Optical imaging systems have greatly extended human visual capabilities,enabling the observation and understanding of diverse phenomena.Imaging technologies span a broad spectrum of wavelengths from x-ray to radio fre...Optical imaging systems have greatly extended human visual capabilities,enabling the observation and understanding of diverse phenomena.Imaging technologies span a broad spectrum of wavelengths from x-ray to radio frequencies and impact research activities and our daily lives.Traditional glass lenses are fabricated through a series of complex processes,while polymers offer versatility and ease of production.However,modern applications often require complex lens assemblies,driving the need for miniaturization and advanced designs with micro-and nanoscale features to surpass the capabilities of traditional fabrication methods.Three-dimensional(3D)printing,or additive manufacturing,presents a solution to these challenges with benefits of rapid prototyping,customized geometries,and efficient production,particularly suited for miniaturized optical imaging devices.Various 3D printing methods have demonstrated advantages over traditional counterparts,yet challenges remain in achieving nanoscale resolutions.Two-photon polymerization lithography(TPL),a nanoscale 3D printing technique,enables the fabrication of intricate structures beyond the optical diffraction limit via the nonlinear process of two-photon absorption within liquid resin.It offers unprecedented abilities,e.g.alignment-free fabrication,micro-and nanoscale capabilities,and rapid prototyping of almost arbitrary complex 3D nanostructures.In this review,we emphasize the importance of the criteria for optical performance evaluation of imaging devices,discuss material properties relevant to TPL,fabrication techniques,and highlight the application of TPL in optical imaging.As the first panoramic review on this topic,it will equip researchers with foundational knowledge and recent advancements of TPL for imaging optics,promoting a deeper understanding of the field.By leveraging on its high-resolution capability,extensive material range,and true 3D processing,alongside advances in materials,fabrication,and design,we envisage disruptive solutions to current challenges and a promising incorporation of TPL in future optical imaging applications.展开更多
The Mathieu beam is a typical nondiffracting beam characterized by its propagation invariance and self-reconstruction.These extraordinary properties have given rise to potentialities for applications such as optical c...The Mathieu beam is a typical nondiffracting beam characterized by its propagation invariance and self-reconstruction.These extraordinary properties have given rise to potentialities for applications such as optical communications,optical trapping,and material processing.However,the experimental generation of Mathieu–Gauss beams possessing high quality and compactness is still challenging.In this work,even and helical Mathieu phase plates with different orders m and ellipticity parameters q are fabricated by femtosecond laser two-photon polymerization.The experimentally generated nondiffracting beams are propagationinvariant in several hundred millimeters,which agree with numerical simulations.This work may promote the miniaturization of the application of nondiffracting beams in micronanooptics.展开更多
In this work, a two-photon polymerization(2PP) processing device was built using the femtosecond laser, and femtosecond laser direct writing was performed on SU-8 photoresist. Due to the 2PP effect of the photoresist ...In this work, a two-photon polymerization(2PP) processing device was built using the femtosecond laser, and femtosecond laser direct writing was performed on SU-8 photoresist. Due to the 2PP effect of the photoresist caused by the femtosecond laser, the polymeric line with size less than the focal spot size is obtained. Based on the Raman spectroscopy characterization of SU-8 polymer before and after 2PP, we research the dynamic process of femtosecond laser induced 2PP. In Raman spectra, some scattering peaks with large intensity variation, such as 1 108 cm^(-1) and 1 183 cm^(-1), indicate that the asymmetric stretching vibration of C-O-C bond in SU-8 polymer is increased. By comparison, we can find that 2PP only affects the light absorption of initiator, but does not affect the monomer polymerization. It is helpful to understand the interaction of photoresist and femtosecond laser, and plays an important role in quantitatively controlling the polymerization degree of SU-8 polymer and improving the processing resolution of 2PP.展开更多
Time-dependent hybrid density functional theory in combination with polarized continuum model is applied to study the solvent effects on the geometrical and electronic structures as well as one- and two-photon absorpt...Time-dependent hybrid density functional theory in combination with polarized continuum model is applied to study the solvent effects on the geometrical and electronic structures as well as one- and two-photon absorption processes, of a newly synthesized asymmetrical charge-transfer organic molecule bis-（4-bromo-phenyl）-[4-（2-pyridin-4-yl-vinyl）phenyl]-amine （BPYPA）. There exist two charge-transfer states for the compound in visible region. The two-photon absorption cross section calculated by a three-state model and solvatochromic shift of the charge-transfer states are found to be solvent-dependent, where a nonmonotonic behaviour with respect to the polarity of the solvents is observed. The numerical results show that the organic molecule exhibits a rather large two-photon absorption cross section as compared with the compound 4-trans-[p-（N, N-Di-n-butylamino）-p-stilbenyl vinyl] pyridine （DBASVP） reported previously, and is predicted to be a good two-photon polymerization initiator. The hydrogen-bond effect is analysed. The computational results are in good agreement with the measurements.展开更多
The rapid miniaturization of electronic devices has fueled unprecedented demand for flexible,high-performance sensors across fields ranging from medical devices to robotics.Despite advances in fabrication techniques,t...The rapid miniaturization of electronic devices has fueled unprecedented demand for flexible,high-performance sensors across fields ranging from medical devices to robotics.Despite advances in fabrication techniques,the development of micro-and nano-scale flexible force sensors with superior sensitivity,stability,and biocompatibility remains a formidable challenge.In this study,we developed a novel conductive photosensitive resin specifically designed for two-photon polymerization,systematically optimized its printing parameters,and improved its structural design,thereby enabling the fabrication of high-precision micro-spring force sensors(MSFS).The proposed photosensitive resin,doped with MXene nanomaterials,combines exceptional mechanical strength and conductivity,overcoming limitations of traditional materials.Using a support vector machine model in machine learning techniques,we optimized the polymerizability of the resin under varied laser parameters,achieving a predictive accuracy of 92.66%.This model significantly reduced trial-and-error in the TPP process,accelerating the discovery of ideal fabrication conditions.Finite element analysis was employed to design and simulate the performance of the MSFS,guiding structural optimization to achieve high sensitivity and mechanical stability.The fabricated MSFS demonstrated outstanding electromechanical performance,with a sensitivity coefficient of 5.65 and a fabrication accuracy within±50 nm,setting a new standard for MSFS precision.This work not only pushes the boundaries of sensor miniaturization but also introduces a scalable,efficient pathway for the rapid design and fabrication of highperformance flexible sensors.展开更多
Temperature is a common and significant physical quantity,particularly under harsh conditions such as a high voltage or strong electric/magnetic fields.In this study,we developed an all-fiber-optic temperature sensor ...Temperature is a common and significant physical quantity,particularly under harsh conditions such as a high voltage or strong electric/magnetic fields.In this study,we developed an all-fiber-optic temperature sensor based on a fiber-end microstructure doped with quantum dots(QDs).The microstructure was fabricated on a fiber tip using twophoton polymerization technology.The results show that the fluorescence intensity of the QD microstructure is reduced with an increase in temperature,and the peak position of photoluminescence exhibits a linear change in the temperature range of 26-70℃.The developed sensor exhibits a high-temperature sensitivity of 135 pm/℃.The proposed method has enormous potential for the development of fiber-end temperature sensors.展开更多
Water monitoring,environmental analysis,cell culture stability,and biomedical applications require precise pH control.Traditional methods,such as pH strips and meters,have limitations:pH strips lack precision,whereas ...Water monitoring,environmental analysis,cell culture stability,and biomedical applications require precise pH control.Traditional methods,such as pH strips and meters,have limitations:pH strips lack precision,whereas electrochemical meters,although more accurate,are fragile,prone to drift,and unsuitable for small volumes.In this paper,we propose a method for the optical detection of pH based on a multiplexed sensor with 4D microcavities fabricated via two-photon polymerization.This approach employs pH-triggered reversible variations in microresonator geometry and integrates hundreds of dual optically coupled 4D microcavities to achieve the detection limit of 0.003 pH units.The proposed solution is a clear example of the use-case-oriented application of two-photon polymerized structures of high optical quality.Owing to the benefits of the multiplexed imaging platform,the dual 4D microresonators can be integrated with other microresonator types for pH-corrected biochemical studies.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
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
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
Core-shell colloidal particles with a polymer layer have broad applications in different areas.Herein,we developed a two-step method combining aqueous surface-initiated photoinduced polymerization-induced self-assembl...Core-shell colloidal particles with a polymer layer have broad applications in different areas.Herein,we developed a two-step method combining aqueous surface-initiated photoinduced polymerization-induced self-assembly and photoinduced seeded reversible addition-fragmentation chain transfer(RAFT)polymerization to prepare a diverse set of core-shell colloidal particles with a well-defined polymer layer.Chemical compositions,structures,and thicknesses of polymer layers could be conveniently regulated by using different types of monomers and feed[monomer]/[chain transfer agent]ratios during seeded RAFT polymerization.展开更多
Copolymers of fluoroethylene and vinyl ethers(FEVE)are soluble and curable at relatively low temperature,and are used as high-performance coatings and paints.Currently,most market-available FEVE products obtained thro...Copolymers of fluoroethylene and vinyl ethers(FEVE)are soluble and curable at relatively low temperature,and are used as high-performance coatings and paints.Currently,most market-available FEVE products obtained through solution polymerization contain a large fraction of organic solvent,and hence,volatile organic compound(VOC)emissions cause environmental issues.In this study,the emulsion copolymerization of chlorotrifluoroethylene(CTFE)and vinyl ethers using an environmentally friendly emulsification system to produce waterborne FEVE was investigated.In addition to mixed nonionic and ionic surfactants,macromolecular monomer with double bond and polyoxyethylene segments were used in the emulsification system.The effect of adding macromolecular monomer and polyoxyethylene segment length of the nonionic surfactant on emulsion copolymerization were analyzed.An optimized emulsifier system for FEVE is proposed,and the prepared FEVE latexes exhibit excellent storage stability and film formation ability.展开更多
Functional hyperbranched polymers,as an important class of materials,are widely applied in diverse areas.Therefore,the development of simple and efficient reactions to prepare hyperbranched polymers is of great signif...Functional hyperbranched polymers,as an important class of materials,are widely applied in diverse areas.Therefore,the development of simple and efficient reactions to prepare hyperbranched polymers is of great significance.In this work,trialdehydes,diamines,and trimethylsilyl cyanide could easily undergo multicomponent polymerization under mild conditions,producing hyperbranched poly(α-aminonitrile)s with high molecular weights(M_(w) up to 4.87×10^(4))in good yields(up to 85%).The hyperbranched poly(α-aminonitrile)s have good solubility in commonly used organic solvents,high thermal stability as well as morphological stability.Furthermore,due to the numerous aldehyde groups in their branched chains,these hb-poly(α-aminonitrile)s can undergo one-pot,two-step,four-component post-polymerization with high efficiency.This work not only confirms the efficiency of our established catalyst-free multicomponent polymerization of aldehydes,amines and trimethylsilyl cyanide,but also provides a versatile and powerful platform for the preparation of functional hyperbranched polymeric materials.展开更多
Solid polymer electrolytes(SPEs)have garnered considerable interest in the field of lithium metal batteries(LMBs)owing to their exceptional mechanical strength,excellent designability,and heightened safety characteris...Solid polymer electrolytes(SPEs)have garnered considerable interest in the field of lithium metal batteries(LMBs)owing to their exceptional mechanical strength,excellent designability,and heightened safety characteristics.However,their inherently low ion transport efficiency poses a major challenge for their application in LMBs.To address this issue,covalent organic framework(COF)with their ordered ion transport channels,chemical stability,large specific surface area,and designable multifunctional sites has shown promising potential to enhance lithium-ion conduction.Here,we prepared an anionic COF,Tp Pa-COOLi,which can catalyze the ring-opening copolymerization of cyclic lactone monomers for the in situ fabrication of SPEs.The design leverages the high specific surface area of COF to facilitate the absorption of polymerization precursor and catalyze the polymerization within the pores,forming additional COF-polymer junctions that enhance ion transport pathways.The partial exfoliation of COF achieved through these junctions improved its dispersion within the polymer matrix,preserving ion transport channels and facilitating ion transport across COF grain boundaries.By controlling variables to alter the crystallinity of Tp Pa-COOLi and the presence of-COOLi substituents,Tp Pa-COOLi with partial long-range order and-COOLi substituents exhibited superior electrochemical performance.This research demonstrates the potential in constructing high-performance SPEs for LMBs.展开更多
Chain-growth radical polymerization of vinyl monomers is essential for producing a wide range of materials with properties tailored to specific applications.However,the inherent resistance of the polymer's C―C ba...Chain-growth radical polymerization of vinyl monomers is essential for producing a wide range of materials with properties tailored to specific applications.However,the inherent resistance of the polymer's C―C backbone to degradation raises significant concerns regarding long-term environmental persistence,which also limits their potential in biomedical applications.To address these challenges,researchers have developed strategies to either degrade preexisting vinyl polymers or incorporate cleavable units into the backbone to modify them with enhanced degradability.This review explores the various approaches aimed at achieving backbone degradability in chain-growth radical polymerization of vinyl monomers,while also highlighting future research directions for the development of application-driven degradable vinyl polymers.展开更多
In recent years,cellulose-based fluorescent polymers have received considerable attention.However,conventional modification methods face challenges such as insolubility in most solvents,fluorescence instability,and en...In recent years,cellulose-based fluorescent polymers have received considerable attention.However,conventional modification methods face challenges such as insolubility in most solvents,fluorescence instability,and environmental risks.In this study,a novel biosynthesis strategy was developed to fabricate fluorescent cellulose by adding fluorescent glucose derivatives to a bacterial fermentation broth.The metabolic activity of bacteria is utilized to achieve in situ polymerization of glucose and its derivatives during the synthesis of bacterial cellulose.Owing to the structural similarity between triphenylamine-modified glucose(TPA-Glc N)and glucose monomers,the TPA-Glc N were efficiently assimilated by the bacterial cells and incorporated into the cellulose matrix,resulting in a uniform distribution of fluorescence.The fluorescence color and intensity of the obtained cellulose could be adjusted by varying the amount of the fluorescent glucose derivatives.Compared to the fluorescent cellulose synthesized through physical dyeing,the fluorescence of the products obtained by in situ polymerization showed higher intensity and stability.Furthermore,fluorescent bacterial cellulose can be hydrolyzed into nanocellulose-based ink,which demonstrates exceptional anti-counterfeiting capabilities under UV light.This biosynthesis method not only overcomes the limitations of traditional modification techniques but also highlights the potential of microbial systems as platforms for synthesizing functional polymers.展开更多
Exploration of new green polymerization strategies for the construction of conjugated polymers is important but challengeable.In this work,a multicomponent polymerization of acetylarenes,alkynones and ammonium acetate...Exploration of new green polymerization strategies for the construction of conjugated polymers is important but challengeable.In this work,a multicomponent polymerization of acetylarenes,alkynones and ammonium acetate for in situ construction of conjugated poly(triarylpyridine)s was developed.The polymerization reactions of diacetylarenes,aromatic dialkynones and NH_(4)OAc were performed in dimethylsulfoxide(DMSO)under heating in the presence of potassium tert-butoxide(t-BuOK),affording four conjugated poly(2,4,6-triarylpyridine)s(PTAPs)in satisfactory yields.The resulting PTAPs have good solubility in common organic solvents and high thermal stability with 5%weight loss temperatures reaching up to 460℃.They are also electrochemically active.The PTAPs incorporating tetraphenylethene units manifest aggregation-induced emission features.Moreover,through simply being doped into poly(vinyl alcohol)(PVA)matrix,the polymer and model compound containing triphenylamine moieties exhibit room-temperature phosphorescence properties with ultralong lifetimes up to 696.2 ms and high quantum yields up to 28.7%.This work not only provides a facile green synthetic route for conjugated polymers but also offers new insights into the design of advanced materials with unique photophysical properties.展开更多
Living cationic polymerization of 4-acetoxystyrene(STO)was conducted in CH_(2)Cl_(2) at-15℃ using a dicumyl chloride(DCC)/SnCl_(4)/nBu_(4)NBr initiating system.Impurity moisture initiation was inhibited by adding pro...Living cationic polymerization of 4-acetoxystyrene(STO)was conducted in CH_(2)Cl_(2) at-15℃ using a dicumyl chloride(DCC)/SnCl_(4)/nBu_(4)NBr initiating system.Impurity moisture initiation was inhibited by adding proton trap 2,6-di-tert-butylpyridine(DTBP),and the controlled initiation of DCC was confirmed by ^(1)H nuclear magnetic resonance(^(1)H-NMR)spectroscopy and matrix-assisted laser desorption ionization time-offlight mass(MALDI-TOF-MS)spectrometry.The polymerization kinetics were analyzed to for optimizing the polymerization rate.Allyl-telechelic PSTOs(allyl-PSTO-allyl)with molecular weight(Mn)range of 3540–7800 g/mol and narrow molecular weight dispersity(Mw/Mn)about 1.25 were prepared through nucleophilic substitution with allyltrimethylsilane(ATMS)at approximately 40%monomer conversion.The experimental results indicate that the substitution efficiency of ATMS increased with higher ATMS concentration,temperature,and extended reaction time.Nearly unity ally-functionality for allyl-PSTO-allyl was achieved by adding sufficient SnCl_(4) prior to the substitution.展开更多
Some novel manganese and nickel complexes were synthesized by reacting manganese(Ⅱ) dichloride and nickel(Ⅱ) dichloride with pyridyl-imine ligands differing in the nature of the substituents at the imino nitrogen at...Some novel manganese and nickel complexes were synthesized by reacting manganese(Ⅱ) dichloride and nickel(Ⅱ) dichloride with pyridyl-imine ligands differing in the nature of the substituents at the imino nitrogen atom. All the complexes were characterized by analytical and infrared data: for some of them single crystals were obtained, and their molecular structure was determined by X-ray diffraction. The complexes were used in association with methylaluminoxane(MAO) for the polymerization of 1,3-butadiene obtaining active and selective catalysts giving predominantly 1,2 polybutadiene in case of manganese catalysts and exclusively cis-1,4 polybutadiene in case of nickel catalysts.展开更多
The performance of hydrogel radical polymerization under ambient conditions is a major challenge because oxygen is an effective radical quencher and the steps to remove or neutralize it are time consuming and laboriou...The performance of hydrogel radical polymerization under ambient conditions is a major challenge because oxygen is an effective radical quencher and the steps to remove or neutralize it are time consuming and laborious.A self-initiating system consisting of transition metals and acetylacetone has been successfully developed.The system is capable of initiating free radical polymerization of hydrogels at room temperature under aerobic conditions,which is attributed to carbon radicals generated by the oxidation of acetylacetone.Some of these carbon radicals reduce oxygen to generate hydroxyl radicals,which together induce self-coagulation of hydrogels.The polymerization system was effective for a variety of monomer and hydrogel swelling and shrinking schemes,and the reaction remained successful when exposed to saturated oxygen.In conclusion,the results demonstrate that the present strategy is an effective approach to addressing the challenge of deoxygenation in polymer synthesis,and provides a convenient method for synthesizing multifunctional hydrogels under ambient conditions.展开更多
基金support from the National Research Foundation (NRF) Singapore, under its Competitive Research Programme Award NRF-CRP20-20170004 and NRF Investigatorship Award NRF-NRFI06-20200005MTC Programmatic Grant M21J9b0085, as well as the Lite-On Project RS-INDUS-00090+5 种基金support from Australian Research Council (DE220101085, DP220102152)grants from German Research Foundation (SCHM2655/15-1, SCHM2655/21-1)Lee-Lucas Chair in Physics and funding by the Australian Research Council DP220102152financial support from the National Natural Science Foundation of China (Grant No. 62275078)Natural Science Foundation of Hunan Province of China (Grant No. 2022JJ20020)Shenzhen Science and Technology Program (Grant No. JCYJ20220530160405013)
文摘Optical imaging systems have greatly extended human visual capabilities,enabling the observation and understanding of diverse phenomena.Imaging technologies span a broad spectrum of wavelengths from x-ray to radio frequencies and impact research activities and our daily lives.Traditional glass lenses are fabricated through a series of complex processes,while polymers offer versatility and ease of production.However,modern applications often require complex lens assemblies,driving the need for miniaturization and advanced designs with micro-and nanoscale features to surpass the capabilities of traditional fabrication methods.Three-dimensional(3D)printing,or additive manufacturing,presents a solution to these challenges with benefits of rapid prototyping,customized geometries,and efficient production,particularly suited for miniaturized optical imaging devices.Various 3D printing methods have demonstrated advantages over traditional counterparts,yet challenges remain in achieving nanoscale resolutions.Two-photon polymerization lithography(TPL),a nanoscale 3D printing technique,enables the fabrication of intricate structures beyond the optical diffraction limit via the nonlinear process of two-photon absorption within liquid resin.It offers unprecedented abilities,e.g.alignment-free fabrication,micro-and nanoscale capabilities,and rapid prototyping of almost arbitrary complex 3D nanostructures.In this review,we emphasize the importance of the criteria for optical performance evaluation of imaging devices,discuss material properties relevant to TPL,fabrication techniques,and highlight the application of TPL in optical imaging.As the first panoramic review on this topic,it will equip researchers with foundational knowledge and recent advancements of TPL for imaging optics,promoting a deeper understanding of the field.By leveraging on its high-resolution capability,extensive material range,and true 3D processing,alongside advances in materials,fabrication,and design,we envisage disruptive solutions to current challenges and a promising incorporation of TPL in future optical imaging applications.
基金supported by the National Natural Science Foundation of China(Grant Nos.62125503 and 62261160388)the Key R&D Program of Hubei Province of China(Grant Nos.2020BAB001 and 2021BAA024)+3 种基金the Key R&D Program of Guangdong Province(Grant No.2018B030325002)the Science and Technology Innovation Commission of Shenzhen(Grant No.JCYJ20200109114018750)the Innovation Project of Optics Valley Laboratory(Grant No.OVL2021BG004)the Fundamental Research Funds for the Central Universities(Grant No.2019kfyRCPY037).
文摘The Mathieu beam is a typical nondiffracting beam characterized by its propagation invariance and self-reconstruction.These extraordinary properties have given rise to potentialities for applications such as optical communications,optical trapping,and material processing.However,the experimental generation of Mathieu–Gauss beams possessing high quality and compactness is still challenging.In this work,even and helical Mathieu phase plates with different orders m and ellipticity parameters q are fabricated by femtosecond laser two-photon polymerization.The experimentally generated nondiffracting beams are propagationinvariant in several hundred millimeters,which agree with numerical simulations.This work may promote the miniaturization of the application of nondiffracting beams in micronanooptics.
基金supported by the National Basic Research Program of China(No.2010CB934101)the National Natural Science Foundation of China(No.11404173)
文摘In this work, a two-photon polymerization(2PP) processing device was built using the femtosecond laser, and femtosecond laser direct writing was performed on SU-8 photoresist. Due to the 2PP effect of the photoresist caused by the femtosecond laser, the polymeric line with size less than the focal spot size is obtained. Based on the Raman spectroscopy characterization of SU-8 polymer before and after 2PP, we research the dynamic process of femtosecond laser induced 2PP. In Raman spectra, some scattering peaks with large intensity variation, such as 1 108 cm^(-1) and 1 183 cm^(-1), indicate that the asymmetric stretching vibration of C-O-C bond in SU-8 polymer is increased. By comparison, we can find that 2PP only affects the light absorption of initiator, but does not affect the monomer polymerization. It is helpful to understand the interaction of photoresist and femtosecond laser, and plays an important role in quantitatively controlling the polymerization degree of SU-8 polymer and improving the processing resolution of 2PP.
基金Project supported by the National Natural Science Foundation of China （Grant No 10274044） and Shandong Natural Science Foundation （Grant No Y2004A08）.
文摘Time-dependent hybrid density functional theory in combination with polarized continuum model is applied to study the solvent effects on the geometrical and electronic structures as well as one- and two-photon absorption processes, of a newly synthesized asymmetrical charge-transfer organic molecule bis-（4-bromo-phenyl）-[4-（2-pyridin-4-yl-vinyl）phenyl]-amine （BPYPA）. There exist two charge-transfer states for the compound in visible region. The two-photon absorption cross section calculated by a three-state model and solvatochromic shift of the charge-transfer states are found to be solvent-dependent, where a nonmonotonic behaviour with respect to the polarity of the solvents is observed. The numerical results show that the organic molecule exhibits a rather large two-photon absorption cross section as compared with the compound 4-trans-[p-（N, N-Di-n-butylamino）-p-stilbenyl vinyl] pyridine （DBASVP） reported previously, and is predicted to be a good two-photon polymerization initiator. The hydrogen-bond effect is analysed. The computational results are in good agreement with the measurements.
文摘The rapid miniaturization of electronic devices has fueled unprecedented demand for flexible,high-performance sensors across fields ranging from medical devices to robotics.Despite advances in fabrication techniques,the development of micro-and nano-scale flexible force sensors with superior sensitivity,stability,and biocompatibility remains a formidable challenge.In this study,we developed a novel conductive photosensitive resin specifically designed for two-photon polymerization,systematically optimized its printing parameters,and improved its structural design,thereby enabling the fabrication of high-precision micro-spring force sensors(MSFS).The proposed photosensitive resin,doped with MXene nanomaterials,combines exceptional mechanical strength and conductivity,overcoming limitations of traditional materials.Using a support vector machine model in machine learning techniques,we optimized the polymerizability of the resin under varied laser parameters,achieving a predictive accuracy of 92.66%.This model significantly reduced trial-and-error in the TPP process,accelerating the discovery of ideal fabrication conditions.Finite element analysis was employed to design and simulate the performance of the MSFS,guiding structural optimization to achieve high sensitivity and mechanical stability.The fabricated MSFS demonstrated outstanding electromechanical performance,with a sensitivity coefficient of 5.65 and a fabrication accuracy within±50 nm,setting a new standard for MSFS precision.This work not only pushes the boundaries of sensor miniaturization but also introduces a scalable,efficient pathway for the rapid design and fabrication of highperformance flexible sensors.
文摘Temperature is a common and significant physical quantity,particularly under harsh conditions such as a high voltage or strong electric/magnetic fields.In this study,we developed an all-fiber-optic temperature sensor based on a fiber-end microstructure doped with quantum dots(QDs).The microstructure was fabricated on a fiber tip using twophoton polymerization technology.The results show that the fluorescence intensity of the QD microstructure is reduced with an increase in temperature,and the peak position of photoluminescence exhibits a linear change in the temperature range of 26-70℃.The developed sensor exhibits a high-temperature sensitivity of 135 pm/℃.The proposed method has enormous potential for the development of fiber-end temperature sensors.
基金the German Federal Ministry for Research and Education(BMBF)for partially funding this work under the VIP+-Programme in the project IntellOSS,03VP08220.
文摘Water monitoring,environmental analysis,cell culture stability,and biomedical applications require precise pH control.Traditional methods,such as pH strips and meters,have limitations:pH strips lack precision,whereas electrochemical meters,although more accurate,are fragile,prone to drift,and unsuitable for small volumes.In this paper,we propose a method for the optical detection of pH based on a multiplexed sensor with 4D microcavities fabricated via two-photon polymerization.This approach employs pH-triggered reversible variations in microresonator geometry and integrates hundreds of dual optically coupled 4D microcavities to achieve the detection limit of 0.003 pH units.The proposed solution is a clear example of the use-case-oriented application of two-photon polymerized structures of high optical quality.Owing to the benefits of the multiplexed imaging platform,the dual 4D microresonators can be integrated with other microresonator types for pH-corrected biochemical studies.
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.
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.
基金support from the Science and Technology Program of Guangzhou(No.2024A04J2821)the National Natural Science Foundation of China(Nos.52222301,22171055)the Guangdong Natural Science Foundation for Distinguished Young Scholar(No.2022B1515020078)。
文摘Core-shell colloidal particles with a polymer layer have broad applications in different areas.Herein,we developed a two-step method combining aqueous surface-initiated photoinduced polymerization-induced self-assembly and photoinduced seeded reversible addition-fragmentation chain transfer(RAFT)polymerization to prepare a diverse set of core-shell colloidal particles with a well-defined polymer layer.Chemical compositions,structures,and thicknesses of polymer layers could be conveniently regulated by using different types of monomers and feed[monomer]/[chain transfer agent]ratios during seeded RAFT polymerization.
基金financially supported by the joint lab of Shanghai Huayi 3F New Materials Co.,Ltd.Donghua University。
文摘Copolymers of fluoroethylene and vinyl ethers(FEVE)are soluble and curable at relatively low temperature,and are used as high-performance coatings and paints.Currently,most market-available FEVE products obtained through solution polymerization contain a large fraction of organic solvent,and hence,volatile organic compound(VOC)emissions cause environmental issues.In this study,the emulsion copolymerization of chlorotrifluoroethylene(CTFE)and vinyl ethers using an environmentally friendly emulsification system to produce waterborne FEVE was investigated.In addition to mixed nonionic and ionic surfactants,macromolecular monomer with double bond and polyoxyethylene segments were used in the emulsification system.The effect of adding macromolecular monomer and polyoxyethylene segment length of the nonionic surfactant on emulsion copolymerization were analyzed.An optimized emulsifier system for FEVE is proposed,and the prepared FEVE latexes exhibit excellent storage stability and film formation ability.
基金financially supported by the Scientific Research Start-up Fund Project of Anhui Polytechnic University for Introducing Talents(No.2022YQQ081)Natural Science Research Project of Anhui Educational Committee(No.2024AH050133)the National Natural Science Foundation of China(No.22001078).
文摘Functional hyperbranched polymers,as an important class of materials,are widely applied in diverse areas.Therefore,the development of simple and efficient reactions to prepare hyperbranched polymers is of great significance.In this work,trialdehydes,diamines,and trimethylsilyl cyanide could easily undergo multicomponent polymerization under mild conditions,producing hyperbranched poly(α-aminonitrile)s with high molecular weights(M_(w) up to 4.87×10^(4))in good yields(up to 85%).The hyperbranched poly(α-aminonitrile)s have good solubility in commonly used organic solvents,high thermal stability as well as morphological stability.Furthermore,due to the numerous aldehyde groups in their branched chains,these hb-poly(α-aminonitrile)s can undergo one-pot,two-step,four-component post-polymerization with high efficiency.This work not only confirms the efficiency of our established catalyst-free multicomponent polymerization of aldehydes,amines and trimethylsilyl cyanide,but also provides a versatile and powerful platform for the preparation of functional hyperbranched polymeric materials.
基金the National Natural Science Foundation of China(grant nos.52020105012 and 523B2025)the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(B21003)the Analysis and Testing Center of HUST for the assistance in analysis and testing。
文摘Solid polymer electrolytes(SPEs)have garnered considerable interest in the field of lithium metal batteries(LMBs)owing to their exceptional mechanical strength,excellent designability,and heightened safety characteristics.However,their inherently low ion transport efficiency poses a major challenge for their application in LMBs.To address this issue,covalent organic framework(COF)with their ordered ion transport channels,chemical stability,large specific surface area,and designable multifunctional sites has shown promising potential to enhance lithium-ion conduction.Here,we prepared an anionic COF,Tp Pa-COOLi,which can catalyze the ring-opening copolymerization of cyclic lactone monomers for the in situ fabrication of SPEs.The design leverages the high specific surface area of COF to facilitate the absorption of polymerization precursor and catalyze the polymerization within the pores,forming additional COF-polymer junctions that enhance ion transport pathways.The partial exfoliation of COF achieved through these junctions improved its dispersion within the polymer matrix,preserving ion transport channels and facilitating ion transport across COF grain boundaries.By controlling variables to alter the crystallinity of Tp Pa-COOLi and the presence of-COOLi substituents,Tp Pa-COOLi with partial long-range order and-COOLi substituents exhibited superior electrochemical performance.This research demonstrates the potential in constructing high-performance SPEs for LMBs.
基金funding from the National Natural Science Foundation of China(No.22401037)funding from JST CREST(No.JPMJCR23L1)。
文摘Chain-growth radical polymerization of vinyl monomers is essential for producing a wide range of materials with properties tailored to specific applications.However,the inherent resistance of the polymer's C―C backbone to degradation raises significant concerns regarding long-term environmental persistence,which also limits their potential in biomedical applications.To address these challenges,researchers have developed strategies to either degrade preexisting vinyl polymers or incorporate cleavable units into the backbone to modify them with enhanced degradability.This review explores the various approaches aimed at achieving backbone degradability in chain-growth radical polymerization of vinyl monomers,while also highlighting future research directions for the development of application-driven degradable vinyl polymers.
基金supported by the National Natural Science Foundation of China(No.22376111)Shandong Provincial Natural Science Foundation(No.ZR2024YQ026)+2 种基金for Excellent Young Scholars,Taishan Scholar Foundation of Shandong Province(No.tsqn202408237)Youth Innovation Team Project for Talent Introduction and Cultivation in Universities of Shandong Province(No.096-1622002)the Research Foundation for Distinguished Scholars of Qingdao Agricultural University(No.663-1117015)。
文摘In recent years,cellulose-based fluorescent polymers have received considerable attention.However,conventional modification methods face challenges such as insolubility in most solvents,fluorescence instability,and environmental risks.In this study,a novel biosynthesis strategy was developed to fabricate fluorescent cellulose by adding fluorescent glucose derivatives to a bacterial fermentation broth.The metabolic activity of bacteria is utilized to achieve in situ polymerization of glucose and its derivatives during the synthesis of bacterial cellulose.Owing to the structural similarity between triphenylamine-modified glucose(TPA-Glc N)and glucose monomers,the TPA-Glc N were efficiently assimilated by the bacterial cells and incorporated into the cellulose matrix,resulting in a uniform distribution of fluorescence.The fluorescence color and intensity of the obtained cellulose could be adjusted by varying the amount of the fluorescent glucose derivatives.Compared to the fluorescent cellulose synthesized through physical dyeing,the fluorescence of the products obtained by in situ polymerization showed higher intensity and stability.Furthermore,fluorescent bacterial cellulose can be hydrolyzed into nanocellulose-based ink,which demonstrates exceptional anti-counterfeiting capabilities under UV light.This biosynthesis method not only overcomes the limitations of traditional modification techniques but also highlights the potential of microbial systems as platforms for synthesizing functional polymers.
基金supported by the National Natural Science Foundation of China(No.22071166)the Priority Academic Program Development of Jiangsu High Education Institutions(PAPD).
文摘Exploration of new green polymerization strategies for the construction of conjugated polymers is important but challengeable.In this work,a multicomponent polymerization of acetylarenes,alkynones and ammonium acetate for in situ construction of conjugated poly(triarylpyridine)s was developed.The polymerization reactions of diacetylarenes,aromatic dialkynones and NH_(4)OAc were performed in dimethylsulfoxide(DMSO)under heating in the presence of potassium tert-butoxide(t-BuOK),affording four conjugated poly(2,4,6-triarylpyridine)s(PTAPs)in satisfactory yields.The resulting PTAPs have good solubility in common organic solvents and high thermal stability with 5%weight loss temperatures reaching up to 460℃.They are also electrochemically active.The PTAPs incorporating tetraphenylethene units manifest aggregation-induced emission features.Moreover,through simply being doped into poly(vinyl alcohol)(PVA)matrix,the polymer and model compound containing triphenylamine moieties exhibit room-temperature phosphorescence properties with ultralong lifetimes up to 696.2 ms and high quantum yields up to 28.7%.This work not only provides a facile green synthetic route for conjugated polymers but also offers new insights into the design of advanced materials with unique photophysical properties.
基金financially supported by the National Natural Science Foundation of China(No.52373011)。
文摘Living cationic polymerization of 4-acetoxystyrene(STO)was conducted in CH_(2)Cl_(2) at-15℃ using a dicumyl chloride(DCC)/SnCl_(4)/nBu_(4)NBr initiating system.Impurity moisture initiation was inhibited by adding proton trap 2,6-di-tert-butylpyridine(DTBP),and the controlled initiation of DCC was confirmed by ^(1)H nuclear magnetic resonance(^(1)H-NMR)spectroscopy and matrix-assisted laser desorption ionization time-offlight mass(MALDI-TOF-MS)spectrometry.The polymerization kinetics were analyzed to for optimizing the polymerization rate.Allyl-telechelic PSTOs(allyl-PSTO-allyl)with molecular weight(Mn)range of 3540–7800 g/mol and narrow molecular weight dispersity(Mw/Mn)about 1.25 were prepared through nucleophilic substitution with allyltrimethylsilane(ATMS)at approximately 40%monomer conversion.The experimental results indicate that the substitution efficiency of ATMS increased with higher ATMS concentration,temperature,and extended reaction time.Nearly unity ally-functionality for allyl-PSTO-allyl was achieved by adding sufficient SnCl_(4) prior to the substitution.
文摘Some novel manganese and nickel complexes were synthesized by reacting manganese(Ⅱ) dichloride and nickel(Ⅱ) dichloride with pyridyl-imine ligands differing in the nature of the substituents at the imino nitrogen atom. All the complexes were characterized by analytical and infrared data: for some of them single crystals were obtained, and their molecular structure was determined by X-ray diffraction. The complexes were used in association with methylaluminoxane(MAO) for the polymerization of 1,3-butadiene obtaining active and selective catalysts giving predominantly 1,2 polybutadiene in case of manganese catalysts and exclusively cis-1,4 polybutadiene in case of nickel catalysts.
基金funded by the National Key R&D Program of China(No.2022YFF0904000)Cross-disciplinary Innovation Project of Jilin University(No.JLUXKJC2021ZZ01)the financial support from National Natural Science Foundation of China(No.62201497).
文摘The performance of hydrogel radical polymerization under ambient conditions is a major challenge because oxygen is an effective radical quencher and the steps to remove or neutralize it are time consuming and laborious.A self-initiating system consisting of transition metals and acetylacetone has been successfully developed.The system is capable of initiating free radical polymerization of hydrogels at room temperature under aerobic conditions,which is attributed to carbon radicals generated by the oxidation of acetylacetone.Some of these carbon radicals reduce oxygen to generate hydroxyl radicals,which together induce self-coagulation of hydrogels.The polymerization system was effective for a variety of monomer and hydrogel swelling and shrinking schemes,and the reaction remained successful when exposed to saturated oxygen.In conclusion,the results demonstrate that the present strategy is an effective approach to addressing the challenge of deoxygenation in polymer synthesis,and provides a convenient method for synthesizing multifunctional hydrogels under ambient conditions.
