The retrospective study by Edwar et al reinforces the role of therapeutic penetrating keratoplasty(PK)as a vital intervention in severe,treatment-resistant infectious keratitis.In advanced cases—often complicated by ...The retrospective study by Edwar et al reinforces the role of therapeutic penetrating keratoplasty(PK)as a vital intervention in severe,treatment-resistant infectious keratitis.In advanced cases—often complicated by trauma,delayed presentation,and corneal perforation—PK restores globe integrity and provides limited visual recovery.However,its application is constrained by graft-related complications and donor shortages,particularly in low-resource settings.These limitations highlight the need for earlier,globe-sparing strategies to prevent progression and reduce surgical demand.Photoactivated chromophore for infectious keratitis-corneal collagen cross-linking(PACK-CXL)has emerged as a promising adjunct or alternative.With both antimicrobial and tissue-stabilizing effects,PACK-CXL may control infection and preserve corneal structure in earlier stages.A layered treatment framework that incorporates PACK-CXL as an initial intervention and reserves PK for refractory cases may help improve clinical outcomes.Further studies are needed to define their best use in practice.展开更多
Based on the characteristics of laser-induced surface ignition,energetic photosensitive films show promising potential to meet the ignition requirements of various energetic materials(EMs).In this study,DATNBI/ferric ...Based on the characteristics of laser-induced surface ignition,energetic photosensitive films show promising potential to meet the ignition requirements of various energetic materials(EMs).In this study,DATNBI/ferric alginate(DI/FeA),DI/cobalt alginate(DI/CoA),and DI/nickel alginate(DI/Ni A)films are fabricated by employing sodium alginate(SA)with a three-dimensional network structure as the film matrix,via ionic cross-linking of SA with Fe^(3+),Co^(2+),and Ni^(2+)ions.The study demonstrates that the ionic cross-linking enhances the hydrophobic performance of the films,with the water contact angle increasing from 82.1° to 123.5°.Concurrently,the films'near-infrared(NIR)light absorption improved.Furthermore,transition metal ions facilitate accelerated electron transfer,thereby catalyzing the thermal decomposition of DATNBI.Under 1064 nm laser irradiation,the DI/Fe A film exhibits exceptional combustion performance,with an ignition delay time as low as 76 ms.It successfully acts as an NIR laser ignition medium to initiate the self-sustained combustion of CL-20.This study demonstrates the synergistic realization of enhanced hydrophobicity,improved photosensitivity,and promoted catalytic decomposition through microstructural design of the material,providing new insights for the design of additive-free EMs in laser ignition applications.展开更多
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polym...To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.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
Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catal...Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.展开更多
Switchable polymerization is emerging as a powerful tool to construct block copolymers directly from mixtures of monomers.However,current achievements typically iterate between two polymerization cycles to afford prod...Switchable polymerization is emerging as a powerful tool to construct block copolymers directly from mixtures of monomers.However,current achievements typically iterate between two polymerization cycles to afford products with fixed sequences and compositions.Herein,we report the triethylborane/1,8-diazabicyclo[5.4.0]undec-7-ene(Et_3B/DBU)pair-mediated four-component switchable polymerization of propylene oxide(PO),CO_(2),phthalic anhydride(PA),and racemic lactide(rac-LA),which enables the on-demand synthesis of four different block copolymers,i.e.,poly(propylene phthalate)-b-polylactide(PPE-b-PLA),PPE-b-PLA-b-poly(propylene carbonate)(PPC),PPE-b-PPC-b-PLA,and PPE-b-PPCb-poly(propylene oxide)(PPO),through rationally modulating the Lewis pair(LP)ratio.Core to this protocol is that increasing the loading of Et_(3)B accelerates the ring-opening of PO while impeding the reactivity of rac-LA,thus allowing for fine-tuning of the thermodynamic and kinetic of the switchable polymerization.Therefore,the four polymerization cycles involving PO/PA ring-opening copolymerization(ROCOP),PO/CO_2 ROCOP,rac-LA ring-opening polymerization(ROP),and PO ROP can be connected and discriminated in precisely programmed manners.展开更多
Polymer binders possess significant potential in alleviating the volume expansion issues of silicon-based anodes,yet remain challenging due to insufficient interfacial interactions with individual components(Si,C,and ...Polymer binders possess significant potential in alleviating the volume expansion issues of silicon-based anodes,yet remain challenging due to insufficient interfacial interactions with individual components(Si,C,and Cu)of the anode.Herein,we report the synthesis of a stable three-dimensional network structure of the PAA-PEA(polyacrylic acid-polyether amines)polymer binder through intermolecular physicochemical dual cross-linking.By incorporating polar functional groups,the binder molecules not only form strong C-O-Si,N-Si,O=C-O-C,and O=C-O-Cu covalent bonds but also enhance non-covalent interactions with Si,C,and Cu,thereby improving adhesion between the binder and each interface of the anode.Furthermore,weak hydrogen bonds,acting as"sacrificial bonds",dissipate energy and disperse accumulated stress,improving the material flexibility.Due to the high mechanical stability of the framework,which combines both rigidity and flexibility and the coupling effect at the three interfaces,the movement and separation of electrode components are effectively restrained,significantly enhancing the cycling stability of silicon-graphite anodes.The PAA-PEA 2000 electrode exhibits a capacity retention of 78% after 500 cycles at a current density of 0.2 A g^(-1).This work provides insights into the mechanism of binders and guides the design of polymer binders for high-performance Si-based electrodes.展开更多
A controlled cross-linking polymerization containing intra- and intermolecular reactions was designed based on random coil morphology of macromolecules in solution. The soluble intramolecular cross-linked maeromolecu...A controlled cross-linking polymerization containing intra- and intermolecular reactions was designed based on random coil morphology of macromolecules in solution. The soluble intramolecular cross-linked maeromolecule （ICM） was successfully synthesized in the system with PVA and MDI. We found an especial dissolving phenomenon, namely the semi-soluble phenomenon when some gels dissolved in DMF. The chain growth process of ICMs was investigated by Transmission electron microscopy （TEM） pictures of samples at different reacting times, in addition, TEM pictures show ICMs have three kinds of styles in structure, viz. ＂globule structure＂, ＂nubby structure＂ and the intervenient between the above two structures, and the efflux time of the ICMs was measured by an Ubbelohde viscosimeter, it was found that the efflux time decreases with the degree ofcrosslink increasing.展开更多
The overall cross-linking copolymerization of acrylic acid and multi-armed cross-linkers are investigated by in situ interferometry. The results show that the more arms the cross-linkers have, the higher the polymeriz...The overall cross-linking copolymerization of acrylic acid and multi-armed cross-linkers are investigated by in situ interferometry. The results show that the more arms the cross-linkers have, the higher the polymerization rate is. However, they also mean the existence of less cross-linking efficiency and some defects in gel network.展开更多
Membrane fouling is always the biggest problem in the practice of membrane separation technologies,which strongly impacts their applicability,separation efficiency,cost effectiveness,and service lifespan.Herein,a simp...Membrane fouling is always the biggest problem in the practice of membrane separation technologies,which strongly impacts their applicability,separation efficiency,cost effectiveness,and service lifespan.Herein,a simple but effective 3D modification approach was designed for permanently functionalizing polymeric membranes by directly cross-linking polyvinyl alcohol(PVA)under gamma-ray irradiation at room temperature without any additives.After the modification,a PVA layer was constructed on the membrane surface and the pore inner surface of polyvinylidene fluoride(PVDF)membranes.This endowed them with good hydrophilicity,low adsorption of protein model foulants,and easy recoverability properties.In addition,the pore size and distribution were customized by controlling the PVA concentration,which enhanced the rejection ability of the resultant membranes and converted them from microfiltration to ultrafiltration.The crosslinked PVA layer was equipped with the resultant membranes with good resistance to chemical cleaning by acidic,alkaline,and oxidative reagents,which could greatly prolong the membrane service lifetime.Furthermore,this approach was demonstrated as a universal method to modify PVDF membranes with other hydrophilic macromolecular modifiers,including polyethylene glycol,sodium alginate,and polyvinyl pyrrolidone.This modification of the membranes effectively endowed them with good hydrophilicity and antifouling properties,as expected.展开更多
Three series of amorphous copolymers containing azobenzene groups with various substituents and certain amounts of crosslinkable acrylic groups were prepared. The cross-linked polymer films were obtained by thermal po...Three series of amorphous copolymers containing azobenzene groups with various substituents and certain amounts of crosslinkable acrylic groups were prepared. The cross-linked polymer films were obtained by thermal polymerization of the acrylic groups in the copolymers, during which, by controlling the time of cross-linking reaction, the films can be made with different cross-linking degree （from 0 to 32%, which was monitored by FT-IR spectra measurement）. Photo-induced alignment process of the films was performed under irradiation with linearly polarized light at 442 nm, and the effect of cross-linking degree on the photo-induced alignment rate was investigated. The dynamics of the photo-induced alignment was analyzed with biexponential curve fitting. The photo-induced alignment rate and the maximum transmittance of the films decreased because of the cross-linking. Furthermore, for the cross-linked samples, it was found that their saturated value of transmittances keep constant after repeated ＂writing＂ and ＂erasing＂ cycles. The findings reveal that the cross-linking of the film can effectively restrain the phototactic mass transport of azopolymer during irradiation by polarized light. The relationship between the cross-linking degree and the photo-induced alignment behavior of azopolymer is discussed in detail.展开更多
A simple and effective photochemical method was developed for cross-linking of polymer gate dielectrics. Laborious synthetic processes for functionalizing polymer dielectrics with photo-cross-linkable groups were avoi...A simple and effective photochemical method was developed for cross-linking of polymer gate dielectrics. Laborious synthetic processes for functionalizing polymer dielectrics with photo-cross-linkable groups were avoided. The photo-cross-linker, BBP-4, was added into host polymers by simple solution blending process, which was capable of abstracting hydrogen atoms from polymers containing active C--H groups upon exposure to ultraviolet （UV） radiation. The cross-linking can be completed with a relatively long wavelength UV light （365 nm）. The approach has been applied to methacrylate and styrenic polymers such as commercial poly（methylmethacrylate） （PMMA）, poly（iso-butylmethacrylate） （PiBMA） and poly（4-methylstyrene） （PMS）. The cross-linked networks enhanced dielectric properties and solvent resistance of the thin films. The bottom-gate organic field-effect transistors （OFETs） through all solution processes on plastic substrate were fabricated. The OFET devices showed low voltage operation and steep subthreshold swing at relatively small gate dielectric capacitance.展开更多
To achieve the target of carbon neutrality,it is crucial to develop an efficient and green synthesis methodology with good atomic economy to achieve sufficient utilization of energy and sustainable development.Photoin...To achieve the target of carbon neutrality,it is crucial to develop an efficient and green synthesis methodology with good atomic economy to achieve sufficient utilization of energy and sustainable development.Photoinduced electron transfer reversible addition-fragmentation chain-transfer(PET-RAFT)polymerization is a precise methodology for constructing polymers with well-defined structures.However,conventional semiconductor-mediated PET-RAFT polymerization still has considerable limitations in terms of efficiency as well as the polymerization environment.Herein,sulfur-doped carbonized polymer dots(CPDs)were hydrothermally synthesized for catalysis of aqueous PET-RAFT polymerization at unprecedented efficiency with a highest propagation rate of 5.05 h-1.The resulting polymers have well-controlled molecular weight and narrow molecular weight dispersion(Ð<1.10).Based on the optoelectronic characterizations,we obtained insights into the photoinduced electron transfer process and proposed the mechanism for CPD-mediated PET-RAFT polymerization.In addition,as-synthesized CPDs for PET-RAFT polymerization were also demonstrated to be suitable for a wide range of light sources(blue/green/solar irradiation),numerous monomers,low catalyst loading(low as 0.01 mg mL^(-1)),and multiple polar solvent environments,all of which allowed to achieve efficiencies much higher than those of existing semiconductor-mediated methods.Finally,the CPDs were confirmed to be non-cytotoxic and catalyzed PET-RAFT polymerization successfully in cell culture media,indicating broad prospects in biomedical fields.展开更多
Selective separation of CO_(2)/CH_(4)and C2 H_(2)/CH_(4)are promising for their high-purity industrial demand and scientific research on account of the similar molecular radius and physical properties.In this work,a u...Selective separation of CO_(2)/CH_(4)and C2 H_(2)/CH_(4)are promising for their high-purity industrial demand and scientific research on account of the similar molecular radius and physical properties.In this work,a unique 3 D microporous MOF material[Cu(SiF6)(sdi)2]·solvents(1,sdi=1,1’-sulfonyldiimidazole)was successfully constructed by cross-linking 1 D coordination polymer chains.The dense functional active sites on the inner walls of the channel of la can provide strong binding affinities to CO_(2),C2 H_(2),and thus effectively improve the gas separation performance of CO_(2)/CH_(4)and C2 H_(2)/CH_(4).展开更多
Narrow-disperse, surface-functionalized ＂living＂ polymer microspheres with uniformly cross-linked structures were prepared by two-stage precipitation copolymerization of styrene and divinylbenzene. The two-stage pre...Narrow-disperse, surface-functionalized ＂living＂ polymer microspheres with uniformly cross-linked structures were prepared by two-stage precipitation copolymerization of styrene and divinylbenzene. The two-stage precipitation polymerization is composed of an initial conventional precipitation polymerization for the nucleation followed by a reverse atom transfer radical polymerization （reverse ATRP） for the controlled polymerization process. The polymerization parameters （including reaction time for the first stage, AIBN amount and monomer loading） have been studied to show significant influences on the morphologies. Moreover, narrower size distribution and an ATRP initiator-functional surface of resulting particles can be obtained by applying reverse ATRP to conventional precipitation polymerization in the second stage. Furthermore, the ＂livingness＂ of the resulting polymer microspheres was testified by their surface modification of poly[2-（dimethylamino） ethyl methacrylate] （PDMAEMA） brushes via surface-initiated ATRP （SI-ATRP）.展开更多
Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to p...Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to prevent degradation and side reactions.In the contribution,histidine N-thiocarboxyanhydride(His-NTA)is directly synthesized in aqueous solution without protection.With the self-catalysis of the imidazole side group,the ring-closing reaction to form His-NTA does not require any activating reagent(e.g.,phosphorus tribromide),which is elucidated by density functional theory(DFT)calculations.His-NTA directly polymerizes into PHis bearing unprotected imidazole groups with designable molecular weights(4.2-7.7 kg/mol)and low dispersities(1.10-1.19).Kinetic experiments and Monte Carlo simulations reveal the elementary reactions and the relationship between the conversion of His-NTA and time during polymerization.Block copolymerization of His-NTA with sarcosine N-thiocarboxyanhydride(Sar-NTA)demonstrate versatile construction of functional polypept(o)ides.The triblock copoly(amino acid)PHis-b-PSar-b-PHis is capable to reversibly coordinate with transition metal ions(Fe^(2+),Co^(2+),Ni^(2+),Cu^(2+)and Zn^(2+))to form pH-sensitive hydrogels.展开更多
Incorporation of acetal groups in the backbone is a potent strategy to create polymers that are cleavable or degradable under acidic conditions.We report here an in-depth study on the ring-closing-opening copolymeriza...Incorporation of acetal groups in the backbone is a potent strategy to create polymers that are cleavable or degradable under acidic conditions.We report here an in-depth study on the ring-closing-opening copolymerization of o-phthalaldehyde(OPA)and epoxide using Lewis pair type two-component organocatalysts for producing acetal-functionalized polyether and polyurethane.Notably,triethylborane as the Lewis acid,in comparison with tri(n-butyl)borane,more effectively enhances the polymerization activity by mitigating borane-induced reduction of the aldehyde group into extra initiating(borinic ester)species.Density functional theory(DFT)calculations present comparable energy barriers of OPA-epoxide cross-propagation and epoxide self-propagation,which is consistent with the experimental finding that an alternating-rich copolymer comprising mostly OPA-epoxide units but also epoxide-epoxide linkages is produced.In particular,when epoxide is added in a large excess,the product becomes a polyether containing acetal functionalities in the central part of the backbone and thus being convertible into polyurethane with refined acid degradability.展开更多
AIM:To compare simultaneous corneal collagen cross-linking(CXL)with intracorneal ring segment(ICRS)implantation versus successive ICRS followed by CXL and detect the impact of the timing of CXL after ICRS implantation...AIM:To compare simultaneous corneal collagen cross-linking(CXL)with intracorneal ring segment(ICRS)implantation versus successive ICRS followed by CXL and detect the impact of the timing of CXL after ICRS implantation in the successive method.METHODS:This is a retrospective study of the records of three groups of patients.Group 1 of 28 patients were operated on with simultaneous ICRS implantation and CXL,group 2 of 32 patients had ICRS implantation followed by CXL after 1mo,and group 3 of 38 patients had ICRS implantation followed by CXL after 3mo.The three groups had follow-up visits after 6,12,and 24mo.RESULTS:The preoperative data,age,and gender differences among 3 groups revealed no significant differences.The postoperative spherical equivalent and best-corrected visual acuity were improved significantly in all groups compared to the baseline,which were more evident in groups 1 and 2.The differences between preoperative and postoperative mean values of mean of K readings(Km)and maximum K reading(Kmax)at 6mo were 4.66 and 4.1 D in group 1,4.43 and 4.64 D in group 2,but 3.2 and 3.4 D in group 3,respectively.The spherical aberrations and the vertical coma showed significant postoperative changes in all groups,and trefoil showed nonsignificant changes.CONCLUSION:Simultaneous and sequential ICRS implantation and CXL at 1mo has similar Km and Kmax better postoperative changes than when both surgeries were done at three-month intervals.展开更多
We report a synthesis of microporous organic nanotube networks（MONNs） by a combination of hyper cross-linking and molecular templating of core-shell bottlebrush copolymers. The intrabrush and interbrush cross-linkin...We report a synthesis of microporous organic nanotube networks（MONNs） by a combination of hyper cross-linking and molecular templating of core-shell bottlebrush copolymers. The intrabrush and interbrush cross-linking of polystyrene（PS） shell layer in the core-shell bottlebrush copolymers led to the formation of micropores and large-sized nanopores（meso/macrospores） in MONNs, respectively, while selective removal of polylactide（PLA） core layer generated mesoporous tubular structure. The size of PLA-templated mesoporous cores and porous structure both at micro-and meso-scale could be controlled by simple tuning of the ratio of core/shell or the PLA core fraction in the bottlebrush precursors. Moreover, the resultant MONNs showed a highly selective adsorption capacity for the positively charged dyes on the basis of multi-porosity and carboxylate group-rich structure. In addition, MONNs also exhibited effective performance in size-selective adsorption of biomacromolecules. This work represents a new avenue for the preparation of MONNs and also provides a new application for molecular bottlebrushes in nanotechnology.展开更多
As a powerful synthetic tool,ruthenium-catalyzed ring-opening metathesis polymerization(ROMP)has been widely utilized to prepare diverse heteroatom-containing polymers.In this contribution,we report the synthesis of t...As a powerful synthetic tool,ruthenium-catalyzed ring-opening metathesis polymerization(ROMP)has been widely utilized to prepare diverse heteroatom-containing polymers.In this contribution,we report the synthesis of the novel imine-based polymer through the copolymerization of cyclooctene with cyclic imine comonomer via ROMP.Because of the efficient hydrolysis reactions of the imine group,the generated copolymer can be easily degraded under mild condition.Moreover,the generated degradable product was the telechelic polymer bearing amine group,which was highly challenged for its direct synthesis.And this telechelic polymer could also be used for the further synthesis of new polymer through post-transformation.The introduction of imine unit in this work provides a new example of the degradable polymer synthesis.展开更多
文摘The retrospective study by Edwar et al reinforces the role of therapeutic penetrating keratoplasty(PK)as a vital intervention in severe,treatment-resistant infectious keratitis.In advanced cases—often complicated by trauma,delayed presentation,and corneal perforation—PK restores globe integrity and provides limited visual recovery.However,its application is constrained by graft-related complications and donor shortages,particularly in low-resource settings.These limitations highlight the need for earlier,globe-sparing strategies to prevent progression and reduce surgical demand.Photoactivated chromophore for infectious keratitis-corneal collagen cross-linking(PACK-CXL)has emerged as a promising adjunct or alternative.With both antimicrobial and tissue-stabilizing effects,PACK-CXL may control infection and preserve corneal structure in earlier stages.A layered treatment framework that incorporates PACK-CXL as an initial intervention and reserves PK for refractory cases may help improve clinical outcomes.Further studies are needed to define their best use in practice.
基金supported by Research Fund of SWUST for PhD(Grant No.22zx7175)Sichuan Science and Technology Program(Grant No.2024NSFSC1097)。
文摘Based on the characteristics of laser-induced surface ignition,energetic photosensitive films show promising potential to meet the ignition requirements of various energetic materials(EMs).In this study,DATNBI/ferric alginate(DI/FeA),DI/cobalt alginate(DI/CoA),and DI/nickel alginate(DI/Ni A)films are fabricated by employing sodium alginate(SA)with a three-dimensional network structure as the film matrix,via ionic cross-linking of SA with Fe^(3+),Co^(2+),and Ni^(2+)ions.The study demonstrates that the ionic cross-linking enhances the hydrophobic performance of the films,with the water contact angle increasing from 82.1° to 123.5°.Concurrently,the films'near-infrared(NIR)light absorption improved.Furthermore,transition metal ions facilitate accelerated electron transfer,thereby catalyzing the thermal decomposition of DATNBI.Under 1064 nm laser irradiation,the DI/Fe A film exhibits exceptional combustion performance,with an ignition delay time as low as 76 ms.It successfully acts as an NIR laser ignition medium to initiate the self-sustained combustion of CL-20.This study demonstrates the synergistic realization of enhanced hydrophobicity,improved photosensitivity,and promoted catalytic decomposition through microstructural design of the material,providing new insights for the design of additive-free EMs in laser ignition applications.
基金the support from the Jiangsu Provincial Senior Talent Program (Dengfeng,Jiangsu University)the support from the National Key R&D Program of China (No.2024YFB3612600)+3 种基金the National Natural Science Foundation of China (Nos.22275098,62288102)Basic Research Program of Jiangsu (No.BK20243057)the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications (No.NY222097)the National Natural Science Foundation of China (No.62205035)。
文摘To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
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financial support from the National Natural Science Foundation of China(Nos.22401274,U23B6011)the Jilin Provincial Science and Technology Department Program(No.20250102070JC)。
文摘Catalysts are key for olefin polymerization reactions and are also ubiquitous in catalysis science.Multinuclear metal catalysts have witnessed enhanced performances in catalytic reactions relative to mononuclear catalysts,but which substantially involve multi-step,tedious,and difficult synthesis.Herein,this study reports an intriguing approach to construct multi-nuclear catalysts for the milestoneα-diimine nickel catalysts using an oligomeric strategy.A polymerizable norbornene unit is incorporated into theα-diimine ligand backbone,leading to the formation of the monomeric nickel catalyst Ni_(1)and its corresponding oligomeric nickel catalysts(Ni_(3)and Ni_(5))with varying degrees of polymerization(DP=3 and 5).Notably,the oligomeric catalyst Ni_(5)was facilely scaled up(50 g-level),showed enhanced thermal stability,exhibited 4.6 times higher activity,and yielded polyethylene elastomer with a 379%increased molecular weight in ethylene polymerization,compared to the monomeric catalyst Ni_(1).Catalytic performance enhancements of oligomeric catalysts were found to be DP-dependent.The kilogram-scale polyethylene,produced using Ni_(5)in a 20 L reactor,presented a highly branched all-hydrocarbon structure,which demonstrated typical elastic properties(tensile strength:4 MPa,elastic recovery:SR=72%)along with great processability(MFI=3.0 g/10 min),insulating characteristics(volume resistivity=2×10^(16)Ω/m),and hydrophobicity(water vapor permeability:0.03 g/m^(2)/day),suggesting potentially practical applications.
基金financially supported by National Key R&D Program Young Scientists Project(No.2023YFC3903100)the National Natural Science Foundation of China(No.22322503)analytical and testing assistance from the Analysis and Testing Center of HUST。
文摘Switchable polymerization is emerging as a powerful tool to construct block copolymers directly from mixtures of monomers.However,current achievements typically iterate between two polymerization cycles to afford products with fixed sequences and compositions.Herein,we report the triethylborane/1,8-diazabicyclo[5.4.0]undec-7-ene(Et_3B/DBU)pair-mediated four-component switchable polymerization of propylene oxide(PO),CO_(2),phthalic anhydride(PA),and racemic lactide(rac-LA),which enables the on-demand synthesis of four different block copolymers,i.e.,poly(propylene phthalate)-b-polylactide(PPE-b-PLA),PPE-b-PLA-b-poly(propylene carbonate)(PPC),PPE-b-PPC-b-PLA,and PPE-b-PPCb-poly(propylene oxide)(PPO),through rationally modulating the Lewis pair(LP)ratio.Core to this protocol is that increasing the loading of Et_(3)B accelerates the ring-opening of PO while impeding the reactivity of rac-LA,thus allowing for fine-tuning of the thermodynamic and kinetic of the switchable polymerization.Therefore,the four polymerization cycles involving PO/PA ring-opening copolymerization(ROCOP),PO/CO_2 ROCOP,rac-LA ring-opening polymerization(ROP),and PO ROP can be connected and discriminated in precisely programmed manners.
基金financial support from the National Natural Science Foundation of China[grant number 21878299]。
文摘Polymer binders possess significant potential in alleviating the volume expansion issues of silicon-based anodes,yet remain challenging due to insufficient interfacial interactions with individual components(Si,C,and Cu)of the anode.Herein,we report the synthesis of a stable three-dimensional network structure of the PAA-PEA(polyacrylic acid-polyether amines)polymer binder through intermolecular physicochemical dual cross-linking.By incorporating polar functional groups,the binder molecules not only form strong C-O-Si,N-Si,O=C-O-C,and O=C-O-Cu covalent bonds but also enhance non-covalent interactions with Si,C,and Cu,thereby improving adhesion between the binder and each interface of the anode.Furthermore,weak hydrogen bonds,acting as"sacrificial bonds",dissipate energy and disperse accumulated stress,improving the material flexibility.Due to the high mechanical stability of the framework,which combines both rigidity and flexibility and the coupling effect at the three interfaces,the movement and separation of electrode components are effectively restrained,significantly enhancing the cycling stability of silicon-graphite anodes.The PAA-PEA 2000 electrode exhibits a capacity retention of 78% after 500 cycles at a current density of 0.2 A g^(-1).This work provides insights into the mechanism of binders and guides the design of polymer binders for high-performance Si-based electrodes.
文摘A controlled cross-linking polymerization containing intra- and intermolecular reactions was designed based on random coil morphology of macromolecules in solution. The soluble intramolecular cross-linked maeromolecule （ICM） was successfully synthesized in the system with PVA and MDI. We found an especial dissolving phenomenon, namely the semi-soluble phenomenon when some gels dissolved in DMF. The chain growth process of ICMs was investigated by Transmission electron microscopy （TEM） pictures of samples at different reacting times, in addition, TEM pictures show ICMs have three kinds of styles in structure, viz. ＂globule structure＂, ＂nubby structure＂ and the intervenient between the above two structures, and the efflux time of the ICMs was measured by an Ubbelohde viscosimeter, it was found that the efflux time decreases with the degree ofcrosslink increasing.
文摘The overall cross-linking copolymerization of acrylic acid and multi-armed cross-linkers are investigated by in situ interferometry. The results show that the more arms the cross-linkers have, the higher the polymerization rate is. However, they also mean the existence of less cross-linking efficiency and some defects in gel network.
基金This work was supported by the National Natural Science Foundation of China(Nos.11875313,12075153,and 11575277).
文摘Membrane fouling is always the biggest problem in the practice of membrane separation technologies,which strongly impacts their applicability,separation efficiency,cost effectiveness,and service lifespan.Herein,a simple but effective 3D modification approach was designed for permanently functionalizing polymeric membranes by directly cross-linking polyvinyl alcohol(PVA)under gamma-ray irradiation at room temperature without any additives.After the modification,a PVA layer was constructed on the membrane surface and the pore inner surface of polyvinylidene fluoride(PVDF)membranes.This endowed them with good hydrophilicity,low adsorption of protein model foulants,and easy recoverability properties.In addition,the pore size and distribution were customized by controlling the PVA concentration,which enhanced the rejection ability of the resultant membranes and converted them from microfiltration to ultrafiltration.The crosslinked PVA layer was equipped with the resultant membranes with good resistance to chemical cleaning by acidic,alkaline,and oxidative reagents,which could greatly prolong the membrane service lifetime.Furthermore,this approach was demonstrated as a universal method to modify PVDF membranes with other hydrophilic macromolecular modifiers,including polyethylene glycol,sodium alginate,and polyvinyl pyrrolidone.This modification of the membranes effectively endowed them with good hydrophilicity and antifouling properties,as expected.
基金This work was supported by the National Natural Science Foundation of China （No.50573071, No.50533040, No.50703038, No.50773075, and No.50640420265）, the National Basic Research Program of China （No.2006cb302900）, and the Chinese Academy of Sciences （No.kjcx2.yw.H02）.
文摘Three series of amorphous copolymers containing azobenzene groups with various substituents and certain amounts of crosslinkable acrylic groups were prepared. The cross-linked polymer films were obtained by thermal polymerization of the acrylic groups in the copolymers, during which, by controlling the time of cross-linking reaction, the films can be made with different cross-linking degree （from 0 to 32%, which was monitored by FT-IR spectra measurement）. Photo-induced alignment process of the films was performed under irradiation with linearly polarized light at 442 nm, and the effect of cross-linking degree on the photo-induced alignment rate was investigated. The dynamics of the photo-induced alignment was analyzed with biexponential curve fitting. The photo-induced alignment rate and the maximum transmittance of the films decreased because of the cross-linking. Furthermore, for the cross-linked samples, it was found that their saturated value of transmittances keep constant after repeated ＂writing＂ and ＂erasing＂ cycles. The findings reveal that the cross-linking of the film can effectively restrain the phototactic mass transport of azopolymer during irradiation by polarized light. The relationship between the cross-linking degree and the photo-induced alignment behavior of azopolymer is discussed in detail.
基金financially supported by the National Natural Science Foundation of China (Nos.21674060,21274087,61674102,and 61334008)National Key R&D Program (No.2016YFB0401100)
文摘A simple and effective photochemical method was developed for cross-linking of polymer gate dielectrics. Laborious synthetic processes for functionalizing polymer dielectrics with photo-cross-linkable groups were avoided. The photo-cross-linker, BBP-4, was added into host polymers by simple solution blending process, which was capable of abstracting hydrogen atoms from polymers containing active C--H groups upon exposure to ultraviolet （UV） radiation. The cross-linking can be completed with a relatively long wavelength UV light （365 nm）. The approach has been applied to methacrylate and styrenic polymers such as commercial poly（methylmethacrylate） （PMMA）, poly（iso-butylmethacrylate） （PiBMA） and poly（4-methylstyrene） （PMS）. The cross-linked networks enhanced dielectric properties and solvent resistance of the thin films. The bottom-gate organic field-effect transistors （OFETs） through all solution processes on plastic substrate were fabricated. The OFET devices showed low voltage operation and steep subthreshold swing at relatively small gate dielectric capacitance.
基金supported by the National Natural Science Foundation of China(NSFC)under Grant No.22035001 and No.52233005.
文摘To achieve the target of carbon neutrality,it is crucial to develop an efficient and green synthesis methodology with good atomic economy to achieve sufficient utilization of energy and sustainable development.Photoinduced electron transfer reversible addition-fragmentation chain-transfer(PET-RAFT)polymerization is a precise methodology for constructing polymers with well-defined structures.However,conventional semiconductor-mediated PET-RAFT polymerization still has considerable limitations in terms of efficiency as well as the polymerization environment.Herein,sulfur-doped carbonized polymer dots(CPDs)were hydrothermally synthesized for catalysis of aqueous PET-RAFT polymerization at unprecedented efficiency with a highest propagation rate of 5.05 h-1.The resulting polymers have well-controlled molecular weight and narrow molecular weight dispersion(Ð<1.10).Based on the optoelectronic characterizations,we obtained insights into the photoinduced electron transfer process and proposed the mechanism for CPD-mediated PET-RAFT polymerization.In addition,as-synthesized CPDs for PET-RAFT polymerization were also demonstrated to be suitable for a wide range of light sources(blue/green/solar irradiation),numerous monomers,low catalyst loading(low as 0.01 mg mL^(-1)),and multiple polar solvent environments,all of which allowed to achieve efficiencies much higher than those of existing semiconductor-mediated methods.Finally,the CPDs were confirmed to be non-cytotoxic and catalyzed PET-RAFT polymerization successfully in cell culture media,indicating broad prospects in biomedical fields.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.91856124 and 21531005)Nature Science Fund of Tianjin,China(No.19JCZDJC37200)。
文摘Selective separation of CO_(2)/CH_(4)and C2 H_(2)/CH_(4)are promising for their high-purity industrial demand and scientific research on account of the similar molecular radius and physical properties.In this work,a unique 3 D microporous MOF material[Cu(SiF6)(sdi)2]·solvents(1,sdi=1,1’-sulfonyldiimidazole)was successfully constructed by cross-linking 1 D coordination polymer chains.The dense functional active sites on the inner walls of the channel of la can provide strong binding affinities to CO_(2),C2 H_(2),and thus effectively improve the gas separation performance of CO_(2)/CH_(4)and C2 H_(2)/CH_(4).
文摘Narrow-disperse, surface-functionalized ＂living＂ polymer microspheres with uniformly cross-linked structures were prepared by two-stage precipitation copolymerization of styrene and divinylbenzene. The two-stage precipitation polymerization is composed of an initial conventional precipitation polymerization for the nucleation followed by a reverse atom transfer radical polymerization （reverse ATRP） for the controlled polymerization process. The polymerization parameters （including reaction time for the first stage, AIBN amount and monomer loading） have been studied to show significant influences on the morphologies. Moreover, narrower size distribution and an ATRP initiator-functional surface of resulting particles can be obtained by applying reverse ATRP to conventional precipitation polymerization in the second stage. Furthermore, the ＂livingness＂ of the resulting polymer microspheres was testified by their surface modification of poly[2-（dimethylamino） ethyl methacrylate] （PDMAEMA） brushes via surface-initiated ATRP （SI-ATRP）.
基金financially supported by the National Natural Science Foundation of China(Nos.22271252 and 22201105)。
文摘Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to prevent degradation and side reactions.In the contribution,histidine N-thiocarboxyanhydride(His-NTA)is directly synthesized in aqueous solution without protection.With the self-catalysis of the imidazole side group,the ring-closing reaction to form His-NTA does not require any activating reagent(e.g.,phosphorus tribromide),which is elucidated by density functional theory(DFT)calculations.His-NTA directly polymerizes into PHis bearing unprotected imidazole groups with designable molecular weights(4.2-7.7 kg/mol)and low dispersities(1.10-1.19).Kinetic experiments and Monte Carlo simulations reveal the elementary reactions and the relationship between the conversion of His-NTA and time during polymerization.Block copolymerization of His-NTA with sarcosine N-thiocarboxyanhydride(Sar-NTA)demonstrate versatile construction of functional polypept(o)ides.The triblock copoly(amino acid)PHis-b-PSar-b-PHis is capable to reversibly coordinate with transition metal ions(Fe^(2+),Co^(2+),Ni^(2+),Cu^(2+)and Zn^(2+))to form pH-sensitive hydrogels.
基金financially supported by the National Key R&D Program of China(No.2022YFC2805103)the National Natural Science Foundation of China(Nos.52022031 and 52263001)the Foundation from Qinghai Science and Technology Department(No.2022-ZJ-944Q)。
文摘Incorporation of acetal groups in the backbone is a potent strategy to create polymers that are cleavable or degradable under acidic conditions.We report here an in-depth study on the ring-closing-opening copolymerization of o-phthalaldehyde(OPA)and epoxide using Lewis pair type two-component organocatalysts for producing acetal-functionalized polyether and polyurethane.Notably,triethylborane as the Lewis acid,in comparison with tri(n-butyl)borane,more effectively enhances the polymerization activity by mitigating borane-induced reduction of the aldehyde group into extra initiating(borinic ester)species.Density functional theory(DFT)calculations present comparable energy barriers of OPA-epoxide cross-propagation and epoxide self-propagation,which is consistent with the experimental finding that an alternating-rich copolymer comprising mostly OPA-epoxide units but also epoxide-epoxide linkages is produced.In particular,when epoxide is added in a large excess,the product becomes a polyether containing acetal functionalities in the central part of the backbone and thus being convertible into polyurethane with refined acid degradability.
文摘AIM:To compare simultaneous corneal collagen cross-linking(CXL)with intracorneal ring segment(ICRS)implantation versus successive ICRS followed by CXL and detect the impact of the timing of CXL after ICRS implantation in the successive method.METHODS:This is a retrospective study of the records of three groups of patients.Group 1 of 28 patients were operated on with simultaneous ICRS implantation and CXL,group 2 of 32 patients had ICRS implantation followed by CXL after 1mo,and group 3 of 38 patients had ICRS implantation followed by CXL after 3mo.The three groups had follow-up visits after 6,12,and 24mo.RESULTS:The preoperative data,age,and gender differences among 3 groups revealed no significant differences.The postoperative spherical equivalent and best-corrected visual acuity were improved significantly in all groups compared to the baseline,which were more evident in groups 1 and 2.The differences between preoperative and postoperative mean values of mean of K readings(Km)and maximum K reading(Kmax)at 6mo were 4.66 and 4.1 D in group 1,4.43 and 4.64 D in group 2,but 3.2 and 3.4 D in group 3,respectively.The spherical aberrations and the vertical coma showed significant postoperative changes in all groups,and trefoil showed nonsignificant changes.CONCLUSION:Simultaneous and sequential ICRS implantation and CXL at 1mo has similar Km and Kmax better postoperative changes than when both surgeries were done at three-month intervals.
基金financially supported by the National Natural Science Foundation of China (Nos. 51273066 and 21574042)Shanghai Pujiang Program (No. 13PJ1402300)
文摘We report a synthesis of microporous organic nanotube networks（MONNs） by a combination of hyper cross-linking and molecular templating of core-shell bottlebrush copolymers. The intrabrush and interbrush cross-linking of polystyrene（PS） shell layer in the core-shell bottlebrush copolymers led to the formation of micropores and large-sized nanopores（meso/macrospores） in MONNs, respectively, while selective removal of polylactide（PLA） core layer generated mesoporous tubular structure. The size of PLA-templated mesoporous cores and porous structure both at micro-and meso-scale could be controlled by simple tuning of the ratio of core/shell or the PLA core fraction in the bottlebrush precursors. Moreover, the resultant MONNs showed a highly selective adsorption capacity for the positively charged dyes on the basis of multi-porosity and carboxylate group-rich structure. In addition, MONNs also exhibited effective performance in size-selective adsorption of biomacromolecules. This work represents a new avenue for the preparation of MONNs and also provides a new application for molecular bottlebrushes in nanotechnology.
基金financially supported by National Key R&D Program of China(No.2021YFA1501700)CAS Project for Young Scientists in Basic Research(No.YSBR-094)+1 种基金Natural Science Foundation of Anhui Province(Nos.2308085Y35 and 2023AH030002)Hefei Natural Science Foundation(No.202304)。
文摘As a powerful synthetic tool,ruthenium-catalyzed ring-opening metathesis polymerization(ROMP)has been widely utilized to prepare diverse heteroatom-containing polymers.In this contribution,we report the synthesis of the novel imine-based polymer through the copolymerization of cyclooctene with cyclic imine comonomer via ROMP.Because of the efficient hydrolysis reactions of the imine group,the generated copolymer can be easily degraded under mild condition.Moreover,the generated degradable product was the telechelic polymer bearing amine group,which was highly challenged for its direct synthesis.And this telechelic polymer could also be used for the further synthesis of new polymer through post-transformation.The introduction of imine unit in this work provides a new example of the degradable polymer synthesis.
