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
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
Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effectiv...Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.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
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
Modern three-dimensional nanofabrication requires both additive and subtractive processes.However,both processes are largely isolated and generally regarded as incompatible with each other.In this study,we developed s...Modern three-dimensional nanofabrication requires both additive and subtractive processes.However,both processes are largely isolated and generally regarded as incompatible with each other.In this study,we developed simultaneous additive and subtractive fabrication processes using two-photon polymerization followed by femtosecond(fs)laser multiphoton ablation.To demonstrate the new capability,submicrometer polymer fibers containing periodic holes of 500-nm diameter and microfluidic channels of 1-mm diameter were successfully fabricated.This method combining both two-photon polymerization and fs laser ablation improves the nanofabrication efficiency and enables the fabrication of complex three-dimensional micro-/nanostructures,promising for a wide range of applications in integrated optics,microfluidics and microelectromechanical systems.展开更多
We developed a novel two-photon polymerization(2PP)configuration for fabrication of high-aspect three-dimensional(3D)structures,with an overall height larger than working distance of the microscope objective used for ...We developed a novel two-photon polymerization(2PP)configuration for fabrication of high-aspect three-dimensional(3D)structures,with an overall height larger than working distance of the microscope objective used for laser beam focusing into a photosensitive material.This method is based on a modified optical 2PP setup,where a microscope objective(1003 high N.A.),immersion oil and cover glass can be moved together into the photosensitive material,resulting in an effective higher and wider objective working range(WOW-2PP).The proposed technique enables the fabrication of high-aspect structures with sub-micrometer process resolution.3D structures with a height of 7 mm are demonstrated,which could hardly be built with the conventional 2PP set-up due to refractive index mismatch and laser beam disturbances.展开更多
In the femtosecond two-photon polymerization(2PP)experimental system,optical aberrations degrade the fabrication quality.To solve this issue,a multichannel interferometric wavefront sensing technique is adopted in the...In the femtosecond two-photon polymerization(2PP)experimental system,optical aberrations degrade the fabrication quality.To solve this issue,a multichannel interferometric wavefront sensing technique is adopted in the adaptive laser processing system with a single phase-only spatial light modulator.2PP fabrications using corrected high-order Bessel beams with the above solution have been conducted,and high-quality microstructure arrays of microtubes with 20μm diameter have been rapidly manufactured.The effectiveness of the proposed scheme is demonstrated by comparing the beam intensity distributions and 2PP results before and after aberration corrections.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
E,E-1,4-Bis（4＇-N,N-diphenylaminostyryl）-2,5-dimethoxybenzene （DPAMOB） has been synthesized by a simple and effective solid phase Wittig reaction and characterized by 1^H NMR spectra and elemental analysis, Linear...E,E-1,4-Bis（4＇-N,N-diphenylaminostyryl）-2,5-dimethoxybenzene （DPAMOB） has been synthesized by a simple and effective solid phase Wittig reaction and characterized by 1^H NMR spectra and elemental analysis, Linear absorption, single-photon induced fluorescence and two-photon induced fluorescence spectra were experimentally studied. The new dye has a large two-photon absorption （TPA） cross-section of σr= 1007,2 GM [1 GM= 1 × 10^-50 cm^4·s/（photon molecule）] at 800 nm measured by the two-photon induced fluorescence method. The experimental results confirm that DPAMOB is a good TPA chromophore and can successfully initiate two-photon photopolymerization of ethoxylated trimethylolpropane triacrylate esters （SR454）. Finally, a microstructure has been fabricated by use of DPAMOB as initiator.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
Binuclear complexes have attracted extensive attention in fields such as catalysis because of their likely bimetallic synergistic effect;however,the mechanism and factors influencing this synergism remain unclear.In t...Binuclear complexes have attracted extensive attention in fields such as catalysis because of their likely bimetallic synergistic effect;however,the mechanism and factors influencing this synergism remain unclear.In this work,six bis-β-ketoimine binuclear titanium complexes4a-4f containing different alkylthio sidearms and configurations were synthesized and characterized by nuclear magnetic resonance hydrogen spectrum(~1H-NMR),nuclear magnetic resonance carbon spectrum(^(13)C-NMR),Fourier transform infrared spectrum(FTIR),and elemental analysis.The intermetallic distances of isomeric complexes 4a,4d,4e and 4f determined through density functional theory(DFT)optimization were in the order 4a<4d<4e<4f and were found to significantly influence the catalytic performance for ethylene(co)polymerization.These complexes could efficiently catalyze ethylene polymerization and ethylene/1-hexene or ethylene/1-octene copolymerization with high activity to produce highmolecular-weight ethylene homo-and co-polymers.Among the three binuclear titanium complexes 4a-4c with similar structures but different lengths of alkylthio sidearms,complex 4a,which contained the shortest methylthio sidearm,exhibited the highest activity for ethylene polymerization and copolymerization with 1-hexene or 1-octene.Additionally,for ethylene/1-hexene or ethylene/1-octene copolymerization,it showed the highest comonomer incorporation compared with propylthio(4b)and octylthio(4c)derivatives because of the smaller steric hindrance of the methyl group in 4a and the more open coordination space for vinyl monomers.Furthermore,among the isomeric complexes 4a,4d,4e and4f,complex 4a with the shortest bimetallic distance also exhibited the highest activity towards ethylene(co)polymerization,and the highest 1-hexene or 1-octene incorporation in comparison with its regioisomeric counterparts 4d,4e and p-phenyl-bridged analog 4f,owing to a more appropriate bimetallic distance that is conducive to a synergistic effect.展开更多
It is important to understand the evolution of the matter on the polymer membrane surface.The in situ and real-time monitoring of the membrane surface will not only favor the investigation of selective layer formation...It is important to understand the evolution of the matter on the polymer membrane surface.The in situ and real-time monitoring of the membrane surface will not only favor the investigation of selective layer formation but can also track the fouling process during operation.Herein,an aggregation-induced emission(AIE)-active polymer membrane was prepared by the interfacial polymerization of a cyclodextrin-based glycocluster(CD@Glucose)and a tetraphenylethylene derivative modified with boronic acid groups(TPEDB)on the surface of a polyacrylonitrile(PAN)ultrafiltration membrane.This interfacial polymerization method can be stacked layer-by-layer to regulate the hydrophilicity and pore structure of the membrane.With the increase in the number of polymer layers,the separation and antifouling properties of the membrane gradually improved.Owing to the AIE property of the crosslinking agent TPEDB,the occurrence of interfacial polymerization and the degree of fouling during membrane operation can be monitored by the fluorescence distribution and intensity.With the aggravation of membrane fouling,the fluorescence decreased gradually,but recovered after cleaning.Therefore,this AIE effect can be used for real-time monitoring of interfacial polymerization as well as membrane fouling.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
Four photopolymerization initiators with D-π-D (D,donor; π,conjugation system) structure have been synthesized by solvent-free reaction and characterized by 1H NMR spectroscopy,IR and elemental analysis. The one-pho...Four photopolymerization initiators with D-π-D (D,donor; π,conjugation system) structure have been synthesized by solvent-free reaction and characterized by 1H NMR spectroscopy,IR and elemental analysis. The one-photon and two-photon excited fluorescence have been investigated in different solvents. Experimental results of the one-photon and two-photon absorption cross sections show different trends in OPA and TPA ability with different substitution groups in donor units.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.
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financially supported by the National Natural Science Foundation of China(No.52473338)the National Natural Science Foundation of China(Nos.52173004 and 51873055)+3 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA0540000)Advanced Materials-National Science and Technology Major Project(No.2025ZD0614000)Hebei Natural Science Foundation(No.E2022202015)Anhui Province Science and Technology Innovation Tackling Key Project(No.202423i08050025)。
文摘Heterogeneous polymerization represents a widely employed method in the polyolefin industry.In recent years,various heterogenization strategies for late transition metal catalysts have been developed,enabling effective control of polymer morphology and optimization of catalytic performance.However,while most studies have focused on designing anchoring groups and advancing support approaches,systematic investigations into how the support influences the catalytic behavior of the late transition metal catalysts.In this work,we fabricated supported α-diimine nickel catalysts by functionalizing the ligand with alkyl alcohol chains of varying lengths and supporting them onto MgCl_(2)supports.The ethylene polymerization behavior of these catalysts was then investigated.By precisely adjusting the alkyl alcohol chain length,the distance between the catalytically active metal center and the support surface was modulated.This approach demonstrates that support-induced steric hindrance effect can be effectively regulated by controlling the separation distance between the metal center and the support surface.
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.
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.
基金This research work was financially supported by National Science Foundation(CMMI 0900419 and 0758199)National Natural Science Foundation of China(grant no.90923039)。
文摘Modern three-dimensional nanofabrication requires both additive and subtractive processes.However,both processes are largely isolated and generally regarded as incompatible with each other.In this study,we developed simultaneous additive and subtractive fabrication processes using two-photon polymerization followed by femtosecond(fs)laser multiphoton ablation.To demonstrate the new capability,submicrometer polymer fibers containing periodic holes of 500-nm diameter and microfluidic channels of 1-mm diameter were successfully fabricated.This method combining both two-photon polymerization and fs laser ablation improves the nanofabrication efficiency and enables the fabrication of complex three-dimensional micro-/nanostructures,promising for a wide range of applications in integrated optics,microfluidics and microelectromechanical systems.
基金This work was supported by the Deutsche Forschungsgemeinschaft(German Research Foundation)Cluster of Excellence REBIRTH and EU/FP7 project Phocam.We thank E Fadeeva and J Koch for helpful technical discussions.
文摘We developed a novel two-photon polymerization(2PP)configuration for fabrication of high-aspect three-dimensional(3D)structures,with an overall height larger than working distance of the microscope objective used for laser beam focusing into a photosensitive material.This method is based on a modified optical 2PP setup,where a microscope objective(1003 high N.A.),immersion oil and cover glass can be moved together into the photosensitive material,resulting in an effective higher and wider objective working range(WOW-2PP).The proposed technique enables the fabrication of high-aspect structures with sub-micrometer process resolution.3D structures with a height of 7 mm are demonstrated,which could hardly be built with the conventional 2PP set-up due to refractive index mismatch and laser beam disturbances.
基金supported by the National Natural Science Foundation of China(Nos.62275191,61605142,and 61827821)the Tianjin Research Program of Application FoundationandAdvancedTechnologyofChina(No.17JCJQJC43500)+2 种基金the Open Fund of the State Key Laboratory of High Field Laser Physics,Shanghai Institute of Optics and Fine Mechanics,Chinese Academy of Sciencesthe European Research Council(No.682032-PULSAR)the Agence Nationale de la Recherche(Nos.ANR-15-IDEX0003 and ANR-17-EURE-0002)。
文摘In the femtosecond two-photon polymerization(2PP)experimental system,optical aberrations degrade the fabrication quality.To solve this issue,a multichannel interferometric wavefront sensing technique is adopted in the adaptive laser processing system with a single phase-only spatial light modulator.2PP fabrications using corrected high-order Bessel beams with the above solution have been conducted,and high-quality microstructure arrays of microtubes with 20μm diameter have been rapidly manufactured.The effectiveness of the proposed scheme is demonstrated by comparing the beam intensity distributions and 2PP results before and after aberration corrections.
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Project supported by the State Key-Program of China （No, 2004CB719803）, the National Natural Science Foundation of China （No. 05173015） and NSFC/RGC （No. 50218001 ）.
文摘E,E-1,4-Bis（4＇-N,N-diphenylaminostyryl）-2,5-dimethoxybenzene （DPAMOB） has been synthesized by a simple and effective solid phase Wittig reaction and characterized by 1^H NMR spectra and elemental analysis, Linear absorption, single-photon induced fluorescence and two-photon induced fluorescence spectra were experimentally studied. The new dye has a large two-photon absorption （TPA） cross-section of σr= 1007,2 GM [1 GM= 1 × 10^-50 cm^4·s/（photon molecule）] at 800 nm measured by the two-photon induced fluorescence method. The experimental results confirm that DPAMOB is a good TPA chromophore and can successfully initiate two-photon photopolymerization of ethoxylated trimethylolpropane triacrylate esters （SR454）. Finally, a microstructure has been fabricated by use of DPAMOB as initiator.
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 Natural Science Foundation of China(No.21172269)the Fundamental Research Funds for the Central Universities,SouthCentral Minzu University(No.CZH24005)。
文摘Binuclear complexes have attracted extensive attention in fields such as catalysis because of their likely bimetallic synergistic effect;however,the mechanism and factors influencing this synergism remain unclear.In this work,six bis-β-ketoimine binuclear titanium complexes4a-4f containing different alkylthio sidearms and configurations were synthesized and characterized by nuclear magnetic resonance hydrogen spectrum(~1H-NMR),nuclear magnetic resonance carbon spectrum(^(13)C-NMR),Fourier transform infrared spectrum(FTIR),and elemental analysis.The intermetallic distances of isomeric complexes 4a,4d,4e and 4f determined through density functional theory(DFT)optimization were in the order 4a<4d<4e<4f and were found to significantly influence the catalytic performance for ethylene(co)polymerization.These complexes could efficiently catalyze ethylene polymerization and ethylene/1-hexene or ethylene/1-octene copolymerization with high activity to produce highmolecular-weight ethylene homo-and co-polymers.Among the three binuclear titanium complexes 4a-4c with similar structures but different lengths of alkylthio sidearms,complex 4a,which contained the shortest methylthio sidearm,exhibited the highest activity for ethylene polymerization and copolymerization with 1-hexene or 1-octene.Additionally,for ethylene/1-hexene or ethylene/1-octene copolymerization,it showed the highest comonomer incorporation compared with propylthio(4b)and octylthio(4c)derivatives because of the smaller steric hindrance of the methyl group in 4a and the more open coordination space for vinyl monomers.Furthermore,among the isomeric complexes 4a,4d,4e and4f,complex 4a with the shortest bimetallic distance also exhibited the highest activity towards ethylene(co)polymerization,and the highest 1-hexene or 1-octene incorporation in comparison with its regioisomeric counterparts 4d,4e and p-phenyl-bridged analog 4f,owing to a more appropriate bimetallic distance that is conducive to a synergistic effect.
基金supported by the Fundamental Research Funds for Central Universities(No.30922010811).
文摘It is important to understand the evolution of the matter on the polymer membrane surface.The in situ and real-time monitoring of the membrane surface will not only favor the investigation of selective layer formation but can also track the fouling process during operation.Herein,an aggregation-induced emission(AIE)-active polymer membrane was prepared by the interfacial polymerization of a cyclodextrin-based glycocluster(CD@Glucose)and a tetraphenylethylene derivative modified with boronic acid groups(TPEDB)on the surface of a polyacrylonitrile(PAN)ultrafiltration membrane.This interfacial polymerization method can be stacked layer-by-layer to regulate the hydrophilicity and pore structure of the membrane.With the increase in the number of polymer layers,the separation and antifouling properties of the membrane gradually improved.Owing to the AIE property of the crosslinking agent TPEDB,the occurrence of interfacial polymerization and the degree of fouling during membrane operation can be monitored by the fluorescence distribution and intensity.With the aggravation of membrane fouling,the fluorescence decreased gradually,but recovered after cleaning.Therefore,this AIE effect can be used for real-time monitoring of interfacial polymerization as well as membrane fouling.
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Supported by the National Natural Science Foundation of China (Grant Nos. 50532030, 50703001 & 20771001)the National Natural Science Foundation of Anhui Province (Grant No. 070414188)+3 种基金Doctoral Program Foundation of the Minis-try of Education of China, Education Committee of Anhui Province (Grant No. 2006KJ032A & KJ2009A52)Team for Scientific Innovation Foundation of Anhui Province (Grant No. 2006KJ007TD)Young Teacher Foundation of Institution of High Education of Anhui Province (Grant No. 2007jq1019)Ministry of Education and Person with Ability Foundation of Anhui University
文摘Four photopolymerization initiators with D-π-D (D,donor; π,conjugation system) structure have been synthesized by solvent-free reaction and characterized by 1H NMR spectroscopy,IR and elemental analysis. The one-photon and two-photon excited fluorescence have been investigated in different solvents. Experimental results of the one-photon and two-photon absorption cross sections show different trends in OPA and TPA ability with different substitution groups in donor units.
