior. Compared with linear polypropylene, the foam morphologies of long chain branching polypropylene were more uniform.
基金financially supported by the National Natural Science Foundation of China(Nos.50633010 and 50973100)
文摘A series of hyperbranched polyurethane-benzyltetrazoles （H-PBTZs） with different linkage structures were synthesized via the polycondensation of hexamethylenediisocyanate as an A2 type monomer with （4-（1H-tetrazol-5- yl）benzyl）-diethanolamine （TBDEA） as a BB＇2 type monomer in the absence of catalyst at different temperatures. The FTIR, and 13C and 1H-NMR spectroscopy were used to characterize the molecular structures of TBDEA and H-PBTZs as well as the counterpart linear polyurethane-benzyltetrazole （L-PBTZ）. The molecular composition was determined by the reaction selectivity that the isocyanate group reacted with the hydroxyl group in diethanolamine segment or the active hydrogen atom on tetrazole ring. Raising reaction temperature was propitious to the reaction of isocyanate group with the active hydrogen atom on tetrazole ring. The degrees of branching （DB） for H-PBTZs obtained from the 1H-NMR spectra increased with raising reaction temperature. The wider molecular weight distribution of 1.7-2.9 for H-PBTZs was obtained via GPC analysis. TGA results showed that H-PBTZs had high thermal stability compared with L-PBTZ.
基金theScienceCouncil,Taiwan(GrantNo.NSC92 2211 E 037and92 2211 E 057)
文摘A vertical (laterally averaged) two-dimensional hydrodynamic model is developed for tides, tidal current, and salinity in a branched estuarine system. The governing equations are solved with the hydrostatic pressure distribution assumption and the Boussinesq approximation. An explicit scheme is employed to solve the continuity equations. The momentum and mass balance equations are solved implicitly in the Cartesian coordinate system. The tributaries are governed by the same dynamic equations. A control volume at the junctions is designed to conserve mass and volume transport in the finite difference schemes, based on the physical principle of continuum medium of fluid. Predictions by the developed model are compared with the analytic solutions of steady wind-driven circulatory flow and tidal flow. The model results for the velocities and water surface elevations coincide with analytic results. The model is then applied to the Tanshui River estuarine system. Detailed model calibration and verification have been conducted with measured water surface elevations, tidal current, and salinity distributions. The overall performance of the model is in qualitative agreement with the available field data. The calibrated and verified numerical model has been used to quantify the tidal prism and flushing rate in the Tanshui River-Tahan Stream, Hsintien Stream, and Keelung River.
基金supported by the National Natural Science Foundation of China(No. 2167020782)
文摘Perfluorooctanoic acid(PFOA) or perfluorooctane sulphonate(PFOS) was one of the most prominent fluorosurfactants and applied widely in firefighting and daily chemical, etc. However, these surfactants have recently been identified as toxic and undegradability in the environment. Developing an efficient approach to environment-friendly fluorosurfactants is essential. A fluorocarbon branched chain strategy was adopted to develop/PFOS substitutes. A series of intermediates of novel branched fluorinated surfactants with CF_3 CF_2CF_2C(CF3)_2 group were synthesized from perfluoro-2-methyl-2-pentene. All the steps were mild, easy-handled and cheap. It is expected to be a very significant direction for the development of non-bioaccumulable alternatives of PFOA or PFOS.
基金Supported by Research Fund for the Doctoral Program of Higher Education,China(Grant No.20131333110008)
文摘Although it is common to eliminate the singularity of parallel mechanism by adding the branched chain with actuation redundancy, there is no theory and method for the configuration synthesis of the branched chain with actuation redundancy in parallel mechanism. Branched chains with actuation redundancy are synthesized for eliminating interior singularity of 3-translational and 1-rotational（3T1R） parallel mechanisms. Guided by the discriminance method of hybrid screw group according to Grassmann line geometry, all the possibilities are listed for the occurrence of interior singularities in 3T1R parallel mechanism. Based on the linear relevance of screw system and the principles of eliminating parallel mechanism singularity with actuation redundancy, different types of branched chains with actuation redundancy are synthesized systematically to indicate the layout and the number of the branched chainsinterior with actuation redundancy. A general method is proposed for the configuration synthesis of the branched chains with actuation redundancy of the redundant parallel mechanism, and it builds a solid foundation for the subsequent performance optimization of the redundant actuation parallel mechanism.
基金financially supported by the company MBD Texinov(France)the company Roquette Frères(France)+4 种基金the ANRTthe framework of the collaborative project Agroboost funded by BPI FranceRhone-Alpes RegionRhone-Alpes FEDERthe Basse Normandie Regional Council
文摘A series of branched poly（butylene succinate）（PBS） were synthesized with several branching agents namely trimethylol propane（TMP）, malic acid, trimesic acid, citric acid and glycerol propoxylate. The structure of the branched polymers was analyzed by SEC and ~1H-NMR. The effect of branching agent structure on crystallization was also investigated and played a significant role. Isothermal studies showed that glycerol propoxylate could act as a nucleating agent. By contrast high content of TMP disturbed the regularity of the chain and hindered the crystallization of PBS. From the non-isothermal kinetic study, it was found that glycerol propoxylate increased noticeably the crystallization rate due to the flexible structure of the branching agent. A secondary nucleation was observed with glycerol propoxylate attributed to the crystallization of amorphous fraction included between crystallites formed at the primary crystallization. Chain topology was obtained through rheological investigations and the synthesized polymers showed a typical behavior of a mixture of linear and randomly branched PBS. The incorporation of branches improved the processability of PBS for film blowing application and the modulus and the stress at break of the resulting film were significantly increased.
基金We sincerely thank Prof. Yong-fang Li for providing the samples. S. Vdovi5 thanks CAS for support through a CAS Research Fellowship for International Young Researchers. This work was supported by National Natural Science Foundation of China, the Chinese Academy of Sciences, and the State Key Project for Fundamental Research.
文摘The structure-property characteristics of a series of newly synthesized intramolecular charge- transfer （ICT） compounds, single-branch monomer with triphenylmethane as electron donor and 2,1,3-benzothiadiazole as acceptor, the corresponding two-branch dimer and three- branch trimer, have been investigated by means of steady-state and femtosecond time- resolved stimulated emission fluorescence depletion （FS TR-SEP FD） techniques in different polar solvents. The TD-DFT calculations are further performed to explain the observed ICT properties. The interpretation of the experimental results is based on the comparative studies of the series of compounds which have increased amount of identical branch moiety. The similarity of the absorption and fluorescence spectra as well as strong solvent-dependence of the spectral properties for the three compounds reveal that the excited state of the dimer and trimer are nearly the same with that of the monomer, which may localize on one branch. It is found that polar excited state emerged through multidimensional intramolecular charge transfer from the donating moiety to the acceptor upon excitation, and quickly relaxed to one branch before emission. Even so, the red-shift in the absorption and emission spectra and decreased fluorescence radiative lifetime with respect to their monomer counterpart still suggest some extent delocalization of excited state in the dimer and trimer upon excitation. The similar behavior of their excited ICT state is demonstrated by FS TR-SEP FD measurements, and shows that the trimer has the largest charge-separate extent in all studied three samples. Finally, steady-state excitation anisotropy measurements has further been carried out to estimate the nature of the optical excitation and the mechanism of energy redistribution among the branches, where no plateau through the ICT band suggests the intramolecular excitation transfer process between the branches in dimer and trimer.
基金This work is supported by Natural Science Foundation of Beijing City (7002006). Elemental analyses were performed by Institute of Chemistry Chinese Academy of Science.
文摘A series of N-phosphoryl branched peptides were synthesized by coupling of various N-phosphoryl amino acids to L-Lysine methyl ester, and their structures were confirmed by 31P NMR, 1H NMR, MS and elemental analysis. The results of cell biological tests indicated that compound 1d and 1e obviously inhibited the growth of both K562 and A2780 cells.
