Archroma becomes the exclusive global distributor of Fibre52®'s patented chemistry-advancing a new standard in sustainable processing.Combined with Archroma's AVITERA®SE dyes,the partnership delivers...Archroma becomes the exclusive global distributor of Fibre52®'s patented chemistry-advancing a new standard in sustainable processing.Combined with Archroma's AVITERA®SE dyes,the partnership delivers the industry's most resource-efficient bleach-and-dye sys-tems.Archroma,a leading global specialty chemicals company committed to sus-tainable innovation,and Innovo Fiber LLC,owner of the patented Fibre52®system,today announced an exclusive global dis-tribution partnership to expand the reach of Fibre52®'s proven low-temperature,bleaching technology with innovative dyeing application to textile mills and brands worldwide.展开更多
Bending is a crucial operation in the sheet forming of Mg alloys for automotive and aerospace applications.In this work,three kinds of sheets from an AZ31 rolled plate,sheared at 0°(S0),45°(S45),and 90°...Bending is a crucial operation in the sheet forming of Mg alloys for automotive and aerospace applications.In this work,three kinds of sheets from an AZ31 rolled plate,sheared at 0°(S0),45°(S45),and 90°(S90)to the rolling direction,were subjected to three-point bending tests.In-situ digital image correlation(DIC)system was employed to capture the strain fields.Electron backscatter diffraction(EBSD)was used to examine the through-thickness microstructures.A crystal plasticity finite element method(CPFEM)incorporating twinning and slip mechanisms was developed to simulate the bending deformation.The texture effect on the neutral layer shift and twinning behaviors was systematically investigated in terms of both experiments and simulations.The results show that CPFEM effectively simulated the texturedependent shifting behaviors of neutral layer and the associated twinning behaviors.Particularly,the spatial distributions of neutral layer across the entire bent plates were captured by both DIC and CPFEM.Additionally,some unusual twinning behaviors were analyzed in depth,such as the{10-12}-{10-12}secondary twins in S90,localized twin bands in S0,and the twin traces difference in S45.These findings reveal a close relationship between the neutral layer shift and twinning activity induced by the initial texture and strain levels.This work provides valuable insights into the bending deformation mechanisms of Mg alloys and has important implications for improving their formability and controlling springback.展开更多
In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still face...In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still faced with defects such as low intrinsic ionic conductivity,a narrow electrochemical window,and poor thermal stability.A crosslinking and fluorination molecular design strategy toward PDOL is proposed to tackle the issues above.The amorphous crosslinked structure effectively improves ionic conductivity by inhibiting long-chain crystallization.Especially,the antioxidant–CF_(3)groups,stable crosslinked structure,and reduced terminal hydroxyl groups significantly enhance the electrochemical oxidation stability with a superb high-voltage window of 4.7 V.In addition,the designed electrolyte also exhibits obviously improved thermal stability with no deformation at 120°C for 5 min.Furthermore,the semi-solid NCM811||Li batteries exhibit a favourable capacity retention of 88.8%after 150 cycles at 0.5 C.Even assembled with NCM622 cathode working at 4.5 V,the semi-solid batteries can still show a satisfactory capacity retention of 85.3%after 100 cycles at 0.5 C.Also,a 0.1 Ah NCM811||Li pouch cell with active materials loading of 9 mg/cm2 demonstrates satisfactory cycling stability and working ability,which shows promising practical application prospects.展开更多
Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this stu...Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this study,a novel p H/glutathione dual-responsive pesticide delivery system was constructed through the synthesis of disulfide-bridged hollow mesoporous organosilica nanospheres(HMONs)via the St??ber method,followed by poly(acrylic acid)(PAA)coating through distillation-precipitation polymerization to form HMONs@PAA nanocomposites.The resulting abamectin-loaded system(Abamectin-HMONs@PAA)demonstrated a 12.73% pesticide loading capacity and significantly improved photostability,retaining twice as much active ingredient as free abamectin after 250 h of UV irradiation(36 W).Release studies revealed p H-and glutathione-dependent characteristics,with cumulative releases in acidic conditions exceeding those in neutral and alkaline environments by 18.66% and 40.98%,respectively,and a 14.2% increase in glutathione-containing solution(0.2 mmol·L^(-1) in 70% ethanol)after 97 h.Bioassays showed superior performance against Plutella xylostella,with a 13.33% reduction in survival rate compared to conventional suspension at equivalent dosage(40 mg·L^(-1)),while maintaining efficacy after extensive rainfall simulation(20 events over 10 days).This study provides a promising approach for developing environmentally responsive nanopesticides with enhanced durability and controlled-release properties,offering significant potential for sustainable crop protection.展开更多
Global land monsoon precipitation(GLMP)is highly sensitive to changes in interhemispheric thermal contrast(ITC).Amplified interhemispheric asymmetries of GLMP due to enhanced ITC driven by high-level anthropogenic emi...Global land monsoon precipitation(GLMP)is highly sensitive to changes in interhemispheric thermal contrast(ITC).Amplified interhemispheric asymmetries of GLMP due to enhanced ITC driven by high-level anthropogenic emissions are expected to simultaneously increase the probability of regional floods and droughts,threatening ecosystems within global terrestrial monsoon regions and the freshwater supply for billions of residents in these areas.In this study,the responses of GLMP to the evolution of ITC toward the carbon neutrality goal are assessed using multimodel outputs from a new model intercomparison project(CovidMIP).The results show that the Northern Hemisphere-Southern Hemisphere(NH-SH)asymmetry of GLMP in boreal summer weakens during the 2040s,as a persistent reduction in well-mixed greenhouse gas(WMGHG)emissions leads to a downward trend in the ITC after 2040.At the same time,the reduction in WMGHG emissions dampens the Eastern Hemisphere-Western Hemisphere(EH-WH)asymmetry of GLMP by inducing La Niña-like cooling and enhancing moisture transport to Inner America.The resulting increases in land monsoon precipitation(LMP)may alleviate drought under the global warming scenario by about 19%-25%and 7%-9%in the WH and SH monsoon regions,respectively.However,a persistent reduction in aerosol emissions in Asia will dominate the increases in LMP in this region until the mid-21st century,and these increases may be approximately 23%-60%of the growth under the global warming scenario.Our results highlight the different rates of response of aerosol and WMGHG concentrations to the carbon neutrality goal,leading to various changes in LMP at global and regional scales.展开更多
Poly(phenylene oxide)(PPO)exhibits excellent dielectric properties,making it an ideal substrate for high-frequency,high-speed copper-clad laminates.The phenolic hydroxyl group at the end of PPO plays a key role in its...Poly(phenylene oxide)(PPO)exhibits excellent dielectric properties,making it an ideal substrate for high-frequency,high-speed copper-clad laminates.The phenolic hydroxyl group at the end of PPO plays a key role in its reactivity.Accurately quantifying the phenolic hydroxyl content in PPO is essential but challenging.In this study,we proposed a method for measuring the phenolic hydroxyl content of PPO using differential UV absorption spectroscopy.In alkaline solutions,the phenolic hydroxyl in PPO completely ionizes to form phenoxide ions,leading to a significant increase in UV absorbance at approximately 250 and 300 nm.Notably,the differential UV absorbance at approximately 300 nm was directly proportional to the phenolic hydroxyl concentration.Using 2,6-dimethylphenol as a standard,a calibration curve was established to relate the phenolic hydroxyl concentration to differential UV absorbance at approximately 300 nm,providing a precise and straightforward method for phenolic hydroxyl quantification in PPO with distinct advantages over conventional techniques.展开更多
Electrocatalytic nitrate reduction reaction(NO3RR)represents a sustainable and environmentally benign route for ammonia(NH3)synthesis.However,NO3RR is still limited by the competition from hydrogen evolution reaction(...Electrocatalytic nitrate reduction reaction(NO3RR)represents a sustainable and environmentally benign route for ammonia(NH3)synthesis.However,NO3RR is still limited by the competition from hydrogen evolution reaction(HER)and the high energy barrier in the hydrogenation step of nitrogen-containing intermediates.Here,we report a selective etching strategy to construct Ru M nanoalloys(M=Fe,Co,Ni,Cu)uniformly dispersed on porous nitrogen-doped carbon substrates for efficient neutral NH3electrosynthesis.Density functional theory calculations confirm that the synergic effect between Ru and transition metal M modulates the electronic structure of the alloy,significantly lowering the energy barrier for the conversion of*NO_(2)to*HNO_(2).Experimentally,the optimized Ru Fe-NC catalyst achieves 100%Faraday efficiency with a high yield rate of 0.83 mg h^(-1)mg^(-1)catat a low potential of-0.1 V vs.RHE,outperforming most reported catalysts.In situ spectroscopic analyses further demonstrate that the Ru M-NC effectively promotes the hydrogenation of nitrogen intermediates while inhibiting the formation of hydrogen radicals,thereby reducing HER competition.The Ru FeNC assembled Zn-NO_(3)^(-)battery achieved a high open-circuit voltage and an outstanding power density and capacity,which drive selective NO_(3)^(-)conversion to NH3.This work provides a powerful synergistic design strategy for efficient NH3electrosynthesis and a general framework for the development of advanced multi-component catalysts for sustainable nitrogen conversion.展开更多
Although poly(urethane-urea)elastomers(PUEs)possess excellent mechanical properties and durability,their inherent flammability and inability to self-repair after damage significantly limits their applications in high-...Although poly(urethane-urea)elastomers(PUEs)possess excellent mechanical properties and durability,their inherent flammability and inability to self-repair after damage significantly limits their applications in high-end fields.To address this challenge,this study employs a supramolecular chemistry approach by simultaneously incorporating multiple hydrogen bonds as dynamic cross-linking points and a phosphorus-nitrogen synergistic flame-retardant structure into the poly(urethane-urea)network.The multiple hydrogen bonds endow the material with efficient intrinsic self-healing capability,while the phosphorus-nitrogen flame retardant ensures outstanding thermal stability and flame resistance,leading to the successful synthesis of a high-performance multifunctional poly(urethane-urea)elastomer.Experimental results demonstrated that when the content of the flame retardant diethyl(2-((2-aminoethyl)amino)ethyl)phosphoramidate(DEPTA)was 10 wt%,the resulting PUE/10%DEPTA achieved a V-0 rating in the vertical burning test,with a limiting oxygen index(LOI)of 30%.Concurrently,the elastomer maintained good toughness,exhibiting a tensile strength of 27.3 MPa,an elongation at break of 601%,and a self-healing efficiency of up to 94.46%.This breakthrough shows significant promise for advanced engineering applications that demand fire safety,structural durability,and extended service life through self-repair.展开更多
This study uses all-atom molecular dynamics simulations to investigate the dislocation propagation, stress transmission, and mechanical properties in poly(p-phenylene terephthalamide) fibers under uniaxial tension. Th...This study uses all-atom molecular dynamics simulations to investigate the dislocation propagation, stress transmission, and mechanical properties in poly(p-phenylene terephthalamide) fibers under uniaxial tension. The results indicate that the dislocation propagates and the stress transfers not only along the fiber axis but also between adjacent molecular chains through hydrogen bonds, demonstrating their influence on the yield behavior. As the degree of polymerization increases, breakage of covalent bonds and interchain slippage contribute to the yield of fibers together. This work provides theoretical guidance for the design and manufacturing of high-performance fibers.展开更多
Bio-based 2,5-furandicarboxylic acid polyesters offer significant promise for reducing energy and environmental crises.However,their intrinsic flammability remains a critical limitation,and conventional flame-retardan...Bio-based 2,5-furandicarboxylic acid polyesters offer significant promise for reducing energy and environmental crises.However,their intrinsic flammability remains a critical limitation,and conventional flame-retardant strategies often compromise their mechanical properties,hindering their practical applications.Herein,a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO)-based comonomer(DDP)was used to synthesize flame-retardant poly(ethylene furandicarboxylate-co-phosphaphenanthrene)(PEFDn).The covalent integration of DDP confers intrinsic flame retardancy,avoiding the plasticization and migration issues associated with additive-type systems.Upon thermal decomposition,the DOPO-derived moieties release phosphoric acid and radical scavengers,promoting char formation and suppressing flame propagation.Furthermore,density functional theory(DFT)calculations combined with non-covalent interaction(NCI)analysis revealed that DOPO dimer molecules adopt a stable parallel-displaced π-π stacking configu ration,potentially facilitating microphase separation and enhancing the energy dissipation capability.PEFD_(10)achieves a UL-94 V-0 rating while simultaneously increasing impact toughness from 1.5 kJ/m^(2) to 14.7 kJ/m^(2).Im portantly,PEFDn maintained acceptable oxygen-barrier properties.PEFD10 also exhibited high transparency and UV-shielding performance.The combination of intrinsic flame safety,im pact-toughness resistance,UV shielding,and an oxygen barrier ensures reliable protection of electrical components and long-term operational stability.The integration of multiple critical properties within a single bio-based material represents a novel approach fo r enabling sustainable polymer solutions for high-pe rformance electrical applications.展开更多
Corn starch(CS)is a renewable,biodegradable polysaccharide valued for its film-forming ability,yet native CS films exhibit lowmechanical strength,highwater sensitivity,and limited thermal stability.This study improves...Corn starch(CS)is a renewable,biodegradable polysaccharide valued for its film-forming ability,yet native CS films exhibit lowmechanical strength,highwater sensitivity,and limited thermal stability.This study improves CS-based films by blending with poly(vinyl alcohol)(PVA)or glycerol(GLY)and using citric acid(CA)as a green,non-toxic cross-linker.Composite films were prepared by casting CS–PVA or CS-GLY with CA at 0%-0.20%(w/w of starch).The influence of CA on physicochemical,mechanical,optical,thermal,and water barrier properties was evaluated.CA crosslinking markedly enhanced the tensile strength,water resistance,and thermal stability of CS-PVA films while increasing transparency in CS–GLY films.At 0.20%CA,the composite achieved 34.99MPa tensile strength,reducedwater vapor permeability,andminimized water uptake.FTIR confirmed ester bond formation between CAand hydroxyl groups of CS,PVA,and GLY,whereas thermal analysis showed higher decomposition temperatures and lower weight loss in crosslinked films.Increasing CA levels also decreased opacity and improved light transmittance,indicating greater homogeneity and reduced crystallinity.This dual-polymer matrix combined with a natural crosslinking strategy provides a sustainable route to high-performance,biodegradable CS-based packaging materials.展开更多
Advanced age impairs bone fracture healing;the underlying mechanism of this phenomenon remains unknown.We determined that apolipoprotein E(ApoE)increases with age and causes poor fracture healing.After deletion of hep...Advanced age impairs bone fracture healing;the underlying mechanism of this phenomenon remains unknown.We determined that apolipoprotein E(ApoE)increases with age and causes poor fracture healing.After deletion of hepatic ApoE expression(ΔApoE),24-month-oldΔApoE mice displayed a 95%reduction in circulating ApoE levels and significantly improved fracture healing.ApoE treatment of aged BMSCs inhibited osteoblast differentiation in tissue culture models;RNA-seq,Western blot,immunofluorescence,and RT-PCR analyses indicated that the Wnt/β-catenin pathway is the target of this inhibition.Indeed,we showed that ApoE had no effect on cultures with stabilizedβ-catenin levels.Next,we determined that Lrp4 serves as the osteoblast cell surface receptor to ApoE,as expression of Lrp4 is required in ApoE-based inhibition of Wnt/β-catenin signaling and osteoblast differentiation.Importantly,we validated this ApoE-Lrp4-Wnt/β-catenin molecular mechanism in human osteoblast differentiation.Finally,we identified an ApoE-neutralizing antibody(NAb)and used it to treat aged,wildtype mice 3 days after fracture surgery resulting in fracture calluses with 35%more bone deposition.Our work here identifies novel liver-to-bone cross-talk and a noninvasive,translatable therapeutic intervention for aged bone regeneration.展开更多
Electronic structure and optical properties of neutral and charged low band gap alternating copolyfluorenes （Green 1, which is based on alternating repeating units consisting of alkyl-substituted fluorene and a thiop...Electronic structure and optical properties of neutral and charged low band gap alternating copolyfluorenes （Green 1, which is based on alternating repeating units consisting of alkyl-substituted fluorene and a thiophene-[1,2,5]thiadiazolo-[3,4]quinoxaline-thiophene （T-TDQ-T） unit were investigated theoretically with time-dependent density functional theory （TD-DFT） method, and their excited state properties were further analyzed with 2D site and 3D cube representations. For neutral Green 1, the band gap, binding energy, exciton binding energy, and nuclear relaxation energy were obtained. The transition dipole moments of neutral and charged Green 1 are compared using 3D transition density, which reveals the orientation and strength of transition dipole moments. The charge redistribution of neutral and charged Green 1 upon excitation are displayed and compared with 3D charge difference density. The electron-hole coherences of neutral and charged Green 1 upon excitation are investigated with 2D site representation （transition density matrix）. The excited state properties of neutral Green 1 calculated with TD-DFT method are compared with that calculated with ZINDO method, which reveals the importance of electron-electron interaction （in TD-DFT） in the excited state properties.展开更多
A series of nickel complexes{4 a:[(2,6-iPr2C6H3)N=CHC16H12O]Ni(Me)(Py),4b:[(2,6-iPr2C6H2OCH3)N=CHC16H12O]-Ni(Me)(Py),4 c:[(2,6-iPr2C6H2Cl)N=CHC16H12O]Ni(Me)(Py),and 4d:[(2,6-iPr2C6H2CF3)N=CHC16H12O]Ni(Me)(Py)}based on...A series of nickel complexes{4 a:[(2,6-iPr2C6H3)N=CHC16H12O]Ni(Me)(Py),4b:[(2,6-iPr2C6H2OCH3)N=CHC16H12O]-Ni(Me)(Py),4 c:[(2,6-iPr2C6H2Cl)N=CHC16H12O]Ni(Me)(Py),and 4d:[(2,6-iPr2C6H2CF3)N=CHC16H12O]Ni(Me)(Py)}based onβ-ketiminato ligands bearing various electron-donating or electron-withdrawing substituents on the para-position of the aniline group were synthesized and unambiguously characterized.The X-ray crystallographic analysis showed that complexes 4 b and 4 d adopted a nearsquare-planar geometry,and the anilines bearing a para-OMe or―CF3 group were found to situate on the axial position of the metal center.All complexes exhibited high activities up to 1.25×10^7–1.35×10^7 g PNB·molNi^–1·h^–1 toward norbornene(NBE)addition polymerization(conversion>91.2%in 2 min)under low loading of B(C6F5)3(B/Ni=3)at 30°C,affording polymers with high molecular weight up to 2.54×10^6–3.18×10^6.Different levels of decrease in catalytic activities could be observed for all catalysts as the reaction temperature increased;4 d bearing a strong electron-withdrawing―CF3 group showed the highest activity at 70°C,while others exhibited notable decrease in catalytic activity with the raise in reaction temperature.Complexes 4 a–4 d showed remarkable tolerance to polar groups and could efficiently promote the copolymerization of NBE with its polar derivatives,including NBE bearing small acetate and hydroxyl group,as well as bulky oligomers,yielding copolymers with high functional NBE incorporations.Novel NBE copolymers with high functional comonomer incorporations and improved solubility were obtained in high yields.展开更多
This article is concerned with the problem of robust dissipative filtering for continuous-time polytopic uncertain neutral systems. The main purpose is to obtain a stable and proper linear filter such that the filteri...This article is concerned with the problem of robust dissipative filtering for continuous-time polytopic uncertain neutral systems. The main purpose is to obtain a stable and proper linear filter such that the filtering error system is strictly dissipative. A new criterion for the dissipativity of neutral systems is first provided in terms of linear matrix inequalities （LMI）. Then, an LMI sufficient condition for the existence of a robust filter is established and a design procedure is proposed for this type of systems. Two numerical examples are given. One illustrates the less conservativeness of the proposed criterion; the other demonstrates the validity of the filtering design procedure.展开更多
Functions of the polyamines in neutral rosin sizing were investigated using X-ray photoelectron spectroscopy (XPS) and laser diffraction particle analysis. The polyamine with a higher charge density and a smaller unit...Functions of the polyamines in neutral rosin sizing were investigated using X-ray photoelectron spectroscopy (XPS) and laser diffraction particle analysis. The polyamine with a higher charge density and a smaller unite size could retain more rosin and cover larger fiber surfaces. The XPS spectra demonstrated that polyallylamine (PAAm) and polyvinylamine (PVAm) could react with a rosin size to form a -OC-N-CO- structure, but polydimethylamino ethyl methacrylate (PDMAEMA) could not. The formation of this structure may be a key step for effective sizing.展开更多
The efficient copolymerization of olefin with polar monomers using nickel-based catalysts presents a longstanding challenge. In this contribution, three phosphine-benzocyclone ligands and corresponding neutral nickel ...The efficient copolymerization of olefin with polar monomers using nickel-based catalysts presents a longstanding challenge. In this contribution, three phosphine-benzocyclone ligands and corresponding neutral nickel catalysts(Ni1: Ar = Ph;Ni2: Ar = 2-(C_(6)H_(5))C_(6)H_(4);Ni3: Ar = 2-[2',6'-(Me O)_(2)-C_(6)H3]C_(6)H_(4)) were prepared and applied for the ethylene polymerization and copolymerization with polar monomers without any cocatalyst. The bulky substituent groups in complexes Ni2 and Ni3 contributed to high catalytic activities(up to 7.24×10^(6) and 9.04×10^(6)g·mol Ni^(-1)·h^(-1), respectively), and produced high-molecular-weight polyethylene(Mw up to 545.7 k Da). Complex Ni3 exhibited high activities for ethylene polymerization at the level of 10^(6) g·mol Ni^(-1)·h^(-1) across a wide range from 30 ℃ to 120 ℃, exhibiting excellent high temperature tolerance. These nickel complexes were also effectively employed in the copolymerization of ethylene with methyl acrylate, ethyl acrylate, butyl acrylate and lauryl acrylate, producing copolymers with high molecular weights(Mw up to 80.5 k Da) and high polar monomer incorporation(up to 8.2 mol%). Microstructure analyses revealed that the introduction of large sterically hindered substituents facilitated the incorporation of polar functional units into the polymer backbone. This study demonstrates the potential of these nickel-based catalysts for efficient copolymerization of olefin with polar monomers.展开更多
Poly(neutral red) film modified carbon fibre microelectrodes offer substantial improvement in voltammetric sensitivity and selectivity towards epinephrine (EP). The poly(neutral red) film was electropolymerized by cyc...Poly(neutral red) film modified carbon fibre microelectrodes offer substantial improvement in voltammetric sensitivity and selectivity towards epinephrine (EP). The poly(neutral red) film was electropolymerized by cycling the potential between -0.8 V and +0.8 V. The anodic stripping voltammetric response for EP was found to be dependent on accumulation time and potential. By using a poly(neutral red) film modified carbon fibre microelectrode with a 1 min preconcentration at -1.2 V in biological phosphate buffer solution (pH=7.4), a good linear relationship between the anodic stripping peak currents and EP concentrations was obtained in the range of 2.0×10 -7 ￣ 2.0×10 -5 mol/L. The detection limit was up to 9.0 ×10 -8 mol/L. Moreover, 400 times higher concentrations of vitamin C did not interfere with the measurement of EP. This method was used for determining EP concentrations in epinephrine hydrochloride injection solution with satisfactory results.展开更多
Smallpox eradication was successful via prophylactic administration of live attenuated vaccinia virus. As a result of the discontinuation of the smallpox immunization program, many individuals are now susceptible to s...Smallpox eradication was successful via prophylactic administration of live attenuated vaccinia virus. As a result of the discontinuation of the smallpox immunization program, many individuals are now susceptible to smallpox virus infection should it be used as a biological weapon. Presently, only individuals at high risk for exposure are required to receive smallpox vaccine, such as laboratory personnel that handle variola/vaccinia virus. This study endeavored to investigate a one-year period of vaccinia virus-specific T cell responses using polychromatic flow cytometry and neutralizing (Nt) antibody responses using plaque reduction neutralization test (PRNT) in individuals receiving primary immunization (n = 5) with ACAM2000<sup>TM</sup> smallpox vaccine. Functional and phenotypic profiles of vaccinia virus-specific T cell responses were characterized. Each single functional measurement {CD107a/b expression, production of interferon g (IFN-g), macrophage inflammatory protein 1b (MIP-1b), interleukin 2 (IL-2), and tumor necrosis factor a (TNF-a)} demonstrated that vaccinia virus-specific CD8<sup>+</sup> T cells were functional at least one time point after vaccination (p ≤ 0.05). However, vaccinia virus-specific CD4<sup>+</sup> T cells were functional only for MIP-1b production (p ≤ 0.05). Vaccinia virus-specific CD8<sup>+</sup> T cells induced in these individuals showed increased polyfunctionality in at least 2 phenotypes relative to pre-vaccination (p ≤ 0.05). Although only three of five individuals (60%) showed positive Nt antibody (titer ≥ 20) at first month after vaccination, all five individuals (100%) demonstrated Nt antibody at 2 months, post-immunization. Interestingly, all vaccinees could retain the Nt antibody for 6 months after primary vaccination. In conclusion, ACAM2000<sup>TM</sup> smallpox vaccine induced both polyfunctional T cell-and Nt antibody-responses in primary immunized individuals.展开更多
A neutral nickel(Ⅱ)catalyst D,{[O-(3-cyclohexyl)(5-Cl)C_6H_2-ortho-C(H)=N-2,6-C_6H_3(i-Pr)_2]Ni(Ph_3P)(Ph)}hasbeen synthesized and characterized by IH-NMR,FTIR and elemental analysis.The results indicate that Al(i-Bu...A neutral nickel(Ⅱ)catalyst D,{[O-(3-cyclohexyl)(5-Cl)C_6H_2-ortho-C(H)=N-2,6-C_6H_3(i-Pr)_2]Ni(Ph_3P)(Ph)}hasbeen synthesized and characterized by IH-NMR,FTIR and elemental analysis.The results indicate that Al(i-Bu)_3 is aneffective cocatalyst for the neutral nickel catalyst.With bis(1,5-cyclooctadiene)nickel(0)[Ni(COD)_2]or Al(i-Bu)_3 as a co-catalyst,the neutral nickel catalyst D is active for ethylene polymerisation and copolymerisation with polar monomers(tert-butyl 10-undecenoate(BU),methyl 10-undecenoate(MU),allyl alcohol(AA)and 4-penten-1-ol(PO))under mild conditions.The resulting polymers were characterized by (?)H-NMR,FTIR,DSC,and GPC.From the comparative studies,Ni(COD)_2 ismore active than Al(i-Bu)_3 for ethylene homopolymerization,while Al(i-Bu)_3 is more effective than Ni(COD)_2 for ethylenecopolymerisation with polar monomers.The polymerization parameters which affect both the catalytic activity and propertiesof the resulting polyethylene were investigated in detail.Under the conditions of 20 μmol catalyst D and Ni(COD)_2/D=3(molar ratio) in 30 mL toluene solution at 45℃,12×105 Pa ethylene for 20 min,the polymerization activity reaches ashigh as 7.29×105 gPE.(mol.Ni.h)^(-1) and M_η,is 7.16×104 g.mol^(-1).For ethylene copolymerization with polar monomers,theeffect of comonomer concentrations was examined.As high as 0.97 mol% of MU,1.06 mol% of BU,1.04 mol% of AA and1.37 mol% of PO were incorporated into the polymer,respectively,catalyzed by D/Al(i-Bu)_3 system.展开更多
文摘Archroma becomes the exclusive global distributor of Fibre52®'s patented chemistry-advancing a new standard in sustainable processing.Combined with Archroma's AVITERA®SE dyes,the partnership delivers the industry's most resource-efficient bleach-and-dye sys-tems.Archroma,a leading global specialty chemicals company committed to sus-tainable innovation,and Innovo Fiber LLC,owner of the patented Fibre52®system,today announced an exclusive global dis-tribution partnership to expand the reach of Fibre52®'s proven low-temperature,bleaching technology with innovative dyeing application to textile mills and brands worldwide.
基金supported by the National Natural Science Foundation of China(No.52371004,52201144,52071040,U20A20230).
文摘Bending is a crucial operation in the sheet forming of Mg alloys for automotive and aerospace applications.In this work,three kinds of sheets from an AZ31 rolled plate,sheared at 0°(S0),45°(S45),and 90°(S90)to the rolling direction,were subjected to three-point bending tests.In-situ digital image correlation(DIC)system was employed to capture the strain fields.Electron backscatter diffraction(EBSD)was used to examine the through-thickness microstructures.A crystal plasticity finite element method(CPFEM)incorporating twinning and slip mechanisms was developed to simulate the bending deformation.The texture effect on the neutral layer shift and twinning behaviors was systematically investigated in terms of both experiments and simulations.The results show that CPFEM effectively simulated the texturedependent shifting behaviors of neutral layer and the associated twinning behaviors.Particularly,the spatial distributions of neutral layer across the entire bent plates were captured by both DIC and CPFEM.Additionally,some unusual twinning behaviors were analyzed in depth,such as the{10-12}-{10-12}secondary twins in S90,localized twin bands in S0,and the twin traces difference in S45.These findings reveal a close relationship between the neutral layer shift and twinning activity induced by the initial texture and strain levels.This work provides valuable insights into the bending deformation mechanisms of Mg alloys and has important implications for improving their formability and controlling springback.
基金the financial support from the National Natural Science Foundation of China (No. 52072390)the National High-Level Talents Special Support Program (Leading Talent of Technological Innovation)+2 种基金the China Postdoctoral Science Foundation (No. 2023M743648)the Young Scientists Fund of the National Natural Science Foundation of China (No. 52302330)the support from the Shanghai Emperor of Cleaning Hi-Tech Co.,LTD
文摘In-situ poly(1,3-dioxolane)(PDOL)-based electrolyte has received extensive attention in the research of lithium metal batteries due to its high stability to lithium anode and simple processing.However,it is still faced with defects such as low intrinsic ionic conductivity,a narrow electrochemical window,and poor thermal stability.A crosslinking and fluorination molecular design strategy toward PDOL is proposed to tackle the issues above.The amorphous crosslinked structure effectively improves ionic conductivity by inhibiting long-chain crystallization.Especially,the antioxidant–CF_(3)groups,stable crosslinked structure,and reduced terminal hydroxyl groups significantly enhance the electrochemical oxidation stability with a superb high-voltage window of 4.7 V.In addition,the designed electrolyte also exhibits obviously improved thermal stability with no deformation at 120°C for 5 min.Furthermore,the semi-solid NCM811||Li batteries exhibit a favourable capacity retention of 88.8%after 150 cycles at 0.5 C.Even assembled with NCM622 cathode working at 4.5 V,the semi-solid batteries can still show a satisfactory capacity retention of 85.3%after 100 cycles at 0.5 C.Also,a 0.1 Ah NCM811||Li pouch cell with active materials loading of 9 mg/cm2 demonstrates satisfactory cycling stability and working ability,which shows promising practical application prospects.
基金financially supported by the Jiangsu Forestry Science and Technology Innovation and Promotion Project(No.LYKJ-Nanjing[2022]02)the Jiangsu Agricultural Science and Technology Innovation Fund(No.CX(23)3090)。
文摘Smart pesticide delivery systems based on stimuli-responsive nanocarriers have attracted considerable attention because of their potential to enhance pesticide efficiency while reducing environmental risks.In this study,a novel p H/glutathione dual-responsive pesticide delivery system was constructed through the synthesis of disulfide-bridged hollow mesoporous organosilica nanospheres(HMONs)via the St??ber method,followed by poly(acrylic acid)(PAA)coating through distillation-precipitation polymerization to form HMONs@PAA nanocomposites.The resulting abamectin-loaded system(Abamectin-HMONs@PAA)demonstrated a 12.73% pesticide loading capacity and significantly improved photostability,retaining twice as much active ingredient as free abamectin after 250 h of UV irradiation(36 W).Release studies revealed p H-and glutathione-dependent characteristics,with cumulative releases in acidic conditions exceeding those in neutral and alkaline environments by 18.66% and 40.98%,respectively,and a 14.2% increase in glutathione-containing solution(0.2 mmol·L^(-1) in 70% ethanol)after 97 h.Bioassays showed superior performance against Plutella xylostella,with a 13.33% reduction in survival rate compared to conventional suspension at equivalent dosage(40 mg·L^(-1)),while maintaining efficacy after extensive rainfall simulation(20 events over 10 days).This study provides a promising approach for developing environmentally responsive nanopesticides with enhanced durability and controlled-release properties,offering significant potential for sustainable crop protection.
基金funded by the National Natural Science Foundation of China(Grant No.42275039)the Meteorological Joint Fund by NSF and CMA(Grant No.U2342224)+1 种基金the National Key R&D Program of China(Grant No.2022YFC3701202)the S&T Development Fund of CAMS(Grant No.2024KJ019)。
文摘Global land monsoon precipitation(GLMP)is highly sensitive to changes in interhemispheric thermal contrast(ITC).Amplified interhemispheric asymmetries of GLMP due to enhanced ITC driven by high-level anthropogenic emissions are expected to simultaneously increase the probability of regional floods and droughts,threatening ecosystems within global terrestrial monsoon regions and the freshwater supply for billions of residents in these areas.In this study,the responses of GLMP to the evolution of ITC toward the carbon neutrality goal are assessed using multimodel outputs from a new model intercomparison project(CovidMIP).The results show that the Northern Hemisphere-Southern Hemisphere(NH-SH)asymmetry of GLMP in boreal summer weakens during the 2040s,as a persistent reduction in well-mixed greenhouse gas(WMGHG)emissions leads to a downward trend in the ITC after 2040.At the same time,the reduction in WMGHG emissions dampens the Eastern Hemisphere-Western Hemisphere(EH-WH)asymmetry of GLMP by inducing La Niña-like cooling and enhancing moisture transport to Inner America.The resulting increases in land monsoon precipitation(LMP)may alleviate drought under the global warming scenario by about 19%-25%and 7%-9%in the WH and SH monsoon regions,respectively.However,a persistent reduction in aerosol emissions in Asia will dominate the increases in LMP in this region until the mid-21st century,and these increases may be approximately 23%-60%of the growth under the global warming scenario.Our results highlight the different rates of response of aerosol and WMGHG concentrations to the carbon neutrality goal,leading to various changes in LMP at global and regional scales.
基金the“Pioneer”and“Leading Goose”R&D Program of Zhejiang(No.2023C01072)the Institute of Zhejiang University-Quzhou for their financial support。
文摘Poly(phenylene oxide)(PPO)exhibits excellent dielectric properties,making it an ideal substrate for high-frequency,high-speed copper-clad laminates.The phenolic hydroxyl group at the end of PPO plays a key role in its reactivity.Accurately quantifying the phenolic hydroxyl content in PPO is essential but challenging.In this study,we proposed a method for measuring the phenolic hydroxyl content of PPO using differential UV absorption spectroscopy.In alkaline solutions,the phenolic hydroxyl in PPO completely ionizes to form phenoxide ions,leading to a significant increase in UV absorbance at approximately 250 and 300 nm.Notably,the differential UV absorbance at approximately 300 nm was directly proportional to the phenolic hydroxyl concentration.Using 2,6-dimethylphenol as a standard,a calibration curve was established to relate the phenolic hydroxyl concentration to differential UV absorbance at approximately 300 nm,providing a precise and straightforward method for phenolic hydroxyl quantification in PPO with distinct advantages over conventional techniques.
基金financially supported by National Natural Science Foundation of China(22466010)Guizhou Provincial Basic Research Program(Natural Science)ZK[2023]47 and key program ZD[2025]075+6 种基金Innovation and Entrepreneurship Project for overseas Talents in Guizhou Province[2022]02Specific Natural Science Foundation of Guizhou University(X202207)the national undergraduate innovation and entrepreneurship training program(gzugc2023006gzusc2024012)SRT project of Guizhou university(2023SRT0292023SRT024)supported by Shanghai Technical Service Center of Science and Engineering Computing,Shanghai University。
文摘Electrocatalytic nitrate reduction reaction(NO3RR)represents a sustainable and environmentally benign route for ammonia(NH3)synthesis.However,NO3RR is still limited by the competition from hydrogen evolution reaction(HER)and the high energy barrier in the hydrogenation step of nitrogen-containing intermediates.Here,we report a selective etching strategy to construct Ru M nanoalloys(M=Fe,Co,Ni,Cu)uniformly dispersed on porous nitrogen-doped carbon substrates for efficient neutral NH3electrosynthesis.Density functional theory calculations confirm that the synergic effect between Ru and transition metal M modulates the electronic structure of the alloy,significantly lowering the energy barrier for the conversion of*NO_(2)to*HNO_(2).Experimentally,the optimized Ru Fe-NC catalyst achieves 100%Faraday efficiency with a high yield rate of 0.83 mg h^(-1)mg^(-1)catat a low potential of-0.1 V vs.RHE,outperforming most reported catalysts.In situ spectroscopic analyses further demonstrate that the Ru M-NC effectively promotes the hydrogenation of nitrogen intermediates while inhibiting the formation of hydrogen radicals,thereby reducing HER competition.The Ru FeNC assembled Zn-NO_(3)^(-)battery achieved a high open-circuit voltage and an outstanding power density and capacity,which drive selective NO_(3)^(-)conversion to NH3.This work provides a powerful synergistic design strategy for efficient NH3electrosynthesis and a general framework for the development of advanced multi-component catalysts for sustainable nitrogen conversion.
文摘Although poly(urethane-urea)elastomers(PUEs)possess excellent mechanical properties and durability,their inherent flammability and inability to self-repair after damage significantly limits their applications in high-end fields.To address this challenge,this study employs a supramolecular chemistry approach by simultaneously incorporating multiple hydrogen bonds as dynamic cross-linking points and a phosphorus-nitrogen synergistic flame-retardant structure into the poly(urethane-urea)network.The multiple hydrogen bonds endow the material with efficient intrinsic self-healing capability,while the phosphorus-nitrogen flame retardant ensures outstanding thermal stability and flame resistance,leading to the successful synthesis of a high-performance multifunctional poly(urethane-urea)elastomer.Experimental results demonstrated that when the content of the flame retardant diethyl(2-((2-aminoethyl)amino)ethyl)phosphoramidate(DEPTA)was 10 wt%,the resulting PUE/10%DEPTA achieved a V-0 rating in the vertical burning test,with a limiting oxygen index(LOI)of 30%.Concurrently,the elastomer maintained good toughness,exhibiting a tensile strength of 27.3 MPa,an elongation at break of 601%,and a self-healing efficiency of up to 94.46%.This breakthrough shows significant promise for advanced engineering applications that demand fire safety,structural durability,and extended service life through self-repair.
基金financially supported by the National Natural Science Foundation of China(Nos.22473105 and 22341302).
文摘This study uses all-atom molecular dynamics simulations to investigate the dislocation propagation, stress transmission, and mechanical properties in poly(p-phenylene terephthalamide) fibers under uniaxial tension. The results indicate that the dislocation propagates and the stress transfers not only along the fiber axis but also between adjacent molecular chains through hydrogen bonds, demonstrating their influence on the yield behavior. As the degree of polymerization increases, breakage of covalent bonds and interchain slippage contribute to the yield of fibers together. This work provides theoretical guidance for the design and manufacturing of high-performance fibers.
基金financially supported by the National Key Research and Development Program of China(No.2021YFB3700300)the National Natural Science Foundation of China(Nos.52573017 and U21B2093)+1 种基金Key Research and Development Program of Ningbo(No.2022Z200)the Zhejiang Provincial Natural Science Foundation(No.LY23E030005)。
文摘Bio-based 2,5-furandicarboxylic acid polyesters offer significant promise for reducing energy and environmental crises.However,their intrinsic flammability remains a critical limitation,and conventional flame-retardant strategies often compromise their mechanical properties,hindering their practical applications.Herein,a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO)-based comonomer(DDP)was used to synthesize flame-retardant poly(ethylene furandicarboxylate-co-phosphaphenanthrene)(PEFDn).The covalent integration of DDP confers intrinsic flame retardancy,avoiding the plasticization and migration issues associated with additive-type systems.Upon thermal decomposition,the DOPO-derived moieties release phosphoric acid and radical scavengers,promoting char formation and suppressing flame propagation.Furthermore,density functional theory(DFT)calculations combined with non-covalent interaction(NCI)analysis revealed that DOPO dimer molecules adopt a stable parallel-displaced π-π stacking configu ration,potentially facilitating microphase separation and enhancing the energy dissipation capability.PEFD_(10)achieves a UL-94 V-0 rating while simultaneously increasing impact toughness from 1.5 kJ/m^(2) to 14.7 kJ/m^(2).Im portantly,PEFDn maintained acceptable oxygen-barrier properties.PEFD10 also exhibited high transparency and UV-shielding performance.The combination of intrinsic flame safety,im pact-toughness resistance,UV shielding,and an oxygen barrier ensures reliable protection of electrical components and long-term operational stability.The integration of multiple critical properties within a single bio-based material represents a novel approach fo r enabling sustainable polymer solutions for high-pe rformance electrical applications.
基金supported through RIIM Competition funding from the Indonesia Endowment Fund for Education Agency,Ministry of Finance of the Republic of Indonesia and National Research and Innovation Agency of Indonesia according to the contract number:61/IV/KS/5/2023 and 2131/UN6.3.1/PT.00/2023.
文摘Corn starch(CS)is a renewable,biodegradable polysaccharide valued for its film-forming ability,yet native CS films exhibit lowmechanical strength,highwater sensitivity,and limited thermal stability.This study improves CS-based films by blending with poly(vinyl alcohol)(PVA)or glycerol(GLY)and using citric acid(CA)as a green,non-toxic cross-linker.Composite films were prepared by casting CS–PVA or CS-GLY with CA at 0%-0.20%(w/w of starch).The influence of CA on physicochemical,mechanical,optical,thermal,and water barrier properties was evaluated.CA crosslinking markedly enhanced the tensile strength,water resistance,and thermal stability of CS-PVA films while increasing transparency in CS–GLY films.At 0.20%CA,the composite achieved 34.99MPa tensile strength,reducedwater vapor permeability,andminimized water uptake.FTIR confirmed ester bond formation between CAand hydroxyl groups of CS,PVA,and GLY,whereas thermal analysis showed higher decomposition temperatures and lower weight loss in crosslinked films.Increasing CA levels also decreased opacity and improved light transmittance,indicating greater homogeneity and reduced crystallinity.This dual-polymer matrix combined with a natural crosslinking strategy provides a sustainable route to high-performance,biodegradable CS-based packaging materials.
基金supported by a Borden Scholars awardDuke Claude D.Pepper Older Americans Independence Center Pilot Award(P30AG028716)by the NIH/NIA(R01AG081393)。
文摘Advanced age impairs bone fracture healing;the underlying mechanism of this phenomenon remains unknown.We determined that apolipoprotein E(ApoE)increases with age and causes poor fracture healing.After deletion of hepatic ApoE expression(ΔApoE),24-month-oldΔApoE mice displayed a 95%reduction in circulating ApoE levels and significantly improved fracture healing.ApoE treatment of aged BMSCs inhibited osteoblast differentiation in tissue culture models;RNA-seq,Western blot,immunofluorescence,and RT-PCR analyses indicated that the Wnt/β-catenin pathway is the target of this inhibition.Indeed,we showed that ApoE had no effect on cultures with stabilizedβ-catenin levels.Next,we determined that Lrp4 serves as the osteoblast cell surface receptor to ApoE,as expression of Lrp4 is required in ApoE-based inhibition of Wnt/β-catenin signaling and osteoblast differentiation.Importantly,we validated this ApoE-Lrp4-Wnt/β-catenin molecular mechanism in human osteoblast differentiation.Finally,we identified an ApoE-neutralizing antibody(NAb)and used it to treat aged,wildtype mice 3 days after fracture surgery resulting in fracture calluses with 35%more bone deposition.Our work here identifies novel liver-to-bone cross-talk and a noninvasive,translatable therapeutic intervention for aged bone regeneration.
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.10505001, No.10875055, No.10874234, and No.10703064） and the Educational Department of Liaoning Province （No.2008228）.
文摘Electronic structure and optical properties of neutral and charged low band gap alternating copolyfluorenes （Green 1, which is based on alternating repeating units consisting of alkyl-substituted fluorene and a thiophene-[1,2,5]thiadiazolo-[3,4]quinoxaline-thiophene （T-TDQ-T） unit were investigated theoretically with time-dependent density functional theory （TD-DFT） method, and their excited state properties were further analyzed with 2D site and 3D cube representations. For neutral Green 1, the band gap, binding energy, exciton binding energy, and nuclear relaxation energy were obtained. The transition dipole moments of neutral and charged Green 1 are compared using 3D transition density, which reveals the orientation and strength of transition dipole moments. The charge redistribution of neutral and charged Green 1 upon excitation are displayed and compared with 3D charge difference density. The electron-hole coherences of neutral and charged Green 1 upon excitation are investigated with 2D site representation （transition density matrix）. The excited state properties of neutral Green 1 calculated with TD-DFT method are compared with that calculated with ZINDO method, which reveals the importance of electron-electron interaction （in TD-DFT） in the excited state properties.
基金financially supported by the National Natural Science Foundation of China (Nos. 21574097 and 21690071)
文摘A series of nickel complexes{4 a:[(2,6-iPr2C6H3)N=CHC16H12O]Ni(Me)(Py),4b:[(2,6-iPr2C6H2OCH3)N=CHC16H12O]-Ni(Me)(Py),4 c:[(2,6-iPr2C6H2Cl)N=CHC16H12O]Ni(Me)(Py),and 4d:[(2,6-iPr2C6H2CF3)N=CHC16H12O]Ni(Me)(Py)}based onβ-ketiminato ligands bearing various electron-donating or electron-withdrawing substituents on the para-position of the aniline group were synthesized and unambiguously characterized.The X-ray crystallographic analysis showed that complexes 4 b and 4 d adopted a nearsquare-planar geometry,and the anilines bearing a para-OMe or―CF3 group were found to situate on the axial position of the metal center.All complexes exhibited high activities up to 1.25×10^7–1.35×10^7 g PNB·molNi^–1·h^–1 toward norbornene(NBE)addition polymerization(conversion>91.2%in 2 min)under low loading of B(C6F5)3(B/Ni=3)at 30°C,affording polymers with high molecular weight up to 2.54×10^6–3.18×10^6.Different levels of decrease in catalytic activities could be observed for all catalysts as the reaction temperature increased;4 d bearing a strong electron-withdrawing―CF3 group showed the highest activity at 70°C,while others exhibited notable decrease in catalytic activity with the raise in reaction temperature.Complexes 4 a–4 d showed remarkable tolerance to polar groups and could efficiently promote the copolymerization of NBE with its polar derivatives,including NBE bearing small acetate and hydroxyl group,as well as bulky oligomers,yielding copolymers with high functional NBE incorporations.Novel NBE copolymers with high functional comonomer incorporations and improved solubility were obtained in high yields.
基金supported by the Major Program of National Natural Science Foundation of China(60710002)the Program for Changjiang Scholars and Innovative Research Team in University.
文摘This article is concerned with the problem of robust dissipative filtering for continuous-time polytopic uncertain neutral systems. The main purpose is to obtain a stable and proper linear filter such that the filtering error system is strictly dissipative. A new criterion for the dissipativity of neutral systems is first provided in terms of linear matrix inequalities （LMI）. Then, an LMI sufficient condition for the existence of a robust filter is established and a design procedure is proposed for this type of systems. Two numerical examples are given. One illustrates the less conservativeness of the proposed criterion; the other demonstrates the validity of the filtering design procedure.
基金This work was supported by International Co-operation Project of Fujian Province(99-I-5).
文摘Functions of the polyamines in neutral rosin sizing were investigated using X-ray photoelectron spectroscopy (XPS) and laser diffraction particle analysis. The polyamine with a higher charge density and a smaller unite size could retain more rosin and cover larger fiber surfaces. The XPS spectra demonstrated that polyallylamine (PAAm) and polyvinylamine (PVAm) could react with a rosin size to form a -OC-N-CO- structure, but polydimethylamino ethyl methacrylate (PDMAEMA) could not. The formation of this structure may be a key step for effective sizing.
基金financially supported by the National Natural Science Foundation of China (No. 52130307)。
文摘The efficient copolymerization of olefin with polar monomers using nickel-based catalysts presents a longstanding challenge. In this contribution, three phosphine-benzocyclone ligands and corresponding neutral nickel catalysts(Ni1: Ar = Ph;Ni2: Ar = 2-(C_(6)H_(5))C_(6)H_(4);Ni3: Ar = 2-[2',6'-(Me O)_(2)-C_(6)H3]C_(6)H_(4)) were prepared and applied for the ethylene polymerization and copolymerization with polar monomers without any cocatalyst. The bulky substituent groups in complexes Ni2 and Ni3 contributed to high catalytic activities(up to 7.24×10^(6) and 9.04×10^(6)g·mol Ni^(-1)·h^(-1), respectively), and produced high-molecular-weight polyethylene(Mw up to 545.7 k Da). Complex Ni3 exhibited high activities for ethylene polymerization at the level of 10^(6) g·mol Ni^(-1)·h^(-1) across a wide range from 30 ℃ to 120 ℃, exhibiting excellent high temperature tolerance. These nickel complexes were also effectively employed in the copolymerization of ethylene with methyl acrylate, ethyl acrylate, butyl acrylate and lauryl acrylate, producing copolymers with high molecular weights(Mw up to 80.5 k Da) and high polar monomer incorporation(up to 8.2 mol%). Microstructure analyses revealed that the introduction of large sterically hindered substituents facilitated the incorporation of polar functional units into the polymer backbone. This study demonstrates the potential of these nickel-based catalysts for efficient copolymerization of olefin with polar monomers.
文摘Poly(neutral red) film modified carbon fibre microelectrodes offer substantial improvement in voltammetric sensitivity and selectivity towards epinephrine (EP). The poly(neutral red) film was electropolymerized by cycling the potential between -0.8 V and +0.8 V. The anodic stripping voltammetric response for EP was found to be dependent on accumulation time and potential. By using a poly(neutral red) film modified carbon fibre microelectrode with a 1 min preconcentration at -1.2 V in biological phosphate buffer solution (pH=7.4), a good linear relationship between the anodic stripping peak currents and EP concentrations was obtained in the range of 2.0×10 -7 ￣ 2.0×10 -5 mol/L. The detection limit was up to 9.0 ×10 -8 mol/L. Moreover, 400 times higher concentrations of vitamin C did not interfere with the measurement of EP. This method was used for determining EP concentrations in epinephrine hydrochloride injection solution with satisfactory results.
文摘Smallpox eradication was successful via prophylactic administration of live attenuated vaccinia virus. As a result of the discontinuation of the smallpox immunization program, many individuals are now susceptible to smallpox virus infection should it be used as a biological weapon. Presently, only individuals at high risk for exposure are required to receive smallpox vaccine, such as laboratory personnel that handle variola/vaccinia virus. This study endeavored to investigate a one-year period of vaccinia virus-specific T cell responses using polychromatic flow cytometry and neutralizing (Nt) antibody responses using plaque reduction neutralization test (PRNT) in individuals receiving primary immunization (n = 5) with ACAM2000<sup>TM</sup> smallpox vaccine. Functional and phenotypic profiles of vaccinia virus-specific T cell responses were characterized. Each single functional measurement {CD107a/b expression, production of interferon g (IFN-g), macrophage inflammatory protein 1b (MIP-1b), interleukin 2 (IL-2), and tumor necrosis factor a (TNF-a)} demonstrated that vaccinia virus-specific CD8<sup>+</sup> T cells were functional at least one time point after vaccination (p ≤ 0.05). However, vaccinia virus-specific CD4<sup>+</sup> T cells were functional only for MIP-1b production (p ≤ 0.05). Vaccinia virus-specific CD8<sup>+</sup> T cells induced in these individuals showed increased polyfunctionality in at least 2 phenotypes relative to pre-vaccination (p ≤ 0.05). Although only three of five individuals (60%) showed positive Nt antibody (titer ≥ 20) at first month after vaccination, all five individuals (100%) demonstrated Nt antibody at 2 months, post-immunization. Interestingly, all vaccinees could retain the Nt antibody for 6 months after primary vaccination. In conclusion, ACAM2000<sup>TM</sup> smallpox vaccine induced both polyfunctional T cell-and Nt antibody-responses in primary immunized individuals.
基金This work was supported by the NSFC(No.2007402820374043)SINOPEC(X500030).
文摘A neutral nickel(Ⅱ)catalyst D,{[O-(3-cyclohexyl)(5-Cl)C_6H_2-ortho-C(H)=N-2,6-C_6H_3(i-Pr)_2]Ni(Ph_3P)(Ph)}hasbeen synthesized and characterized by IH-NMR,FTIR and elemental analysis.The results indicate that Al(i-Bu)_3 is aneffective cocatalyst for the neutral nickel catalyst.With bis(1,5-cyclooctadiene)nickel(0)[Ni(COD)_2]or Al(i-Bu)_3 as a co-catalyst,the neutral nickel catalyst D is active for ethylene polymerisation and copolymerisation with polar monomers(tert-butyl 10-undecenoate(BU),methyl 10-undecenoate(MU),allyl alcohol(AA)and 4-penten-1-ol(PO))under mild conditions.The resulting polymers were characterized by (?)H-NMR,FTIR,DSC,and GPC.From the comparative studies,Ni(COD)_2 ismore active than Al(i-Bu)_3 for ethylene homopolymerization,while Al(i-Bu)_3 is more effective than Ni(COD)_2 for ethylenecopolymerisation with polar monomers.The polymerization parameters which affect both the catalytic activity and propertiesof the resulting polyethylene were investigated in detail.Under the conditions of 20 μmol catalyst D and Ni(COD)_2/D=3(molar ratio) in 30 mL toluene solution at 45℃,12×105 Pa ethylene for 20 min,the polymerization activity reaches ashigh as 7.29×105 gPE.(mol.Ni.h)^(-1) and M_η,is 7.16×104 g.mol^(-1).For ethylene copolymerization with polar monomers,theeffect of comonomer concentrations was examined.As high as 0.97 mol% of MU,1.06 mol% of BU,1.04 mol% of AA and1.37 mol% of PO were incorporated into the polymer,respectively,catalyzed by D/Al(i-Bu)_3 system.
