The mitigation of under-coordinated Pb^(2+)(halide vacancy)defect remains an imperative challenge in the perovskite solar cells,especially printable mesoscopic perovskite solar cells(FP-PsCs).Here we re port a commerc...The mitigation of under-coordinated Pb^(2+)(halide vacancy)defect remains an imperative challenge in the perovskite solar cells,especially printable mesoscopic perovskite solar cells(FP-PsCs).Here we re port a commercial-available polyazin anticancer drug Sapanisertib as coordination passivator of halide vacancies in FP-PSCs,thereby achieving the photoelectric conversion efficiency(PCE)to 18.46%,along with a record certified PCE of 18.27%.In polazin Sapanisertib(Sap),there exists two kinds of nitrogen atoms:in-aromatic ring(in purine and oxazole rings,IAR-Ns)and out-aromatic ring(substituted amino groups,OAR-Ns).Through multiple characterizations,and DFT calculations show that substituted amino groups OAR-Ns hardly get interaction with the halide vacancy due to the distribution of charge density in Sapanisertib.Our work suggests that the selective coordination is of great significance for the design of high-performance passivators for printable mesoscopic perovskite solar cells.展开更多
Aggregation-induced emission(AIE) has drawn great attention worldwide for its unique optical phenomenon and huge potential applications. Since coined by Ben Zhong Tang et al. in 2001, AIE has been deeply investigated ...Aggregation-induced emission(AIE) has drawn great attention worldwide for its unique optical phenomenon and huge potential applications. Since coined by Ben Zhong Tang et al. in 2001, AIE has been deeply investigated and widely utilized in many important areas, such as organic light-emitting diode(OLED), sensor, and bio-imaging. Herein, we highlight some important progress of AIE in these eighteen years, including the exploration of internal mechanism and potential applications. Furthermore,some other interestingly emissive behaviors, originating but distinguishing from the AIE concept, are presented. It is anticipated an overall understanding about AIE could be easily caught from this short review for scientists, no matter whether they are involved in this exciting and rising research area or not.展开更多
Molecularly near-infrared(NIR) theranostics, combining in vivo sensing and tumor-specific therapeutic capability within one molecular system, have received considerable attention in recent years. Compared with the vis...Molecularly near-infrared(NIR) theranostics, combining in vivo sensing and tumor-specific therapeutic capability within one molecular system, have received considerable attention in recent years. Compared with the visible fluorescence imaging, NIR imaging(emission wavelength at 650–900 nm) possesses unique advantages including the minimum photodamage to biological samples, deep penetration, and low interference from auto-fluorescence. In over past decades, there has been an explosive development in the design of molecular imaging contrasts and imaging-guided therapeutics. In this review, we have sumarried the strategies of the NIR theranostics for imaging and tumor-specific chemotherapy applications in living systems. It is noted that the molecularly NIR theranostic design strategy could address current challenges of real-time in vivo sense-and-release for the intelligent biosensing and personalized treatment.展开更多
Glutathione(GSH)plays a critical role in maintaining oxidation-reduction homeostasis in biological systems.Considering the detection of GSH by fluorescence sensors is limited by either the short wavelength emission or...Glutathione(GSH)plays a critical role in maintaining oxidation-reduction homeostasis in biological systems.Considering the detection of GSH by fluorescence sensors is limited by either the short wavelength emission or the poor photostability,a highly stable colorimetric and ratiometric NIR fluorescent sensor(DCM-S)for GSH detection has been constructed on the basis of dicyanomethylene-4H-pyran(DCM)chromophore.The specific disulfide bond is incorporated via a carbamate linker as the GSH responsive group,which simultaneously blue-shifts and quenches the fluorescence.Upon addition of GSH,DCM-S exhibits outstanding colorimetric(from yellow to red)and ratiometric fluorescent response with the 6-fold enhancement of NIR fluorescence at 665 nm in quantum yield.More importantly,the GSH-treated DCM-S(DCM-NH_2 actually)possesses 20-fold longer fluorescence half-life period as well as much better photostability than the FDA-approved ICG.Finally,the ratiometric detection of GSH is also successfully operated in the living cell imaging,exhibiting NIR fluorescence and large Stokes shift(215 nm)with nearly no background fluorescence interference.As a consequence,DCM-S can be utilized as colorimetric and ratiometric NIR fluorescent sensor for GSH,with a great potential in the development of GSH-induced drug delivery system.展开更多
Fluorescence imaging in the near-infrared(NIR)window(750-900 nm)is one of the most popular work modes in biomedical sciences and clinical procedures for visualization of cells and tissues.
A novel versatile dicyanomethylene-4H-pyran (DCM) based derivative bearing ferrocenyl group (DCM-N-Fc) is designed as modulator to construct "off-on" logic operation. The optical properties of DCM-N-Fc are chara...A novel versatile dicyanomethylene-4H-pyran (DCM) based derivative bearing ferrocenyl group (DCM-N-Fc) is designed as modulator to construct "off-on" logic operation. The optical properties of DCM-N-Fc are characterized by absorption and steady-state fluorescence technique, showing that the fluorescence from DCM ehromophore via intramolecular charge transfer (ICT) is strongly quenched by photoinduced electron transfer (PET) process from ferrocene moiety. In contrast with the references (DCM-N and DCM-Fc), the fluorescence of DCM-N-Fc can be triggered by oxidizing ferrocenyl unit either chemically or electrochemically, exhibiting a characteristic emission modulation at around 610 nm with an electrofluorochromic behavior. Furthermore, the free energy and the fluorescence lifetime in the PET path verify the thermodynamic feasibility. Cyclic voltammetry, absorption spectroscopy, time-resolved fluorescence as well as DFT calculation have been used to elaborate the manipulation via both PET and ICT processes.展开更多
Uni-directional multi-state fluorochromic scaffolds are valuable photofunctional molecules and yet scarce. We report a general approach for their design, i.e., mechanodonor-acceptor coupling(MDAC). A photochromic mole...Uni-directional multi-state fluorochromic scaffolds are valuable photofunctional molecules and yet scarce. We report a general approach for their design, i.e., mechanodonor-acceptor coupling(MDAC). A photochromic molecule is a mechanodonor, due to its capability to convert photonic energy into mechanical force. Upon proper coupling, it can be used to drive a mechanochromic molecule for uni-directional multi-state fluorochromism. The embodiment of this approach is a rhodamine-dithienylethylene hydride(RDH), which has been successfully employed in super-resolution localization microscopy.展开更多
Three structural modifications with incorporation of alkyl,alkoxy and vinyl bond into the skeleton of thiophene bridge in D-π-A featured organic sensitizers are specifically developed for insight into their influence...Three structural modifications with incorporation of alkyl,alkoxy and vinyl bond into the skeleton of thiophene bridge in D-π-A featured organic sensitizers are specifically developed for insight into their influences on photophysical,electrochemical as well as photovoltaic properties in nanocrystalline TiO_2-based dye sensitized solar cells(DSSCs).The insertion of vinyl bond into the conjugation bridge leads to the molecular planar configuration,and the conjugation bridge of 3,4-ethylenedioxythiophene(EDOT)is prone to positively shift its highest occupied molecular orbital(HOMO).The electrochemical impedance spectroscopy(EIS)results indicate that the grafted long alkyl chain onto thiophene is favorable to suppress dye aggregation when adsorbed onto TiO_2film and modification on interface of TiO_2/dye/electrolyte,resulting in a relatively high open-circuit voltage(V_(oc)).Under optimized conditions,dye LS-4 bearing hexylthiophene as the conjugation bridge shows a relatively high overall conversion efficiency of5.45%,with a photocurrent of 11.61 mA cm^(-2),V_(oc)of 744 mV.展开更多
Identification of fluorescent biomarkers with peptide ligand-directed receptors for diagnosis or theranostic of pancreatic ductal adenocarcinoma (PDAC) is still challenging. As potential prognostic/predictive bioimagi...Identification of fluorescent biomarkers with peptide ligand-directed receptors for diagnosis or theranostic of pancreatic ductal adenocarcinoma (PDAC) is still challenging. As potential prognostic/predictive bioimaging targets, both aminopeptidase N(APN, known as CD13) and Caveolin-1 are found as upregulation on the cell membrane surface of PDAC, in which APN is the principal receptor of the cyclic peptide cNGR (Asn-Gly-Arg, NGR) and Caveolin-1 can synergistically mediate endocytosis in this receptor-targeted process. Herein, we conjugate cNGR to dicyanomethylene-4H-pyran (DCM) chromophore to develop a synergistic-targeted near-infrared (NIR) fluorescent probe DCM-cNGR with strongly intrinsic NIR fluorescence, stable optical performance, low cytotoxicity, and rapid accumulation in PANC-1 cells with the synergistic overexpressed APN receptor-targeted and Caveolin-1-mediated endocytosis. As demonstrated, DCM-cNGR can realize noninvasive NIR imaging for targeting PANC-1 tumor in vivo after intravenous injection into PANC-1 xenograft tumor of nude mice, making a great promise to improve the precision diagnosis and therapy of pancreatic cancer with real time tracing and bioimaging of PDAC in vitro and in vivo.展开更多
基金supported financially by the National Natural Science Foundation of China(Nos.21421004 and 22075083)the Programme of Introducing Talents of Discipline to Universities(No.B16017).
文摘The mitigation of under-coordinated Pb^(2+)(halide vacancy)defect remains an imperative challenge in the perovskite solar cells,especially printable mesoscopic perovskite solar cells(FP-PsCs).Here we re port a commercial-available polyazin anticancer drug Sapanisertib as coordination passivator of halide vacancies in FP-PSCs,thereby achieving the photoelectric conversion efficiency(PCE)to 18.46%,along with a record certified PCE of 18.27%.In polazin Sapanisertib(Sap),there exists two kinds of nitrogen atoms:in-aromatic ring(in purine and oxazole rings,IAR-Ns)and out-aromatic ring(substituted amino groups,OAR-Ns).Through multiple characterizations,and DFT calculations show that substituted amino groups OAR-Ns hardly get interaction with the halide vacancy due to the distribution of charge density in Sapanisertib.Our work suggests that the selective coordination is of great significance for the design of high-performance passivators for printable mesoscopic perovskite solar cells.
基金supported by the Starting Grants of Tianjin University and Tianjin Government
文摘Aggregation-induced emission(AIE) has drawn great attention worldwide for its unique optical phenomenon and huge potential applications. Since coined by Ben Zhong Tang et al. in 2001, AIE has been deeply investigated and widely utilized in many important areas, such as organic light-emitting diode(OLED), sensor, and bio-imaging. Herein, we highlight some important progress of AIE in these eighteen years, including the exploration of internal mechanism and potential applications. Furthermore,some other interestingly emissive behaviors, originating but distinguishing from the AIE concept, are presented. It is anticipated an overall understanding about AIE could be easily caught from this short review for scientists, no matter whether they are involved in this exciting and rising research area or not.
基金supported by the National Natural Science Foundation of China (Nos.2 788102, 21421004, 21636002, 21622602 and 21908060)National Key Research and Development Program (No. 2017YFC0906902)+2 种基金Shanghai Municipal Science and Technology Major Project (No. 2018SHZDZX03)the Innovation Program of Shanghai Municipal Education Commission, Scientific Committee of Shanghai (No. 15XD1501400)China Postdoctoral Science Foundation (No. 2019M651417)
文摘Molecularly near-infrared(NIR) theranostics, combining in vivo sensing and tumor-specific therapeutic capability within one molecular system, have received considerable attention in recent years. Compared with the visible fluorescence imaging, NIR imaging(emission wavelength at 650–900 nm) possesses unique advantages including the minimum photodamage to biological samples, deep penetration, and low interference from auto-fluorescence. In over past decades, there has been an explosive development in the design of molecular imaging contrasts and imaging-guided therapeutics. In this review, we have sumarried the strategies of the NIR theranostics for imaging and tumor-specific chemotherapy applications in living systems. It is noted that the molecularly NIR theranostic design strategy could address current challenges of real-time in vivo sense-and-release for the intelligent biosensing and personalized treatment.
基金the National Basic Research Program(2013CB733700)the National Natural Science Foundation of China for Creative Research Groups(21421004)+2 种基金Distinguished Young Scholars(21325625)the Oriental Scholarship,the Fundamental Research Funds for the Central Universities(WJ1416005)Science and Technology Commission of Shanghai Municipality(15XD1501400)
文摘Glutathione(GSH)plays a critical role in maintaining oxidation-reduction homeostasis in biological systems.Considering the detection of GSH by fluorescence sensors is limited by either the short wavelength emission or the poor photostability,a highly stable colorimetric and ratiometric NIR fluorescent sensor(DCM-S)for GSH detection has been constructed on the basis of dicyanomethylene-4H-pyran(DCM)chromophore.The specific disulfide bond is incorporated via a carbamate linker as the GSH responsive group,which simultaneously blue-shifts and quenches the fluorescence.Upon addition of GSH,DCM-S exhibits outstanding colorimetric(from yellow to red)and ratiometric fluorescent response with the 6-fold enhancement of NIR fluorescence at 665 nm in quantum yield.More importantly,the GSH-treated DCM-S(DCM-NH_2 actually)possesses 20-fold longer fluorescence half-life period as well as much better photostability than the FDA-approved ICG.Finally,the ratiometric detection of GSH is also successfully operated in the living cell imaging,exhibiting NIR fluorescence and large Stokes shift(215 nm)with nearly no background fluorescence interference.As a consequence,DCM-S can be utilized as colorimetric and ratiometric NIR fluorescent sensor for GSH,with a great potential in the development of GSH-induced drug delivery system.
文摘Fluorescence imaging in the near-infrared(NIR)window(750-900 nm)is one of the most popular work modes in biomedical sciences and clinical procedures for visualization of cells and tissues.
基金supported by the National Key Research and Development Program(2016YFA0200300)the National Natural Science Foundation of China for Distinguished Young Scholars(21325625)and Key Project(21636002)+2 种基金Natural Science Foundation of China(1607044)Oriental Scholarship,Fundamental Research Funds for the Central Universities(WJ1416005,2016 MS108)Science and Technology Commission of Shanghai Municipality(15XD1501400)
文摘A novel versatile dicyanomethylene-4H-pyran (DCM) based derivative bearing ferrocenyl group (DCM-N-Fc) is designed as modulator to construct "off-on" logic operation. The optical properties of DCM-N-Fc are characterized by absorption and steady-state fluorescence technique, showing that the fluorescence from DCM ehromophore via intramolecular charge transfer (ICT) is strongly quenched by photoinduced electron transfer (PET) process from ferrocene moiety. In contrast with the references (DCM-N and DCM-Fc), the fluorescence of DCM-N-Fc can be triggered by oxidizing ferrocenyl unit either chemically or electrochemically, exhibiting a characteristic emission modulation at around 610 nm with an electrofluorochromic behavior. Furthermore, the free energy and the fluorescence lifetime in the PET path verify the thermodynamic feasibility. Cyclic voltammetry, absorption spectroscopy, time-resolved fluorescence as well as DFT calculation have been used to elaborate the manipulation via both PET and ICT processes.
基金the National Natural Science Foundation of China(21822805,21922704,21877069,21908065,22078098)China Postdoctoral Science Foundation(2019M651427,2020T130197)the Commission of Science and Technology of Shanghai Municipality(18430711000)。
文摘Uni-directional multi-state fluorochromic scaffolds are valuable photofunctional molecules and yet scarce. We report a general approach for their design, i.e., mechanodonor-acceptor coupling(MDAC). A photochromic molecule is a mechanodonor, due to its capability to convert photonic energy into mechanical force. Upon proper coupling, it can be used to drive a mechanochromic molecule for uni-directional multi-state fluorochromism. The embodiment of this approach is a rhodamine-dithienylethylene hydride(RDH), which has been successfully employed in super-resolution localization microscopy.
基金supported by the Science Fund for Creative Research Groups(21421004)Distinguished Young Scholars, the National Natural Science Foundation of China(21325625)+4 种基金Oriental Scholarship,Programme of Introducing Talents of Discipline to UniversitiesScience and Technology Commission of Shanghai Municipality (14YF1410500 and 15XD1501400)Shanghai Young Teacher Supporting Foundation(ZZEGD14011)School Funding of Shanghai Second Polytechnic University(EGD14XQD08)"Shu Guang" project(13SG55)
文摘Three structural modifications with incorporation of alkyl,alkoxy and vinyl bond into the skeleton of thiophene bridge in D-π-A featured organic sensitizers are specifically developed for insight into their influences on photophysical,electrochemical as well as photovoltaic properties in nanocrystalline TiO_2-based dye sensitized solar cells(DSSCs).The insertion of vinyl bond into the conjugation bridge leads to the molecular planar configuration,and the conjugation bridge of 3,4-ethylenedioxythiophene(EDOT)is prone to positively shift its highest occupied molecular orbital(HOMO).The electrochemical impedance spectroscopy(EIS)results indicate that the grafted long alkyl chain onto thiophene is favorable to suppress dye aggregation when adsorbed onto TiO_2film and modification on interface of TiO_2/dye/electrolyte,resulting in a relatively high open-circuit voltage(V_(oc)).Under optimized conditions,dye LS-4 bearing hexylthiophene as the conjugation bridge shows a relatively high overall conversion efficiency of5.45%,with a photocurrent of 11.61 mA cm^(-2),V_(oc)of 744 mV.
基金supported by the National Basic Research Program of China (2013CB733700)the National Natural Science Foundation of China for Creative Research Groups (21421004)+6 种基金Key Project (21636002)Distinguished Young Scholars (21325625)NSFC/Chinathe Oriental ScholarshipScience and Technology Commission of Shanghai Municipality (15XD1501400)the Fundamental Research Funds for the Central Universities (222201717003)Program of Introducing Talents of Discipline to Universities (B16017)
文摘Identification of fluorescent biomarkers with peptide ligand-directed receptors for diagnosis or theranostic of pancreatic ductal adenocarcinoma (PDAC) is still challenging. As potential prognostic/predictive bioimaging targets, both aminopeptidase N(APN, known as CD13) and Caveolin-1 are found as upregulation on the cell membrane surface of PDAC, in which APN is the principal receptor of the cyclic peptide cNGR (Asn-Gly-Arg, NGR) and Caveolin-1 can synergistically mediate endocytosis in this receptor-targeted process. Herein, we conjugate cNGR to dicyanomethylene-4H-pyran (DCM) chromophore to develop a synergistic-targeted near-infrared (NIR) fluorescent probe DCM-cNGR with strongly intrinsic NIR fluorescence, stable optical performance, low cytotoxicity, and rapid accumulation in PANC-1 cells with the synergistic overexpressed APN receptor-targeted and Caveolin-1-mediated endocytosis. As demonstrated, DCM-cNGR can realize noninvasive NIR imaging for targeting PANC-1 tumor in vivo after intravenous injection into PANC-1 xenograft tumor of nude mice, making a great promise to improve the precision diagnosis and therapy of pancreatic cancer with real time tracing and bioimaging of PDAC in vitro and in vivo.