The construction of novel inorganic‐organic hybrid nanomaterials for synchronous photocatalyticremoval of heavy metal ions and organic pollutants has received significant attention.We successfullysynthesized gold‐lo...The construction of novel inorganic‐organic hybrid nanomaterials for synchronous photocatalyticremoval of heavy metal ions and organic pollutants has received significant attention.We successfullysynthesized gold‐loaded graphene oxide/PDPB(polymer poly(diphenylbutadiyne))composites(Au‐GO/PDPB)through a facile mechanical agitation and photoreduction method.The compositeswere characterized by XPS and TEM images,which confirmed the presence of GO and Au nanoparticleson the PDPB.The as‐prepared Au‐GO/PDPB composites displayed enhanced photocatalytic activity compared with that of pure PDPB for the synchronous photoreduction of hexavalent chromium(Cr(VI))and photo‐oxidation of phenol.We also determined the optimal loading mass of GO and Au nanoparticles on the PDPB;the Au1‐GO2/PDPB(2.0wt%GO and1.0wt%Au)composite displayed the best photocatalytic activity among all the catalysts.Our study provides a facile way to prepare inorganic‐organic composites for the synchronous photocatalytic removal of heavy metal ions and organic pollutants.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
The existence and risk of emerging organic contaminants(EOCs)have been under consideration and paid much effort to degrade these pollutants.Fenton system is one of the most widely used technologies to solve this probl...The existence and risk of emerging organic contaminants(EOCs)have been under consideration and paid much effort to degrade these pollutants.Fenton system is one of the most widely used technologies to solve this problem.The original Fenton system relies on the hydroxyl radicals produced by Fe(Ⅱ)/H_(2)O_(2) to oxidize the organic contaminants.However,the application of the Fenton system is limited by its low iron cycling efficiency and the high risks of hydrogen peroxide transportation and storage.The introduction of external energy(including light and electricity etc.)can effectively promote the Fe(Ⅲ)/Fe(Ⅱ)cycle and the reduction of oxygen to produce hydrogen peroxide in situ.This review introduces three in-situ Fenton systems,which are electro-Fenton,Photo-Fenton,and chemical reaction.The mechanism,influencing factors,and catalysts of these three in-situ Fenton systems in degrading EOCs are discussed systematically.This review strengthens the understanding of Fenton and in-situ Fenton systems in degradation,offering further insight into the real application of the in-situ Fenton system in the removal of EOCs.展开更多
Saccharide sensing is a very meaningful research topic as saccharides are involved in many biological activities.However,it is challenging to design molecular sensors for saccharides because this family of compounds i...Saccharide sensing is a very meaningful research topic as saccharides are involved in many biological activities.However,it is challenging to design molecular sensors for saccharides because this family of compounds is hydromimetic in aqueous solutions and shares a similar chemical structure.In this review,research progress in the development of porphyrin-based saccharide sensors is described with representative examples.We focus on using porphyrin as the signal reporter because porphyrins exhibit unique advantages in high chemical stability,long emission wavelength,and multiple structural modification strategies.Reported literature results have been classified into mainly two sections according to the general working principles of the porphyrin sensor molecules.In the first section,recognition unit,design strategy and sensing performance of traditional porphyrin-based selective saccharide sensors are discussed.While in the second section,development of porphyrin-based sensor arrays for pattern recognition of saccharides has been summarized.Looking through the design strategy and sensing performance of reported achievements,it is reasonable to anticipate a bright future for designing practical porphyrin-based saccharide sensors.展开更多
Novel perylene bisimide dyes bay-functionalized with naphthalimide chromophores have been prepared conveniently by coupling of 1,8-naphthalimide and dibromoperylene bisimides. Their optical properties were investigate...Novel perylene bisimide dyes bay-functionalized with naphthalimide chromophores have been prepared conveniently by coupling of 1,8-naphthalimide and dibromoperylene bisimides. Their optical properties were investigated by UV-vis and fluorescence spectroscopy. The absorption spectra of these compounds showed wide spectral responses from 300 to 700 nm, which would be potentials for application as organic solar cells.展开更多
Cosensitization based on two or multiple dyes as "dye cocktails" can hit the target on compensating and broadening light-harvesting region.Two indoline D-A-π-A motif sensitizers(WS-2 and WS-39) that possess...Cosensitization based on two or multiple dyes as "dye cocktails" can hit the target on compensating and broadening light-harvesting region.Two indoline D-A-π-A motif sensitizers(WS-2 and WS-39) that possess similar light response area but distinctly reversed feature in photovoltaic performance are selected as the specific cosensitization couple. That is, WS-2 shows quite high photocurrent but low photovoltage, and WS-39 gives relatively low photocurrent but quite high photo voltage. Due to the obvious "barrel effect",both dyes show medium PCE around8.50%. In contrast with the previous cosensitization strategy mostly focused on the compensation of light response region, herein we perform different cosensitization sequence, for taking insight into the balance of photocurrent and photo voltage, and achieving the synergistic improvement in power conversion efficiency(PCE). Electronic impedance spectra(EIS) indicate that exploiting dye WS-39 with high V_(OC) value as the primary sensitizer can repress the charge recombination more effectively, resulting in superior V_(OC) rather than using dye WS-2 with high J_(SC)as the primary sensitizer. As a consequence, a high PCE value of 9.48% is obtained with the delicate cosensitization using WS-39 as primary dye and WS-2 as accessory dye, which is higher than the corresponding devices sensitized by each individual dye(around 8.48-8.67%). It provides an effective optimizing strategy of cosensitization how to combine the individual dye advantages for developing highly efficient solar cells.展开更多
A distinctive method is proposed by simply utilizing ultrasonic technique in Ti02 electrode fabrication in order to improve the optoelectronic performance of dye-sensitized solar cells （DSSCs）. Dye molecules are at ...A distinctive method is proposed by simply utilizing ultrasonic technique in Ti02 electrode fabrication in order to improve the optoelectronic performance of dye-sensitized solar cells （DSSCs）. Dye molecules are at random and single molecular state in the ultrasonic field and the ultrasonic wave favors the diffusion and adsorption processes of dye molecules. As a result, the introduction of ultrasonic technique at room temperature leads to faster and more well-distributed dye adsorption on TiO2 as well as higher cell efficiency than regular deposition, thus the fabrication time is markedly reduced. It is found that the device based on 40 kHz ultrasonic （within 1 h） with N719 exhibits a Voc of 789 mV, Jsc of 14.94 mA]cm2 and fill factor （FF） of 69.3, yielding power conversion efficiency （PCE） of 8.16%, which is higher than device regularly dyed for 12 h （PCE = 8.06%）. In addition, the DSSC devices obtain the best efficiency （PCE = 8.68%） when the ultrasonic deposition time increases to 2.5 h. The DSSCs fabricated via ultrasonic technique presents more dye loading, larger photocurrent, less charge recombination and higher photovoltage. The charge extraction and electron impedance spectroscopy （EIS） were performed to understand the influence of ultrasonic technique on the electron recombination and performance of DSSCs.展开更多
Urinary microalbumin(mALB)serves as an exceptionally sensitive indicator for the early detection of kidney damage,playing a pivotal role in identifying chronic renal failure and kidney lesions in individuals.Neverthel...Urinary microalbumin(mALB)serves as an exceptionally sensitive indicator for the early detection of kidney damage,playing a pivotal role in identifying chronic renal failure and kidney lesions in individuals.Nevertheless,the currentfluores-cent methodologies for point-of-care(POC)diagnosis of mALB in real urine still exhibit suboptimal performance.Herein,the development and synthesis of QM-N2,an albumin-activated near-infrared(NIR)aggregation-induced emission(AIE)fluorescent probe,are presented.The strategic incorporation and positioning of quaternary ammonium salts within the quinoline-malononitrile(QM)scaffold sig-nificantly influence solubility and luminescence characteristics.Specifically,the quaternary ammonium salt-free variant,QM-OH,and the quaternary ammonium salt integrated at the donor function group(DFG)site,QM-N1,display limited solubility in aqueous solutions while demonstrating a distinctfluorescence signal.Conversely,the incorporation of quaternary ammonium salt at the conformational functional group(CFG)site in QM-N2 imparts superior dispersibility in water and reduces the initialfluorescence.Furthermore,the integration of a well-defined D-π-A struc-ture within QM-N2 enables itself with near-infrared emission,which is crucial for mitigating interference from autofluorescence present in urine samples.Upon inter-action with albumin,QM-N2 forms a tight bond with the IIA site of the subdomain of human serum albumin(HSA),inducing alterations in protein configuration and constraining the intrinsic motion offluorescent molecules.This interaction inducesfluorescence,facilitating the sensitive detection of trace albumin.Ultimately,QM-N2 is applied for POC testing of mALB using portable equipment,particularly in the diagnosis of mALB-related diseases,notably chronic renal failure.This positioning underscores its potential as an ideal candidate for self-health measurement at home or in community hospitals.展开更多
In the past decades,porphyrins,phthalocyanines and related materials have attracted significant attention due to their diverse and brilliant structures[1,2],as well as their unique electronic structures and photophysi...In the past decades,porphyrins,phthalocyanines and related materials have attracted significant attention due to their diverse and brilliant structures[1,2],as well as their unique electronic structures and photophysical properties which could be applicable in a wide range of areas[3–5].展开更多
In situ studies of catalysts play valuable roles in observing phase transformation, understanding the corresponding surface chemistry and the mechanism of the reaction. In this paper, ceria promoted cobalt oxide was p...In situ studies of catalysts play valuable roles in observing phase transformation, understanding the corresponding surface chemistry and the mechanism of the reaction. In this paper, ceria promoted cobalt oxide was prepared by the calcination method and investigated for the CO oxidation. The microstructure and morphology of CeO2-Co3O4 were investigated by the Scanning Electron Microscope, High-resolution transmission electron microscopy, Raman and X-ray photoelectron spectroscopy characterization. The effect of CeO2 doping on Co3O4 for CO oxidation was characterized by in situ X-ray Diffraction (in situ XRD) and in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS). In situ XRD was carried out under H2 atmosphere to evaluate the redox property of catalysts. The results indicated that the ceria doping can enhance the reducibility of Co2+ and promote the Co3+-Co2+-Co3+ cycle, owing to the oxygen replenish property of CeO2. Furthermore, adsorbed carbonate species on the surface of CeO2-Co3O4 were investigated by in situ-DRIFTS experiment. It was turned out that carbonate species on ceria promoted cobalt oxide catalysts showed different IR peaks compared with pure cobalt oxide. The carbonate species on ceria promoted catalyst are more active, and similar to free state carbonate species with weak bonding to catalyst surface, which can effectively inhibit catalyst inactivation. This study revealed the mechanism of ceria promoting CO oxidation over cobalt oxide, which will provide theoretical support for the design of efficient CO oxidation catalysts.展开更多
A novel complex ZnTPPL1·3DMF 1（TPP = tetraphenylporphyrin,L1 = N-（4-（9-carbazolyl） phenyl）-N,N-di（4-pyridyl）amine） was prepared by a hydrothermal method and characterized by elemental analysis,IR,and sing...A novel complex ZnTPPL1·3DMF 1（TPP = tetraphenylporphyrin,L1 = N-（4-（9-carbazolyl） phenyl）-N,N-di（4-pyridyl）amine） was prepared by a hydrothermal method and characterized by elemental analysis,IR,and single-crystal X-ray diffraction analysis.Compound 1 crystallizes in triclinic,space group P1 with a = 13.3082（2）,b = 14.3276（2）,c = 18.6120（3） ,α = 109.853（1）,β = 95.054（1）,γ = 98.832（1）°,V = 3260.57（9） 3,Z = 2,Dc = 1.334 g/cm3,C81H69N11O3Zn,Mr = 1309.84,μ（MoKα） = 0.438 mm-1,F（000） = 1372,GOF = 1.159,the final R = 0.0482 and wR = 0.1479 for 12091 observed reflections（Ⅰ 〉 2σ（Ⅰ））.Crystal structure analyses revealed that L1 utilizes one pyridyl N atom to bind Zn via axial coordination,affording a 1：1 complex.The binding constant was estimated to be 1.74（7） × 10^4 M^-1 from electronic spectra measurements.展开更多
Bulk heterojunction(BHJ) solar cells based on small molecules have attracted potential attention due to their promise of conveniently defined structures, high absorption coefficients, solution process-ability and easy...Bulk heterojunction(BHJ) solar cells based on small molecules have attracted potential attention due to their promise of conveniently defined structures, high absorption coefficients, solution process-ability and easy fabrication. Three D—A—D—A type organic semiconductors(WS-31,WS-32 and WS-52) are synthesized, based on the indoline donor and benzotriazole auxiliary acceptor core, along with either bare thiophene or rigid cyclopentadithiophene as π bridge, rhodanine or carbonocyanidate as end-group. Their HOMO orbitals are delocalized throughout the whole molecules. Whereas the LUMOs are mainly localized on the acceptor part of structure, which reach up to benzothiadiazole, but no distribution on indoline donor. The first excitations for WS-31 and WS-32 are mainly originated by electron transition from HOMO to LUMO level, while for WS-52, partly related to transition between HOMO and LUMO+1 level. The small organic molecules are applied as donor components in bulk heterojunction(BHJ) organic solar cells, using PC_(61)BM as acceptor material to check their photovoltaic performances. The BHJ solar cells based on blended layer of WS-31:PC_(61)BM and WS-32:PC_(61)BM processed with chloroform show overall photoelectric conversion efficiency(PCE) of 0.56% and 1.02%, respectively. WS-32 based BHJ solar cells show a higher current density originated by its relatively larger driving force of photo-induced carrier in photo-active layer to LUMO of PC_(61)BM.展开更多
Graphene is a two-dimensional nanomaterial with huge surface area,high carrier mobility and high mechanical strength.Because of its great potential in nanotechnology and environmental protection,it has attracted much ...Graphene is a two-dimensional nanomaterial with huge surface area,high carrier mobility and high mechanical strength.Because of its great potential in nanotechnology and environmental protection,it has attracted much attention in environmental and energy fields since its discovery in 2004.Although graphene is a star material,many reviews have introduced its use in terms of energy,the research progress in the field of environment,especially water pollution control,has been rarely reported.Here,we review exhaustively the research progress of graphene-based materials in environmental pollution remediation in the past ten years.Firstly,the advantages and classification of graphene were introduced.Secondly,the research progress and main achievements of graphene and its composites in the fields of photocatalytic degradation,pollutant adsorption and water treatment were emphatically described,and the mechanism of action in the above fields was summarized.Finally,we discuss the problems existing in the preparation and summarize the application of graphene in the environment.展开更多
Analyses of the physiology and pathology of active biochemical species in their native contexts are critical for early diagnosis and therapy. Optical imaging has emerged as one of the promising modalities for noninvas...Analyses of the physiology and pathology of active biochemical species in their native contexts are critical for early diagnosis and therapy. Optical imaging has emerged as one of the promising modalities for noninvasive and real-time visualization of important biomolecules or biological events, and it has witnessed major advances in the field of imaging in vitro and in vivo. In this review, we present a survey of common approaches and tactics for enhanced targetability, response rate, and photostability in bioimaging applications. Recently developed and representative examples are illustrated on the cellular and tissue levels.展开更多
In recent years,fluorescent probes have gained significant prominence in the field of substance analysis and detection[1–4].The development of high-performance volatile amine gas sensors is crucial for applications i...In recent years,fluorescent probes have gained significant prominence in the field of substance analysis and detection[1–4].The development of high-performance volatile amine gas sensors is crucial for applications in food quality control,disease monitoring,and environmental protection[2].展开更多
BODIPY-based fluorescent chemosensors bearing sulfoxide function were designed and evaluated. Thiols triggered sulfoxide→sulfide transduction in these probes leads to an obvious red-shift in absorption and dramatic f...BODIPY-based fluorescent chemosensors bearing sulfoxide function were designed and evaluated. Thiols triggered sulfoxide→sulfide transduction in these probes leads to an obvious red-shift in absorption and dramatic fluorescence enhancement with distinctly ratiometric features, enabling the accurate assay ofthiols in living cells.展开更多
Infinite coordination polymers are recognized as excellent platform for functionalization.Dithienylethene motifs,which are one of the most attractive functional moieties,were incorporated into an infinite coordination...Infinite coordination polymers are recognized as excellent platform for functionalization.Dithienylethene motifs,which are one of the most attractive functional moieties,were incorporated into an infinite coordination polymer,to deliver a‘‘smart’’porous material that can response to external stimuli.The obtained dithienylethene-based infinite coordination polymers（named Cu-DTEDBA）share the advantages of both infinite coordination polymers（porosity and stability）and dithienylethene motifs（photochromism）.The physical and chemical properties of Cu-DTEDBA were characterized by FTIR,TEM,SEM,XRD,TGA,UV–vis,EDX and BET.Moreover,the combination of dithienylethene and infinite coordination polymers gives rise to a synergistic effect,which induces functional behaviors of ammonia sensor applications.Both open and closed forms of Cu-DTEDBA exhibit distinct colorimetric change upon exposure to gaseous ammonia,which is not observed in dithienylethene free molecules.展开更多
Cysteine is well-known to be an important biothiol and related to many diseases. However, the in vivo detection of endogenous cysteine still suffers from lacking small-molecule fluorophores with both excitation and em...Cysteine is well-known to be an important biothiol and related to many diseases. However, the in vivo detection of endogenous cysteine still suffers from lacking small-molecule fluorophores with both excitation and emission in the near-infrared(650-900 nm)/shortwave-infrared region. Herein, we report a molecular engineering strategy for shortwave infrared(SWIR, 900-1700 nm) sensing of cysteine, which integrated an excited-state intermolecular proton transfer(ESIPT) building block into the intramolecular charge transfer(ICT) scaffold. The obtained novel fluorophore SH-OH displays a maximum absorption at the NIR region, and emission at the SWIR region. We introduce the cysteine-recognition moiety to SH-OH structure, and demonstrate sensing of endogenous cysteine in living animals, using the SWIR emission as a reliable off-on fluorescence signal. This fluorophore design strategy of cooperation of ICT and ESIPT processes expands the in vivo sensing toolbox for accurate analysis in clinical applications.展开更多
In the presence of In/CuCl, ethyl 4-bromo-4,4-difluoro-3-oxo-2-（triphenylphosphoranylidene）butanoate reacted with various aldehydes in aqueous medium at room temperature to give the a,a-difluorinated β-hydroxy carb...In the presence of In/CuCl, ethyl 4-bromo-4,4-difluoro-3-oxo-2-（triphenylphosphoranylidene）butanoate reacted with various aldehydes in aqueous medium at room temperature to give the a,a-difluorinated β-hydroxy carbonyl compounds. Furthermore, treating Reformatsky addition compounds with 1 equiv, of sodium hydroxide in the mixture of tetrahydrofuran and water afforded gem-difluoromethylenated 2-triphenylphosphoranylidene δ-lactones in excellent yields.展开更多
Dye-sensitized solar cells （DSSCs） cannot be developed without the research on sensitizers. As the key of light harvesting and electron generation, thousands of sensitizers have been designed for the application in ...Dye-sensitized solar cells （DSSCs） cannot be developed without the research on sensitizers. As the key of light harvesting and electron generation, thousands of sensitizers have been designed for the application in DSSC devices. Among them, organic sensitizers have drawn a lot of attention because of the flexible molecular design, easy synthesis and good photovoltaic performance. Recently, new record photovoltaic conversion efficiencies of 11.5% for DSSCs with iodide electrolyte and 14.3% for DSSCs with cobalt electrolyte and co-sensitization have been achieved with organic sensitizers. Here we focus on the donor design and modification of organic sensitizers. Several useful strategies and corresponding typical examples are presented.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 by the National Natural Science Foundation of China(21577036,21377038,21237003,21677048)the National Basic Research Program of China(973 Program,2013CB632403)+1 种基金State Key Research Development Program of China(2016YFA0204200)the Fundamental Research Funds for the Central Universities(22A201514021)~~
文摘The construction of novel inorganic‐organic hybrid nanomaterials for synchronous photocatalyticremoval of heavy metal ions and organic pollutants has received significant attention.We successfullysynthesized gold‐loaded graphene oxide/PDPB(polymer poly(diphenylbutadiyne))composites(Au‐GO/PDPB)through a facile mechanical agitation and photoreduction method.The compositeswere characterized by XPS and TEM images,which confirmed the presence of GO and Au nanoparticleson the PDPB.The as‐prepared Au‐GO/PDPB composites displayed enhanced photocatalytic activity compared with that of pure PDPB for the synchronous photoreduction of hexavalent chromium(Cr(VI))and photo‐oxidation of phenol.We also determined the optimal loading mass of GO and Au nanoparticles on the PDPB;the Au1‐GO2/PDPB(2.0wt%GO and1.0wt%Au)composite displayed the best photocatalytic activity among all the catalysts.Our study provides a facile way to prepare inorganic‐organic composites for the synchronous photocatalytic removal of heavy metal ions and organic pollutants.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
基金supported by the National Natural Science Foundation of China(No.21906056No.22176060)+2 种基金the Undergraduate Training Program on Innovation and Entrepreneurship(S202110251087)the Science and Technology Commission of Shanghai Municipality(22ZR1418600)Shanghai Municipal Science and Technology(No.20DZ2250400).
文摘The existence and risk of emerging organic contaminants(EOCs)have been under consideration and paid much effort to degrade these pollutants.Fenton system is one of the most widely used technologies to solve this problem.The original Fenton system relies on the hydroxyl radicals produced by Fe(Ⅱ)/H_(2)O_(2) to oxidize the organic contaminants.However,the application of the Fenton system is limited by its low iron cycling efficiency and the high risks of hydrogen peroxide transportation and storage.The introduction of external energy(including light and electricity etc.)can effectively promote the Fe(Ⅲ)/Fe(Ⅱ)cycle and the reduction of oxygen to produce hydrogen peroxide in situ.This review introduces three in-situ Fenton systems,which are electro-Fenton,Photo-Fenton,and chemical reaction.The mechanism,influencing factors,and catalysts of these three in-situ Fenton systems in degrading EOCs are discussed systematically.This review strengthens the understanding of Fenton and in-situ Fenton systems in degradation,offering further insight into the real application of the in-situ Fenton system in the removal of EOCs.
基金financially supported by the National Natural Science Foundation of China(Nos.22278229,22131005 and 21904066)333 High Level Talent Project of Jiangsu Province.
文摘Saccharide sensing is a very meaningful research topic as saccharides are involved in many biological activities.However,it is challenging to design molecular sensors for saccharides because this family of compounds is hydromimetic in aqueous solutions and shares a similar chemical structure.In this review,research progress in the development of porphyrin-based saccharide sensors is described with representative examples.We focus on using porphyrin as the signal reporter because porphyrins exhibit unique advantages in high chemical stability,long emission wavelength,and multiple structural modification strategies.Reported literature results have been classified into mainly two sections according to the general working principles of the porphyrin sensor molecules.In the first section,recognition unit,design strategy and sensing performance of traditional porphyrin-based selective saccharide sensors are discussed.While in the second section,development of porphyrin-based sensor arrays for pattern recognition of saccharides has been summarized.Looking through the design strategy and sensing performance of reported achievements,it is reasonable to anticipate a bright future for designing practical porphyrin-based saccharide sensors.
基金This work was supported by National Natural Science Foundation of China and Shanghai Science Committee.
文摘Novel perylene bisimide dyes bay-functionalized with naphthalimide chromophores have been prepared conveniently by coupling of 1,8-naphthalimide and dibromoperylene bisimides. Their optical properties were investigated by UV-vis and fluorescence spectroscopy. The absorption spectra of these compounds showed wide spectral responses from 300 to 700 nm, which would be potentials for application as organic solar cells.
基金supported by NSFC for Creative Research Groups(21421004) and Distinguished Young Scholars(21325625),NSFC/ChinaOriental Scholarship+4 种基金Fundamental Research Funds for the Central Universities(WJ1416005 and WJ1315025)Scientific Committee of Shanghai(14ZR1409700and 15XD1501400)Programme of Introducing Talents of Discipline to Universities(B16017)Science Foundation for the Excellent Youth Scholars of Hebei Education Department(Y2012017)Science Foundation for Oversea Scholars of Hebei(C201400324)
文摘Cosensitization based on two or multiple dyes as "dye cocktails" can hit the target on compensating and broadening light-harvesting region.Two indoline D-A-π-A motif sensitizers(WS-2 and WS-39) that possess similar light response area but distinctly reversed feature in photovoltaic performance are selected as the specific cosensitization couple. That is, WS-2 shows quite high photocurrent but low photovoltage, and WS-39 gives relatively low photocurrent but quite high photo voltage. Due to the obvious "barrel effect",both dyes show medium PCE around8.50%. In contrast with the previous cosensitization strategy mostly focused on the compensation of light response region, herein we perform different cosensitization sequence, for taking insight into the balance of photocurrent and photo voltage, and achieving the synergistic improvement in power conversion efficiency(PCE). Electronic impedance spectra(EIS) indicate that exploiting dye WS-39 with high V_(OC) value as the primary sensitizer can repress the charge recombination more effectively, resulting in superior V_(OC) rather than using dye WS-2 with high J_(SC)as the primary sensitizer. As a consequence, a high PCE value of 9.48% is obtained with the delicate cosensitization using WS-39 as primary dye and WS-2 as accessory dye, which is higher than the corresponding devices sensitized by each individual dye(around 8.48-8.67%). It provides an effective optimizing strategy of cosensitization how to combine the individual dye advantages for developing highly efficient solar cells.
基金supported by the Science Fund for Creative Research Groups(21421004)the National Basic Research 973 Program(2013CB733700)NSFC/China(21172073,21372082,21572062 and 91233207)
文摘A distinctive method is proposed by simply utilizing ultrasonic technique in Ti02 electrode fabrication in order to improve the optoelectronic performance of dye-sensitized solar cells （DSSCs）. Dye molecules are at random and single molecular state in the ultrasonic field and the ultrasonic wave favors the diffusion and adsorption processes of dye molecules. As a result, the introduction of ultrasonic technique at room temperature leads to faster and more well-distributed dye adsorption on TiO2 as well as higher cell efficiency than regular deposition, thus the fabrication time is markedly reduced. It is found that the device based on 40 kHz ultrasonic （within 1 h） with N719 exhibits a Voc of 789 mV, Jsc of 14.94 mA]cm2 and fill factor （FF） of 69.3, yielding power conversion efficiency （PCE） of 8.16%, which is higher than device regularly dyed for 12 h （PCE = 8.06%）. In addition, the DSSC devices obtain the best efficiency （PCE = 8.68%） when the ultrasonic deposition time increases to 2.5 h. The DSSCs fabricated via ultrasonic technique presents more dye loading, larger photocurrent, less charge recombination and higher photovoltage. The charge extraction and electron impedance spectroscopy （EIS） were performed to understand the influence of ultrasonic technique on the electron recombination and performance of DSSCs.
基金National Key Research and Development Program of China,Grant/Award Number:2021YFA0910000NSFC,Grant/Award Numbers:22222803,91959202,21974047+1 种基金China Postdoctoral Science Foundation,Grant/Award Number:2022M72142Shanghai Municipal Science and Technology Major Project,Grant/Award Number:2018SHZDZX03。
文摘Urinary microalbumin(mALB)serves as an exceptionally sensitive indicator for the early detection of kidney damage,playing a pivotal role in identifying chronic renal failure and kidney lesions in individuals.Nevertheless,the currentfluores-cent methodologies for point-of-care(POC)diagnosis of mALB in real urine still exhibit suboptimal performance.Herein,the development and synthesis of QM-N2,an albumin-activated near-infrared(NIR)aggregation-induced emission(AIE)fluorescent probe,are presented.The strategic incorporation and positioning of quaternary ammonium salts within the quinoline-malononitrile(QM)scaffold sig-nificantly influence solubility and luminescence characteristics.Specifically,the quaternary ammonium salt-free variant,QM-OH,and the quaternary ammonium salt integrated at the donor function group(DFG)site,QM-N1,display limited solubility in aqueous solutions while demonstrating a distinctfluorescence signal.Conversely,the incorporation of quaternary ammonium salt at the conformational functional group(CFG)site in QM-N2 imparts superior dispersibility in water and reduces the initialfluorescence.Furthermore,the integration of a well-defined D-π-A struc-ture within QM-N2 enables itself with near-infrared emission,which is crucial for mitigating interference from autofluorescence present in urine samples.Upon inter-action with albumin,QM-N2 forms a tight bond with the IIA site of the subdomain of human serum albumin(HSA),inducing alterations in protein configuration and constraining the intrinsic motion offluorescent molecules.This interaction inducesfluorescence,facilitating the sensitive detection of trace albumin.Ultimately,QM-N2 is applied for POC testing of mALB using portable equipment,particularly in the diagnosis of mALB-related diseases,notably chronic renal failure.This positioning underscores its potential as an ideal candidate for self-health measurement at home or in community hospitals.
文摘In the past decades,porphyrins,phthalocyanines and related materials have attracted significant attention due to their diverse and brilliant structures[1,2],as well as their unique electronic structures and photophysical properties which could be applicable in a wide range of areas[3–5].
基金supported by the State Key Research Development Program of China(2016YFA0204200)the National Natural Science Foundation of China(21822603,21577036,21773062)+3 种基金the Shanghai Pujiang Program(17PJD011)the Zhejiang public welfare technology research plan/rural agriculture(LGN18B010001)the Zhejiang provincial Collaborative Innovation Center of Agricultural Biological Resources Biochemical Manufacturing(NO:2016KF0005)the scientific research project of Zhejiang provincial education department(Y201839892)~~
文摘In situ studies of catalysts play valuable roles in observing phase transformation, understanding the corresponding surface chemistry and the mechanism of the reaction. In this paper, ceria promoted cobalt oxide was prepared by the calcination method and investigated for the CO oxidation. The microstructure and morphology of CeO2-Co3O4 were investigated by the Scanning Electron Microscope, High-resolution transmission electron microscopy, Raman and X-ray photoelectron spectroscopy characterization. The effect of CeO2 doping on Co3O4 for CO oxidation was characterized by in situ X-ray Diffraction (in situ XRD) and in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS). In situ XRD was carried out under H2 atmosphere to evaluate the redox property of catalysts. The results indicated that the ceria doping can enhance the reducibility of Co2+ and promote the Co3+-Co2+-Co3+ cycle, owing to the oxygen replenish property of CeO2. Furthermore, adsorbed carbonate species on the surface of CeO2-Co3O4 were investigated by in situ-DRIFTS experiment. It was turned out that carbonate species on ceria promoted cobalt oxide catalysts showed different IR peaks compared with pure cobalt oxide. The carbonate species on ceria promoted catalyst are more active, and similar to free state carbonate species with weak bonding to catalyst surface, which can effectively inhibit catalyst inactivation. This study revealed the mechanism of ceria promoting CO oxidation over cobalt oxide, which will provide theoretical support for the design of efficient CO oxidation catalysts.
基金Supported by the Shanghai Pujiang Program (08PJ14037),NNSFC,SRF for ROCS,and SEM
文摘A novel complex ZnTPPL1·3DMF 1（TPP = tetraphenylporphyrin,L1 = N-（4-（9-carbazolyl） phenyl）-N,N-di（4-pyridyl）amine） was prepared by a hydrothermal method and characterized by elemental analysis,IR,and single-crystal X-ray diffraction analysis.Compound 1 crystallizes in triclinic,space group P1 with a = 13.3082（2）,b = 14.3276（2）,c = 18.6120（3） ,α = 109.853（1）,β = 95.054（1）,γ = 98.832（1）°,V = 3260.57（9） 3,Z = 2,Dc = 1.334 g/cm3,C81H69N11O3Zn,Mr = 1309.84,μ（MoKα） = 0.438 mm-1,F（000） = 1372,GOF = 1.159,the final R = 0.0482 and wR = 0.1479 for 12091 observed reflections（Ⅰ 〉 2σ（Ⅰ））.Crystal structure analyses revealed that L1 utilizes one pyridyl N atom to bind Zn via axial coordination,affording a 1：1 complex.The binding constant was estimated to be 1.74（7） × 10^4 M^-1 from electronic spectra measurements.
基金supported by the NSFC for Creative Research Groups(21421004)Distinguished Young Scholars(21325625)+4 种基金NSFC/China,Science and Technology Commission of Shanghai Municipality(14YF1410500 and 15XD1501400)Shanghai Young Teacher Supporting Foundation(ZZEGD14011)Program for Professor of Special Appointment(Eastern Scholar)"Shu Guang" project supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation(13SG55)Grants of computing timeat the C3SE supercomputing Center at Chalmers(Gteborg)
文摘Bulk heterojunction(BHJ) solar cells based on small molecules have attracted potential attention due to their promise of conveniently defined structures, high absorption coefficients, solution process-ability and easy fabrication. Three D—A—D—A type organic semiconductors(WS-31,WS-32 and WS-52) are synthesized, based on the indoline donor and benzotriazole auxiliary acceptor core, along with either bare thiophene or rigid cyclopentadithiophene as π bridge, rhodanine or carbonocyanidate as end-group. Their HOMO orbitals are delocalized throughout the whole molecules. Whereas the LUMOs are mainly localized on the acceptor part of structure, which reach up to benzothiadiazole, but no distribution on indoline donor. The first excitations for WS-31 and WS-32 are mainly originated by electron transition from HOMO to LUMO level, while for WS-52, partly related to transition between HOMO and LUMO+1 level. The small organic molecules are applied as donor components in bulk heterojunction(BHJ) organic solar cells, using PC_(61)BM as acceptor material to check their photovoltaic performances. The BHJ solar cells based on blended layer of WS-31:PC_(61)BM and WS-32:PC_(61)BM processed with chloroform show overall photoelectric conversion efficiency(PCE) of 0.56% and 1.02%, respectively. WS-32 based BHJ solar cells show a higher current density originated by its relatively larger driving force of photo-induced carrier in photo-active layer to LUMO of PC_(61)BM.
基金supported by the State Key Research Development Program of China(No.2016YFA0204200)National Natural Science Foundation of China(Nos.21822603,21811540394,5171101651,21677048,21773062,21577036)+1 种基金Shanghai Pujiang Program(No.17PJD011)the Fundamental Research Funds for the Central Universities(No.22A201514021)。
文摘Graphene is a two-dimensional nanomaterial with huge surface area,high carrier mobility and high mechanical strength.Because of its great potential in nanotechnology and environmental protection,it has attracted much attention in environmental and energy fields since its discovery in 2004.Although graphene is a star material,many reviews have introduced its use in terms of energy,the research progress in the field of environment,especially water pollution control,has been rarely reported.Here,we review exhaustively the research progress of graphene-based materials in environmental pollution remediation in the past ten years.Firstly,the advantages and classification of graphene were introduced.Secondly,the research progress and main achievements of graphene and its composites in the fields of photocatalytic degradation,pollutant adsorption and water treatment were emphatically described,and the mechanism of action in the above fields was summarized.Finally,we discuss the problems existing in the preparation and summarize the application of graphene in the environment.
基金supported by National Natural Science Foundation of China for Science Center Program (21788102)National Key Research and Development Program (2016YFA0200300)+1 种基金Natural Science Foundation of China (21636002)National Postdoctoral Program for Innovative Talents (BX201700075)
文摘Analyses of the physiology and pathology of active biochemical species in their native contexts are critical for early diagnosis and therapy. Optical imaging has emerged as one of the promising modalities for noninvasive and real-time visualization of important biomolecules or biological events, and it has witnessed major advances in the field of imaging in vitro and in vivo. In this review, we present a survey of common approaches and tactics for enhanced targetability, response rate, and photostability in bioimaging applications. Recently developed and representative examples are illustrated on the cellular and tissue levels.
文摘In recent years,fluorescent probes have gained significant prominence in the field of substance analysis and detection[1–4].The development of high-performance volatile amine gas sensors is crucial for applications in food quality control,disease monitoring,and environmental protection[2].
基金We gratefully acknowledge the financial support by the National Natural Science Foundation of China （Nos. 21172071, 21190033 and 21372083）.
文摘BODIPY-based fluorescent chemosensors bearing sulfoxide function were designed and evaluated. Thiols triggered sulfoxide→sulfide transduction in these probes leads to an obvious red-shift in absorption and dramatic fluorescence enhancement with distinctly ratiometric features, enabling the accurate assay ofthiols in living cells.
基金supported by National Basic Research Program of China (No. 2013CB733501)National Natural Science Foundation of China (Nos. 91334203, 21376074, 21402050)Fundamental Research Funds for the Central Universities of China (No. WK1314008)
文摘Infinite coordination polymers are recognized as excellent platform for functionalization.Dithienylethene motifs,which are one of the most attractive functional moieties,were incorporated into an infinite coordination polymer,to deliver a‘‘smart’’porous material that can response to external stimuli.The obtained dithienylethene-based infinite coordination polymers（named Cu-DTEDBA）share the advantages of both infinite coordination polymers（porosity and stability）and dithienylethene motifs（photochromism）.The physical and chemical properties of Cu-DTEDBA were characterized by FTIR,TEM,SEM,XRD,TGA,UV–vis,EDX and BET.Moreover,the combination of dithienylethene and infinite coordination polymers gives rise to a synergistic effect,which induces functional behaviors of ammonia sensor applications.Both open and closed forms of Cu-DTEDBA exhibit distinct colorimetric change upon exposure to gaseous ammonia,which is not observed in dithienylethene free molecules.
基金supported by the National Natural Science Foundation of China (Nos.21878087,21908060)the Innovation Program of Shanghai Municipal Education Commission,Shuguang Program (No.18SG27)+1 种基金the NIH guidelines for the care and use of laboratory animals (NIH Publication No.85-23,Rev.1985)approved by the Institutional Animal Care and Use Committee of National Tissue Engineering Center (Shanghai,China)。
文摘Cysteine is well-known to be an important biothiol and related to many diseases. However, the in vivo detection of endogenous cysteine still suffers from lacking small-molecule fluorophores with both excitation and emission in the near-infrared(650-900 nm)/shortwave-infrared region. Herein, we report a molecular engineering strategy for shortwave infrared(SWIR, 900-1700 nm) sensing of cysteine, which integrated an excited-state intermolecular proton transfer(ESIPT) building block into the intramolecular charge transfer(ICT) scaffold. The obtained novel fluorophore SH-OH displays a maximum absorption at the NIR region, and emission at the SWIR region. We introduce the cysteine-recognition moiety to SH-OH structure, and demonstrate sensing of endogenous cysteine in living animals, using the SWIR emission as a reliable off-on fluorescence signal. This fluorophore design strategy of cooperation of ICT and ESIPT processes expands the in vivo sensing toolbox for accurate analysis in clinical applications.
基金Project supported by the National Natural Science Foundation of China （NNSFC） （Nos. 20972050, 21172148）.
文摘In the presence of In/CuCl, ethyl 4-bromo-4,4-difluoro-3-oxo-2-（triphenylphosphoranylidene）butanoate reacted with various aldehydes in aqueous medium at room temperature to give the a,a-difluorinated β-hydroxy carbonyl compounds. Furthermore, treating Reformatsky addition compounds with 1 equiv, of sodium hydroxide in the mixture of tetrahydrofuran and water afforded gem-difluoromethylenated 2-triphenylphosphoranylidene δ-lactones in excellent yields.
文摘Dye-sensitized solar cells （DSSCs） cannot be developed without the research on sensitizers. As the key of light harvesting and electron generation, thousands of sensitizers have been designed for the application in DSSC devices. Among them, organic sensitizers have drawn a lot of attention because of the flexible molecular design, easy synthesis and good photovoltaic performance. Recently, new record photovoltaic conversion efficiencies of 11.5% for DSSCs with iodide electrolyte and 14.3% for DSSCs with cobalt electrolyte and co-sensitization have been achieved with organic sensitizers. Here we focus on the donor design and modification of organic sensitizers. Several useful strategies and corresponding typical examples are presented.
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.
