By using one-dimensional tight-binding model modified to include electron-electric field interaction and electron-electron interaction,we theoretically explore the polarization process of exciton and biexciton in cis-...By using one-dimensional tight-binding model modified to include electron-electric field interaction and electron-electron interaction,we theoretically explore the polarization process of exciton and biexciton in cis-polyacetylene.The dynamical simulation is performed by adopting the non-adiabatic evolution approach.The results show that under the effect of moderate electric field,when the strength of electron-electron interaction is weak,the singlet exciton is stable but its polarization presents obvious oscillation.With the enhancement of interaction,it is dissociated into polaron pairs,the spin-flip of which can be observed through modulating the interaction strength.For the triplet exciton,the strong electron-electron interaction restrains its normal polarization,but it is still stable.In the case of biexciton,the strong electron-electron interaction not only dissociate it,but also flip its charge distribution.The yield of the possible states formed after the dissociation of exciton and biexciton is also calculated.展开更多
With tunable local electronic environment,high mass density of MN4sites,and ease of preparation,metal-organic conjugated coordinative polymer(CCP) with inherent electronic conductivity provides a promising alternative...With tunable local electronic environment,high mass density of MN4sites,and ease of preparation,metal-organic conjugated coordinative polymer(CCP) with inherent electronic conductivity provides a promising alternative to the well-known M-N-C electrocatalysts.Herein,the coordination reaction between Cu^(2+)and 1,2,4,5-tetraaminobenzene(TAB) was conducted on the surface of metallic Cu nanowires,forming a thin layer of CuN4-based CCP(Cu-TAB) on the Cu nanowire.More importantly,interfacial transfer of electrons from Cu core to the CuN4-based CCP nanoshell was observed within the resulting CuTAB@Cu,which was found to enrich the local electronic density of the CuN4sites.As such,the CuTAB@Cu demonstrates much improved affinity to the*COOH intermediate formed from the rate determining step;the energy barrier for C-C coupling,which is critical to convert CO_(2)into C2products,is also decreased.Accordingly,it delivers a current density of-9.1 mA cm^(-2)at a potential as high as 0.558 V(vs.RHE) in H-type cell and a Faraday efficiency of 46.4% for ethanol.This work emphasizes the profound role of interfacial interaction in tuning the local electronic structure and activating the CuN4-based CCPs for efficient electroreduction of CO_(2).展开更多
A photocatalyst of nanometer TiO2/conjugated polymer complex was successfully synthesized and characterized by spectroscopic methods and photocatalytic experiments. The complex photocatalyst could be activated by abso...A photocatalyst of nanometer TiO2/conjugated polymer complex was successfully synthesized and characterized by spectroscopic methods and photocatalytic experiments. The complex photocatalyst could be activated by absorbing both ultraviolet and visible light (λ = 190-800 nm). Methylene blue (MB) could be degraded more efficiently on the complex photocatalyst than on the TiO2 under natural light. The conjugated polymer played a promoting role in the photocatalytic degradation of MB. The calcination temperature had an important effect in degradation of dye and could be summarized as 260℃ 〉 300 ℃ 〉 340 ℃ 〉 220 ℃ 〉 180 ℃.展开更多
Soft-stamped nanoimprint lithography(NIL) is considered as one of the most effective processes of nanoscale patterning because of its low cost and high throughput. In this work, this method is used to emboss the pol...Soft-stamped nanoimprint lithography(NIL) is considered as one of the most effective processes of nanoscale patterning because of its low cost and high throughput. In this work, this method is used to emboss the poly(9, 9-dioctylfluorene)film. By reducing the linewidth of the nanogratings on the stamp, the orientations of nanocrystals are confined along the grating vector in the nanoimprint process, where the confinement linewidth is comparable to the geometrical size of the nanocrystal. When the linewidth is about 400 nm, the poly(9, 9-dioctylfluorene)(PFO) nanocrystals could be orderly arranged in the nanogratings, so that both pattern transfer and well-aligned nanocrystal arrangement could be achieved in a single step by the soft-stamped NIL. The relevant mechanism of the nanocrystalline alignment in these nanogratings is fully discussed. The modulation of nanocrystal alignment is of benefit to the charge mobilities and other performances of PFO-based devices for the future applications.展开更多
A novel bipolar conjugated polymer containing triphenylamine and 1, 3, 4-oxadiazole units was synthesized by Suzuki reaction. Its structure and properties were characterized by NMR, IR, UV-Vis, PL spectroscopy and el...A novel bipolar conjugated polymer containing triphenylamine and 1, 3, 4-oxadiazole units was synthesized by Suzuki reaction. Its structure and properties were characterized by NMR, IR, UV-Vis, PL spectroscopy and electrochemical measurement. The photoluminescent spectroscopy and cyclic voltammograms measurement demonstrated that the resulting polymer shows blue emission (477 nm) and possesses both electron and hole-transporting property.展开更多
According to the one-dimensional tight-binding Su-Schrieffer-Heeger model, we have investigated the effects of charged polarons on the static polarizability, axx, and the second order hyperpolarizabilities, γxxxx, of...According to the one-dimensional tight-binding Su-Schrieffer-Heeger model, we have investigated the effects of charged polarons on the static polarizability, axx, and the second order hyperpolarizabilities, γxxxx, of conjugated polymers. Our results are consistent qualitatively with previous ab initio and semi-empirical calculations. The origin of the universal growth is discussed using a local-view formalism that is based on the local atomic charge derivatives. Furthermore, combining the Su Schrieffer-Heeger model and the extended Hubbard model, we have investigated systematically the effects of electron-electron interactions on αxx and γxxxx of charged polymer chains. For a fixed value of the nearest-neighbour interaction V, the values of αxx and γxxxx increase as the on-site Coulomb interaction U increases for U 〈 Uc and decrease with U for U 〉 Uc, where Uc is a critical value of U at which the static polarizability or the second order hypcrpolarizability reaches a maximal value of αxx or γxxxx. It is found that the effect of the e-e interaction on the value of αxx is dependent on the ratio between U and V for either a short or a long charged polymer. Whereas, that effect on the value of γxxxx is sensitive both to the ratio of U to V and to the size of the molecule.展开更多
A novel soluble conjugated copolymer (propionic acid)-co-(propargyl alcohol) (PA-co-OHP) has been synthesized for the first time using a new palladium acetylide catalyst Pd(PPh3)(2)(C=CC(CH3)(2)OH)(2)(PPB). Thin film ...A novel soluble conjugated copolymer (propionic acid)-co-(propargyl alcohol) (PA-co-OHP) has been synthesized for the first time using a new palladium acetylide catalyst Pd(PPh3)(2)(C=CC(CH3)(2)OH)(2)(PPB). Thin film resistive humidity sensor based oil the copolymer doped with HClO4 was prepared. The impedance of the sensor changed from 10(3)similar to 10(7) Omega in 95%similar to 30%RH, and the response of that is very quick (<6 sec.). Preliminary results show the copolymer is a promising humidity sensitive material.展开更多
^13C spin-lattice relaxation times (T1) of a conjugated polymer MEH-PPV in polymer/ layered silicate nanocomposites together with the steady state fluorescence emission and transient fluorescence decay measurements ...^13C spin-lattice relaxation times (T1) of a conjugated polymer MEH-PPV in polymer/ layered silicate nanocomposites together with the steady state fluorescence emission and transient fluorescence decay measurements have been investigated. The T1 values of the conjugated carbons decrease dramatically according to the reduction of polymer concentration in the nano composites, while the fluorescence life times (τ) show a linear prolonging tendency. The results are explained from the point of view of molecular dynamics.展开更多
Short wave near-infrared(SWIR,900-1700 nm)fluorescence imaging has attracted extensive research interest from scientists due to its high imaging quality.However,the variety of SWIR fluorescence imaging agents are quit...Short wave near-infrared(SWIR,900-1700 nm)fluorescence imaging has attracted extensive research interest from scientists due to its high imaging quality.However,the variety of SWIR fluorescence imaging agents are quite limited and the corresponding quantum efficiency is rela-tively low.In this work,a novel conjugated polymer PDTSDTBT was reported,consisting of a donor unit with a tetrahedral Si(sp3)named DTS and an acceptor unit named DTBT with branched side chains.The design approach of endowing the donor-acceptor structure with the branched side chains successfully increase the fluorescence quantum efficiency.The polymer was prepared into nanoparticles by nanoprecipitation.The PDTSDTBT nanoparticles showed an absorption peak of 626 nm and fluorescence emission peak of 924 nm.The quantum efficiency of the nanoparticles is 0.53%,which is higher than that of nanotube fluorophores(0.4%).The nanoparticles also demonstrate a photothermal effect,the temperature of nanoparticles solution could reach 45℃under excitation by 660 nm laser.Therefore,the PDTSDTBT nanoparticles is an excellent fluorescent imaging agent with potential photothermal applications.展开更多
We have studied the electric-field-driven motion of a polaron by solving the time-dependent SchrSdinger equation nonadiabatically and the lattice equation of motion simultaneously. It is found that the polaron may exp...We have studied the electric-field-driven motion of a polaron by solving the time-dependent SchrSdinger equation nonadiabatically and the lattice equation of motion simultaneously. It is found that the polaron may experience two sequent transitions under high fields; one is the transition from the subsonic to the supersonic state, and the other from the supersonic to dissociated state. The acoustic mode is decoupled from the charge when the polaron moves at a speed faster than the sound speed, and then the optical mode is decoupled at the second transition to make the polaron dissociate completely.展开更多
The absorption,scattering,and autofluorescence of biological tissues in short-wave infrared re-gion(SWIR,900-1700 nm)are relatively low,so SWIR fluorescence usually has deeper pene-tration into living tissues,and can ...The absorption,scattering,and autofluorescence of biological tissues in short-wave infrared re-gion(SWIR,900-1700 nm)are relatively low,so SWIR fluorescence usually has deeper pene-tration into living tissues,and can show a higher signal-to-noise ratio when used for imaging in vivo.However,there are few types of organic SWIR fluorescent materials currently.In this work,p-azaquinodimethane(p-AQM)with a quinoid structure is used as the acceptor unit,and car-bazole or fluorene with sp3 hybridization are used as the donor units,two conjugated polymers were synthesized.The quinone structure is conducive to the redshift of absorption and fluores-cence spectra,and the sp3 hybridization structure is conducive to weakening the aggregation quenching of polymer fluorescence.PF and PCz exhibited absorption peaks of 492 nm and 508 nm,respectively.The emission peaks of the two polymers are 920 nm and 950 nm,respec-tively,both in the short-wave near infrared region.The quantum yield(QY)of PF and PCz is 0.4%and 0.3%,respectively.展开更多
Photoacoustic imaging(PAI)is a hybrid imaging method based on photoacoustic(PA)effects,which is able to capture the structure,function,and molecular information of biological tissues with high resolution.To date,thera...Photoacoustic imaging(PAI)is a hybrid imaging method based on photoacoustic(PA)effects,which is able to capture the structure,function,and molecular information of biological tissues with high resolution.To date,therapeutic techniques under the guidance of PAI have provided new strategies for accurate diagnosis and precise treatment of tumors.In particular,conjugated polymer nanoparticles have been extensively inspected for PA-based cancer theranostics largely due to their superior optical properties such as tunable spectrum and large absorption coefficient and their good biocompatibility,and abundant functional groups.This mini-review mainly focuses on the recent advances toward the development of novel conjugated polymer nanoparticles for PA-based multimodal imaging and cancer photothermal therapy.展开更多
A new type of chiral conjugated polymers 6a-d has been synthesized by the reaction of (R)-2,2'-dihydroxy-1,1'-binaphthyl-6,6'-dicarbaldehyde 5 with corresponding diamine in the presence of acetic acid.
Within a Su-Schriffer-Heeger model modified to include electron-electron interaction and an external electric field, we investigate the dynamics of oppositely charged polarons in a polymer chain in the presence of bot...Within a Su-Schriffer-Heeger model modified to include electron-electron interaction and an external electric field, we investigate the dynamics of oppositely charged polarons in a polymer chain in the presence of both electron-phonon and electron-electron interactions under the influence of an external electric field. We adopt a multi-configurational time-dependent Hartree-Fock method for the time-dependent Schrodinger equation and the Newtonian equation of motion for a lattice. Our results show that the on-site Coulomb interaction is of fundamental importance and favors the recombination between the pairs of polarons, and the yield of excitons depends crucially on the strength of the on-site Coulomb interaction U. Furthermore, the influence of the nearest neighbor interaction V is also discussed.展开更多
Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safet...Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safety compared with inorganic PTMs. However, so far, only a few NIR-Ⅱresponsive organic PTMs was explored, and their photothermal conversion efficiencies(PCEs) still remain relatively low. Herein, donor–acceptor conjugated diradical polymers with open-shell characteristics are explored for synergistically photothermal immunotherapy of metastatic tumors in the NIR-Ⅱ window. By employing side-chain regulation, the conjugated diradical polymer TTB-2 with obvious NIR-Ⅱ absorption was developed, and its nanoparticles realize a record-breaking PCE of 87.7% upon NIR-Ⅱ light illustration. In vitro and in vivo experiments demonstrate that TTB-2 nanoparticles show good tumor photoablation with navigation of photoacoustic imaging in the NIR-Ⅱ window, without any side-effect. Moreover, by combining with PD-1 antibody,the pulmonary metastasis of breast cancer is high-effectively prevented by the efficient photo-immunity effect. Thus, this study explores superior PTMs for cancer metastasis theranostics in the NIR-Ⅱ window, offering a new horizon in developing radical-characteristic NIR-Ⅱ photothermal materials.展开更多
In this work,semirigid linkers of the alkyl-thiophene-alkyl structure are developed to construct double-cable polymers.Three alkyl units,propyl(C3H6),hexyl(C6H12),and dodecyl(C12H24),are applied as semirigid linkers,y...In this work,semirigid linkers of the alkyl-thiophene-alkyl structure are developed to construct double-cable polymers.Three alkyl units,propyl(C3H6),hexyl(C6H12),and dodecyl(C12H24),are applied as semirigid linkers,yielding three double-cable polymers:PBC6-T,PBC12-T,and PBC24-T,respectively.PBC12-T which uses C6H12-thiophene-C6H12 linkers is found to exhibit the best device efficiency of 5.56%,while PBC6-T and PBC24-T with shorter or longer linkers yield device efficiencies of only 2.65%and 1.09%in single-component organic solar cells(SCOSCs).Further studies reveal that PBC12-T exhibits higher crystallinity and improved charge transport,resulting in better efficiencies.Our work provides an approach to construct double-cable conjugated polymers with long alkyl linkers,and it shows the importance of the linker length for the photovoltaic performance of SCOSCs.展开更多
Designing cost-effective and high-performing metal catalysts is significant for many renewable energy conversion technologies.Lowering metal loading without sacrificing activity and durability is highly desired for th...Designing cost-effective and high-performing metal catalysts is significant for many renewable energy conversion technologies.Lowering metal loading without sacrificing activity and durability is highly desired for the catalyst design,especially for those reactions where the noble metals deliver the best catalyzing performance.Single-atom catalysts(SACs)with maximal metalatom utilization,homogeneous and tailorable active sites have emerged as promising catalyst candidates,where the local coordination structures of the metal atoms in SACs largely determine the reaction kinetics.Previous design strategies of constructing strong metal-support interactions can stabilize the individual metal atoms in SACs,but present obstacles to provide a flexible manipulation platform for elaborately tailoring the coordination structures to achieve performance optimization towards a specifically targeted reaction.Here,for the proof-of-concept study,we report a novel design of SAC with iridium(Ir)single atoms supported on conjugated polymer,in which the adsorption energies of reaction intermediates on Ir atoms and the reaction kinetics towards acidic water oxidation can be readily optimized through modulating the formed cation-πinteractions that can be tailored by adjusting the molecular structures of conjugated polymers.This strategy establishes a general route to develop targeted SACs for various catalytic reactions.展开更多
The photovoltaic properties of double-cable conjugated polymers are significantly influenced by the length of the alkyl linkers that connect donor backbones and acceptor side units. In this study, a series of 2-(3-oxo...The photovoltaic properties of double-cable conjugated polymers are significantly influenced by the length of the alkyl linkers that connect donor backbones and acceptor side units. In this study, a series of 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile(IC)-based double-cable polymers with alkyl linkers ranging from C_8H_(16)to C_(16)H_(32)(Px, x = 8, 10, 12, 14, 16) were synthesized for single-component organic solar cells(SCOSCs). Among these, the linker length x = 12(P12) is found to optimize the power conversion efficiencies(PCEs) in SCOSCs. Specifically, PCEs increase from P8 to P12 and then decline from P12to P16. Detailed investigations of optical absorption, charge transport, and morphology provide insights into the underlying factors contributing to these PCE variations. The findings indicate that the exceptional photovoltaic properties observed in P12 can be attributed to three key factors: A delicate balance between enhanced charge separation facilitated by the increased spacer length and reduced crystallinity resulting from longer spacers, higher charge mobilities, and well-balanced hole/electron transport characteristics. This study highlights the critical role of linker length in determining the photovoltaic properties of double-cable conjugated polymer-based SCOSCs and offers valuable guidance for the design of novel double-cable conjugated polymers.展开更多
Wearable biosensors have received great interest as patient-friendly diagnostic technologies because of their high flexibility and conformability.The growing research and utilization of novel materials in designing we...Wearable biosensors have received great interest as patient-friendly diagnostic technologies because of their high flexibility and conformability.The growing research and utilization of novel materials in designing wearable biosensors have accelerated the development of point-of-care sensing platforms and implantable biomedical devices in human health care.Among numerous potential materials,conjugated polymers(CPs)are emerging as ideal choices for constructing high-performance wearable biosensors because of their outstanding conductive and mechanical properties.Recently,CPs have been extensively incorporated into various wearable biosensors to monitor a range of target biomolecules.However,fabricating highly reliable CP-based wearable biosensors for practical applications remains a significant challenge,necessitating novel developmental strategies for enhancing the viability of such biosensors.Accordingly,this review aims to provide consolidated scientific evidence by summarizing and evaluating recent studies focused on designing and fabricating CP-based wearable biosensors,thereby facilitating future research.Emphasizing the superior properties and benefits of CPs,this review aims to clarify their potential applicability within this field.Furthermore,the fundamentals and main components of CP-based wearable biosensors and their sensing mechanisms are discussed in detail.The recent advancements in CP nanostructures and hybridizations for improved sensing performance,along with recent innovations in next-generation wearable biosensors are highlighted.CPbased wearable biosensors have been—and will continue to be—an ideal platform for developing effective and user-friendly diagnostic technologies for human health monitoring.展开更多
Comprehensive Summary Conjugated polymers(CPs)containing quinoidal units are promising in n-type organic thermoelectric materials because of their deep-positioned lowest unoccupied molecular orbital(LUMO)energy levels...Comprehensive Summary Conjugated polymers(CPs)containing quinoidal units are promising in n-type organic thermoelectric materials because of their deep-positioned lowest unoccupied molecular orbital(LUMO)energy levels and planar conjugated backbones.Herein,three CPs have been synthesized by copolymerizing an indandione-terminated quinoidal unit with bithiophene derivatives.Owning to the high electron affinity of the indandione-terminated quinoidal unit,all polymers showed deep LUMO energy levels below-4.10 eV.Incorporating electron-withdrawing substituents(F or CN)on the bithiophene comonomer can further downshift the LUMO energy levels.As a result,a more efficient n-doping process can be realized when employing 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine(N-DMBI)as the dopant.Ultimately,the polymer with CN substituents delivered the best thermoelectric performance with a power factor of up to 2.14μW·m^(−1)·K^(−2),because it possessed the lowest LUMO energy level among the three CPs.This work highlights that the modulation of LUMO energy level is an effective strategy to optimize the thermoelectric performance of CPs.展开更多
基金Project supported by the Natural Science Foundation of Shandong Province,China(Grant No.ZR2020MA070).
文摘By using one-dimensional tight-binding model modified to include electron-electric field interaction and electron-electron interaction,we theoretically explore the polarization process of exciton and biexciton in cis-polyacetylene.The dynamical simulation is performed by adopting the non-adiabatic evolution approach.The results show that under the effect of moderate electric field,when the strength of electron-electron interaction is weak,the singlet exciton is stable but its polarization presents obvious oscillation.With the enhancement of interaction,it is dissociated into polaron pairs,the spin-flip of which can be observed through modulating the interaction strength.For the triplet exciton,the strong electron-electron interaction restrains its normal polarization,but it is still stable.In the case of biexciton,the strong electron-electron interaction not only dissociate it,but also flip its charge distribution.The yield of the possible states formed after the dissociation of exciton and biexciton is also calculated.
基金The National Key Research and Development Program of China(2021YFA1502000 and 2022YFA1505300)the National Natural Science Foundation of China (22288102, 22072124)+1 种基金support from Beijing Synchrotron Radiation Facility (1W1B, BSRF)China Scholarship Council for the financial support。
文摘With tunable local electronic environment,high mass density of MN4sites,and ease of preparation,metal-organic conjugated coordinative polymer(CCP) with inherent electronic conductivity provides a promising alternative to the well-known M-N-C electrocatalysts.Herein,the coordination reaction between Cu^(2+)and 1,2,4,5-tetraaminobenzene(TAB) was conducted on the surface of metallic Cu nanowires,forming a thin layer of CuN4-based CCP(Cu-TAB) on the Cu nanowire.More importantly,interfacial transfer of electrons from Cu core to the CuN4-based CCP nanoshell was observed within the resulting CuTAB@Cu,which was found to enrich the local electronic density of the CuN4sites.As such,the CuTAB@Cu demonstrates much improved affinity to the*COOH intermediate formed from the rate determining step;the energy barrier for C-C coupling,which is critical to convert CO_(2)into C2products,is also decreased.Accordingly,it delivers a current density of-9.1 mA cm^(-2)at a potential as high as 0.558 V(vs.RHE) in H-type cell and a Faraday efficiency of 46.4% for ethanol.This work emphasizes the profound role of interfacial interaction in tuning the local electronic structure and activating the CuN4-based CCPs for efficient electroreduction of CO_(2).
文摘A photocatalyst of nanometer TiO2/conjugated polymer complex was successfully synthesized and characterized by spectroscopic methods and photocatalytic experiments. The complex photocatalyst could be activated by absorbing both ultraviolet and visible light (λ = 190-800 nm). Methylene blue (MB) could be degraded more efficiently on the complex photocatalyst than on the TiO2 under natural light. The conjugated polymer played a promoting role in the photocatalytic degradation of MB. The calcination temperature had an important effect in degradation of dye and could be summarized as 260℃ 〉 300 ℃ 〉 340 ℃ 〉 220 ℃ 〉 180 ℃.
基金Project supported by the National Natural Science Foundation of China(Grant No.21204058)
文摘Soft-stamped nanoimprint lithography(NIL) is considered as one of the most effective processes of nanoscale patterning because of its low cost and high throughput. In this work, this method is used to emboss the poly(9, 9-dioctylfluorene)film. By reducing the linewidth of the nanogratings on the stamp, the orientations of nanocrystals are confined along the grating vector in the nanoimprint process, where the confinement linewidth is comparable to the geometrical size of the nanocrystal. When the linewidth is about 400 nm, the poly(9, 9-dioctylfluorene)(PFO) nanocrystals could be orderly arranged in the nanogratings, so that both pattern transfer and well-aligned nanocrystal arrangement could be achieved in a single step by the soft-stamped NIL. The relevant mechanism of the nanocrystalline alignment in these nanogratings is fully discussed. The modulation of nanocrystal alignment is of benefit to the charge mobilities and other performances of PFO-based devices for the future applications.
基金This work was supported by the National Natural Science Foundation of China (No. 29725410 and 29992530) and Chinese Academy of Sciences (KJ951-A1-501-01).
文摘A novel bipolar conjugated polymer containing triphenylamine and 1, 3, 4-oxadiazole units was synthesized by Suzuki reaction. Its structure and properties were characterized by NMR, IR, UV-Vis, PL spectroscopy and electrochemical measurement. The photoluminescent spectroscopy and cyclic voltammograms measurement demonstrated that the resulting polymer shows blue emission (477 nm) and possesses both electron and hole-transporting property.
基金Project supported by the National Natural Science Foundation of China(Grant No.10574037)the Program for New Century Excellent Talents in University of Ministry of Education of China(Grant No.NCET-05-0262)+3 种基金the Hebei Provincial Outstanding Youth Science Fund(Grant No.A2009001512)the Key Project of Ministry of Education of China(Grant No.210021)the Natural Science Fund of Hebei Province,China(Grant No.A2010000357)the Educational Commission of Hebei Province, China(Grant No.2007124)
文摘According to the one-dimensional tight-binding Su-Schrieffer-Heeger model, we have investigated the effects of charged polarons on the static polarizability, axx, and the second order hyperpolarizabilities, γxxxx, of conjugated polymers. Our results are consistent qualitatively with previous ab initio and semi-empirical calculations. The origin of the universal growth is discussed using a local-view formalism that is based on the local atomic charge derivatives. Furthermore, combining the Su Schrieffer-Heeger model and the extended Hubbard model, we have investigated systematically the effects of electron-electron interactions on αxx and γxxxx of charged polymer chains. For a fixed value of the nearest-neighbour interaction V, the values of αxx and γxxxx increase as the on-site Coulomb interaction U increases for U 〈 Uc and decrease with U for U 〉 Uc, where Uc is a critical value of U at which the static polarizability or the second order hypcrpolarizability reaches a maximal value of αxx or γxxxx. It is found that the effect of the e-e interaction on the value of αxx is dependent on the ratio between U and V for either a short or a long charged polymer. Whereas, that effect on the value of γxxxx is sensitive both to the ratio of U to V and to the size of the molecule.
文摘A novel soluble conjugated copolymer (propionic acid)-co-(propargyl alcohol) (PA-co-OHP) has been synthesized for the first time using a new palladium acetylide catalyst Pd(PPh3)(2)(C=CC(CH3)(2)OH)(2)(PPB). Thin film resistive humidity sensor based oil the copolymer doped with HClO4 was prepared. The impedance of the sensor changed from 10(3)similar to 10(7) Omega in 95%similar to 30%RH, and the response of that is very quick (<6 sec.). Preliminary results show the copolymer is a promising humidity sensitive material.
基金supported by the National Natural Science Foundation of China(Grant No.20023003).
文摘^13C spin-lattice relaxation times (T1) of a conjugated polymer MEH-PPV in polymer/ layered silicate nanocomposites together with the steady state fluorescence emission and transient fluorescence decay measurements have been investigated. The T1 values of the conjugated carbons decrease dramatically according to the reduction of polymer concentration in the nano composites, while the fluorescence life times (τ) show a linear prolonging tendency. The results are explained from the point of view of molecular dynamics.
基金supported by the National Natural Science Foundation of China(21807062,21976099 and 31570355)the Shandong Provincial Natural Science Foundation(ZR2018BB014)+2 种基金the Source Innovation Project of Qingdao(171183jch)Qingdao Postdoctoral Applied Research Project(2018111)National College Students Innova-tion and Entrepreneurship Training Program(201910429007)
文摘Short wave near-infrared(SWIR,900-1700 nm)fluorescence imaging has attracted extensive research interest from scientists due to its high imaging quality.However,the variety of SWIR fluorescence imaging agents are quite limited and the corresponding quantum efficiency is rela-tively low.In this work,a novel conjugated polymer PDTSDTBT was reported,consisting of a donor unit with a tetrahedral Si(sp3)named DTS and an acceptor unit named DTBT with branched side chains.The design approach of endowing the donor-acceptor structure with the branched side chains successfully increase the fluorescence quantum efficiency.The polymer was prepared into nanoparticles by nanoprecipitation.The PDTSDTBT nanoparticles showed an absorption peak of 626 nm and fluorescence emission peak of 924 nm.The quantum efficiency of the nanoparticles is 0.53%,which is higher than that of nanotube fluorophores(0.4%).The nanoparticles also demonstrate a photothermal effect,the temperature of nanoparticles solution could reach 45℃under excitation by 660 nm laser.Therefore,the PDTSDTBT nanoparticles is an excellent fluorescent imaging agent with potential photothermal applications.
基金Project supported by the Major Program of the National Natural Science Foundation of China (Grant Nos 10474056, 90403110 and 10574082).
文摘We have studied the electric-field-driven motion of a polaron by solving the time-dependent SchrSdinger equation nonadiabatically and the lattice equation of motion simultaneously. It is found that the polaron may experience two sequent transitions under high fields; one is the transition from the subsonic to the supersonic state, and the other from the supersonic to dissociated state. The acoustic mode is decoupled from the charge when the polaron moves at a speed faster than the sound speed, and then the optical mode is decoupled at the second transition to make the polaron dissociate completely.
基金supported by the National Natural Science Foundation of China(Grant Nos.21807062 and 21976099)the Shandong Provincial Natural Science Foundation(ZR2018BB014)+3 种基金the Department of Science and Technology of Shan-dong Province(2019GGX102020)the Source In-novation Project of Qingdao(171183jch)Qingdao Postdoctoral Applied Research Project(2018111)National College Students Innovation and En-trepreneurship Training Program(201910429007)
文摘The absorption,scattering,and autofluorescence of biological tissues in short-wave infrared re-gion(SWIR,900-1700 nm)are relatively low,so SWIR fluorescence usually has deeper pene-tration into living tissues,and can show a higher signal-to-noise ratio when used for imaging in vivo.However,there are few types of organic SWIR fluorescent materials currently.In this work,p-azaquinodimethane(p-AQM)with a quinoid structure is used as the acceptor unit,and car-bazole or fluorene with sp3 hybridization are used as the donor units,two conjugated polymers were synthesized.The quinone structure is conducive to the redshift of absorption and fluores-cence spectra,and the sp3 hybridization structure is conducive to weakening the aggregation quenching of polymer fluorescence.PF and PCz exhibited absorption peaks of 492 nm and 508 nm,respectively.The emission peaks of the two polymers are 920 nm and 950 nm,respec-tively,both in the short-wave near infrared region.The quantum yield(QY)of PF and PCz is 0.4%and 0.3%,respectively.
基金We acknowledge financial support from grants MYRG2014-00093-FHS,MYRG 2015-00036-FHS,MYRG2016-00110-FHS and MYRG2018-00081-FHS from the University of Macao in Macao and grants FDCT 0011/2018/A1 and FDCT 025/2015/A1 from the Macao government.
文摘Photoacoustic imaging(PAI)is a hybrid imaging method based on photoacoustic(PA)effects,which is able to capture the structure,function,and molecular information of biological tissues with high resolution.To date,therapeutic techniques under the guidance of PAI have provided new strategies for accurate diagnosis and precise treatment of tumors.In particular,conjugated polymer nanoparticles have been extensively inspected for PA-based cancer theranostics largely due to their superior optical properties such as tunable spectrum and large absorption coefficient and their good biocompatibility,and abundant functional groups.This mini-review mainly focuses on the recent advances toward the development of novel conjugated polymer nanoparticles for PA-based multimodal imaging and cancer photothermal therapy.
文摘A new type of chiral conjugated polymers 6a-d has been synthesized by the reaction of (R)-2,2'-dihydroxy-1,1'-binaphthyl-6,6'-dicarbaldehyde 5 with corresponding diamine in the presence of acetic acid.
基金Supported by the National Natural Science Foundation of China under Grant No 11474218
文摘Within a Su-Schriffer-Heeger model modified to include electron-electron interaction and an external electric field, we investigate the dynamics of oppositely charged polarons in a polymer chain in the presence of both electron-phonon and electron-electron interactions under the influence of an external electric field. We adopt a multi-configurational time-dependent Hartree-Fock method for the time-dependent Schrodinger equation and the Newtonian equation of motion for a lattice. Our results show that the on-site Coulomb interaction is of fundamental importance and favors the recombination between the pairs of polarons, and the yield of excitons depends crucially on the strength of the on-site Coulomb interaction U. Furthermore, the influence of the nearest neighbor interaction V is also discussed.
基金The work was financially supported by the National Natural Science Foundation of China(No.52173135,22207024)Jiangsu Specially Appointed Professorship,Leading Talents of Innovation and Entrepreneurship of Gusu(ZXL2022496)the Suzhou Science and Technology Program(SKY2022039).
文摘Massive efforts have been concentrated on the advance of eminent near-infrared(NIR) photothermal materials(PTMs) in the NIR-Ⅱ window(1000–1700 nm), especially organic PTMs because of their intrinsic biological safety compared with inorganic PTMs. However, so far, only a few NIR-Ⅱresponsive organic PTMs was explored, and their photothermal conversion efficiencies(PCEs) still remain relatively low. Herein, donor–acceptor conjugated diradical polymers with open-shell characteristics are explored for synergistically photothermal immunotherapy of metastatic tumors in the NIR-Ⅱ window. By employing side-chain regulation, the conjugated diradical polymer TTB-2 with obvious NIR-Ⅱ absorption was developed, and its nanoparticles realize a record-breaking PCE of 87.7% upon NIR-Ⅱ light illustration. In vitro and in vivo experiments demonstrate that TTB-2 nanoparticles show good tumor photoablation with navigation of photoacoustic imaging in the NIR-Ⅱ window, without any side-effect. Moreover, by combining with PD-1 antibody,the pulmonary metastasis of breast cancer is high-effectively prevented by the efficient photo-immunity effect. Thus, this study explores superior PTMs for cancer metastasis theranostics in the NIR-Ⅱ window, offering a new horizon in developing radical-characteristic NIR-Ⅱ photothermal materials.
基金the Beijing Natural Science Foundation(No.JQ21006)the Ministry of Science and Technology(No.2018YFA0208504)+3 种基金the National Natural Science Foundation(Nos.92163128,52073016,21905018)of Chinathe Fundamental Research Funds for the Central Universities(Nos.buctrc201828,XK1802-2)Open Project of State Key Laboratory of Organic-Inorganic Composites(No.oic-202201006)Open Project of State Key Laboratory of Supramolecular Structure and Materials(No.sklssm202209).
文摘In this work,semirigid linkers of the alkyl-thiophene-alkyl structure are developed to construct double-cable polymers.Three alkyl units,propyl(C3H6),hexyl(C6H12),and dodecyl(C12H24),are applied as semirigid linkers,yielding three double-cable polymers:PBC6-T,PBC12-T,and PBC24-T,respectively.PBC12-T which uses C6H12-thiophene-C6H12 linkers is found to exhibit the best device efficiency of 5.56%,while PBC6-T and PBC24-T with shorter or longer linkers yield device efficiencies of only 2.65%and 1.09%in single-component organic solar cells(SCOSCs).Further studies reveal that PBC12-T exhibits higher crystallinity and improved charge transport,resulting in better efficiencies.Our work provides an approach to construct double-cable conjugated polymers with long alkyl linkers,and it shows the importance of the linker length for the photovoltaic performance of SCOSCs.
基金supported by National Natural Science Foundation of China(52103260,52373211,52161135302)Natural Science Foundation of Jiangsu Province(BK20210482,BK20221099)China Postdoctoral Science Foundation(2023T160274,2021M690067)。
文摘Designing cost-effective and high-performing metal catalysts is significant for many renewable energy conversion technologies.Lowering metal loading without sacrificing activity and durability is highly desired for the catalyst design,especially for those reactions where the noble metals deliver the best catalyzing performance.Single-atom catalysts(SACs)with maximal metalatom utilization,homogeneous and tailorable active sites have emerged as promising catalyst candidates,where the local coordination structures of the metal atoms in SACs largely determine the reaction kinetics.Previous design strategies of constructing strong metal-support interactions can stabilize the individual metal atoms in SACs,but present obstacles to provide a flexible manipulation platform for elaborately tailoring the coordination structures to achieve performance optimization towards a specifically targeted reaction.Here,for the proof-of-concept study,we report a novel design of SAC with iridium(Ir)single atoms supported on conjugated polymer,in which the adsorption energies of reaction intermediates on Ir atoms and the reaction kinetics towards acidic water oxidation can be readily optimized through modulating the formed cation-πinteractions that can be tailored by adjusting the molecular structures of conjugated polymers.This strategy establishes a general route to develop targeted SACs for various catalytic reactions.
基金jointly supported by the Beijing Natural Science Foundation (Nos.2212045 and JQ21006)the National Natural Science Foundation of China (Nos.21905158, 52073016 and 92163128)+2 种基金further supported by the Fundamental Research Funds for the Central Universities (Nos.buctrc202111, buctrc201828, and XK1802-2)the Opening Foundation of State Key Laboratory of Organic-Inorganic Composites of Beijing University of Chemical Technology (No.oic-202201006)Jiangxi Provincial Department of Science and Technology (Nos.20202ACBL213004, 20212BCJ23035, jxsq2019102004)。
文摘The photovoltaic properties of double-cable conjugated polymers are significantly influenced by the length of the alkyl linkers that connect donor backbones and acceptor side units. In this study, a series of 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile(IC)-based double-cable polymers with alkyl linkers ranging from C_8H_(16)to C_(16)H_(32)(Px, x = 8, 10, 12, 14, 16) were synthesized for single-component organic solar cells(SCOSCs). Among these, the linker length x = 12(P12) is found to optimize the power conversion efficiencies(PCEs) in SCOSCs. Specifically, PCEs increase from P8 to P12 and then decline from P12to P16. Detailed investigations of optical absorption, charge transport, and morphology provide insights into the underlying factors contributing to these PCE variations. The findings indicate that the exceptional photovoltaic properties observed in P12 can be attributed to three key factors: A delicate balance between enhanced charge separation facilitated by the increased spacer length and reduced crystallinity resulting from longer spacers, higher charge mobilities, and well-balanced hole/electron transport characteristics. This study highlights the critical role of linker length in determining the photovoltaic properties of double-cable conjugated polymer-based SCOSCs and offers valuable guidance for the design of novel double-cable conjugated polymers.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea Government(MSIT)(No.NRF-2021R1A2C2004109)the Korea Institute for Advancement of Technology(KIAT)grant funded by the Korea Government(MOTIE)(No.P0020612,2022 The Competency Development Program for Industry Specialist).
文摘Wearable biosensors have received great interest as patient-friendly diagnostic technologies because of their high flexibility and conformability.The growing research and utilization of novel materials in designing wearable biosensors have accelerated the development of point-of-care sensing platforms and implantable biomedical devices in human health care.Among numerous potential materials,conjugated polymers(CPs)are emerging as ideal choices for constructing high-performance wearable biosensors because of their outstanding conductive and mechanical properties.Recently,CPs have been extensively incorporated into various wearable biosensors to monitor a range of target biomolecules.However,fabricating highly reliable CP-based wearable biosensors for practical applications remains a significant challenge,necessitating novel developmental strategies for enhancing the viability of such biosensors.Accordingly,this review aims to provide consolidated scientific evidence by summarizing and evaluating recent studies focused on designing and fabricating CP-based wearable biosensors,thereby facilitating future research.Emphasizing the superior properties and benefits of CPs,this review aims to clarify their potential applicability within this field.Furthermore,the fundamentals and main components of CP-based wearable biosensors and their sensing mechanisms are discussed in detail.The recent advancements in CP nanostructures and hybridizations for improved sensing performance,along with recent innovations in next-generation wearable biosensors are highlighted.CPbased wearable biosensors have been—and will continue to be—an ideal platform for developing effective and user-friendly diagnostic technologies for human health monitoring.
基金supported by National Key R&D Program of China(2021YFA0717900)National Natural Science Foundation of China(52073209,52121002 and 22222506)the Fundamental Research Funds forthe Central Universities.
文摘Comprehensive Summary Conjugated polymers(CPs)containing quinoidal units are promising in n-type organic thermoelectric materials because of their deep-positioned lowest unoccupied molecular orbital(LUMO)energy levels and planar conjugated backbones.Herein,three CPs have been synthesized by copolymerizing an indandione-terminated quinoidal unit with bithiophene derivatives.Owning to the high electron affinity of the indandione-terminated quinoidal unit,all polymers showed deep LUMO energy levels below-4.10 eV.Incorporating electron-withdrawing substituents(F or CN)on the bithiophene comonomer can further downshift the LUMO energy levels.As a result,a more efficient n-doping process can be realized when employing 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine(N-DMBI)as the dopant.Ultimately,the polymer with CN substituents delivered the best thermoelectric performance with a power factor of up to 2.14μW·m^(−1)·K^(−2),because it possessed the lowest LUMO energy level among the three CPs.This work highlights that the modulation of LUMO energy level is an effective strategy to optimize the thermoelectric performance of CPs.