Patients with pancreatic cancer(PCa)have a poor prognosis apart from the few suitable for surgery.Photodynamic therapy(PDT)is a minimally invasive treatment modality whose efficacy and safety in treating unresectable ...Patients with pancreatic cancer(PCa)have a poor prognosis apart from the few suitable for surgery.Photodynamic therapy(PDT)is a minimally invasive treatment modality whose efficacy and safety in treating unresectable localized PCa have been corroborated in clinic.Yet,it suffers from certain limitations during clinical exploitation,including insufficient photosensitizers(PSs)delivery,tumor-oxygenation dependency,and treatment escape of aggressive tumors.To overcome these obstacles,an increasing number of researchers are currently on a quest to develop photosensitizer nanoparticles(NPs)by the use of a variety of nanocarrier systems to improve cellular uptake and biodistribution of photosensitizers.Encapsulation of PSs with NPs endows them significantly higher accumulation within PCa tumors due to the increased solubility and stability in blood circulation.A number of approaches have been explored to produce NPs co-delivering multi-agents affording PDT-based synergistic therapies for improved response rates and durability of response after treatment.This review provides an overview of available data regarding the design,methodology,and oncological outcome of the innovative NPs-based PDT of PCa.展开更多
Photocatalytic splitting of hydrogen sulfide(H2S) for hydrogen evolution is a promising method to solve the energy and environmental issues.In this work,S,N-codoped carbon dots(S,N-CDs)/graphitic carbon nitride(g-C3N4...Photocatalytic splitting of hydrogen sulfide(H2S) for hydrogen evolution is a promising method to solve the energy and environmental issues.In this work,S,N-codoped carbon dots(S,N-CDs)/graphitic carbon nitride(g-C3N4) nanosheet is synthesized by hydrothermal method as an efficient photocatalyst for the decomposition of H2S.In addition to the characterization of the morphology and structure,chemical state,optical and electrochemical performances of S,N-CDs/g-C3N4,hydrogen evolution tests show that the activity of g-C3N4 is improved by introducing S,N-CDs,and the enhancement depends strongly on the wavelength of incident light.The photocatalytic hydrogen production rate of S,N-CDs/g-C3N4 composite reaches 832 μmol g-1h-1, which is 38 times to that of g-C3N4 under irradiation at 460 nm.Density functional theory calculations and electron paramagnetic resonance as well as photoluminescence technologies have altogether authenticated that the unique wavelength-dependent photosensitization of S,N-CDs on g-C3N4;meanwhile,a good match between the energy level of S,N-CDs and g-C3N4 is pivotal for the effective photocatalytic activity.Our work has unveiled the detailed mechanism of the photocatalytic activity enhancement in S,N-CDs/g-C3N4 composite and showed its potential in photocatalytic splitting of H2S for hydrogen evolution.展开更多
A nanomicelle(denoted as TPGS/Ppa)was fabricated via the coassembly of the amphiphilic D-α-tocopheryl polyethylene glycol 1000 succinate(TPGS)and the hydrophobic photosensitizer pyropheophorbide a(Ppa)for photodynami...A nanomicelle(denoted as TPGS/Ppa)was fabricated via the coassembly of the amphiphilic D-α-tocopheryl polyethylene glycol 1000 succinate(TPGS)and the hydrophobic photosensitizer pyropheophorbide a(Ppa)for photodynamic therapy(PDT).The obtained nanomicelle possessed a spherical structure with a diameter of(18.0±2.2)nm and a zeta potential of approximately -18 mV.Besides,the nanomicelle exhibited excellent photostability,biocompatibility,and phototoxicity,and could effectively reach the tumor region via the enhanced permeability and retention effect.Additionally,it could be found that the TPGS/Ppa nanomicelle exhibited higher phototoxicity against 4T1 murine mammary cancer cells than free Ppa.In the 4T1 tumor-bearing mouse model,the nanomicelle showed an excellent antitumor therapeutic effect.This study develops a new type of photodynamic nanomicelle TPGS/Ppa,which can increase the accumulation of drugs and prolong their tumor retention time,providing a feasible strategy for realizing the delivery of small-molecule hydrophobic drugs and tumor PDT.展开更多
Dual-functional aggregation-induced photosensitizers(AIE-PSs)with singlet oxygen generation(SOG)ability and bright fluorescence in aggregated state have received much attention in image-guided photodynamic therapy(PDT...Dual-functional aggregation-induced photosensitizers(AIE-PSs)with singlet oxygen generation(SOG)ability and bright fluorescence in aggregated state have received much attention in image-guided photodynamic therapy(PDT).However,designing an AIE-PS with both high SOG and intense fluorescence via molecular design is still challenging.In this work,we report a new nanohybrid consisting of gold nanostar(AuNS)and AIE-PS dots with enhanced fluorescence and photosensitization for theranostic applications.The spectral overlap between the extinction of AuNS and fluorescence emission of AIE-PS dots(665 nm)is carefully selected using five different AuNSs with distinct localized surface plasmon(LSPR)peaks.Results show that all the AuNS s can enhance the 1 O2 production of AIE-PS dots,among which the AuNS with LSPR peak at 585 nm exhibited the highest 1 O2 enhancement factor of15-fold with increased fluorescence brightness.To the best of our knowledge,this is the highest enhancement factor reported for the metalenhanced singlet oxygen generation systems.The Au585@AIE-PS nanodots were applied for simultaneous fluorescence imaging and photodynamic ablation of HeLa cancer cells with strongly enhanced PDT efficiency in vitro.This study provides a better understanding of the metal-enhanced AIE-PS nanohybrid systems,opening up new avenue towards advanced image-guided PDT with greatly improved efficacy.展开更多
Singlet oxygen(1 O2) plays an important role in various applications, such as in the photodynamic therapy(PDT) of cancers,photodynamic inactivation of microorganisms, photo-degradation of toxic compounds, and photo-ox...Singlet oxygen(1 O2) plays an important role in various applications, such as in the photodynamic therapy(PDT) of cancers,photodynamic inactivation of microorganisms, photo-degradation of toxic compounds, and photo-oxidation in synthetic chemistry. Recently,water-soluble metal nanoclusters(NCs) have been utilized as photosensitizers for the generation of highly reactive 1 O2 because of their high water solubility, low toxicity, and surface functionalizability for targeted substances. In the case of metal NC-based photosensitizers, the photo-physical properties depend on the core size of the NCs and the core/ligand interfacial structures. A wide range of atomically precise gold NCs have been reported; however, reports on the synthesis of atomically precise silver NCs are limited due to the high reactivity and low photostability(i.e., easy oxidation) of Ag NCs. In addition, there have been few reports on what kinds of metal NCs can generate large amounts of 1 O2. In this study, we developed a new one-pot synthesis method of water-soluble Ag7(MBISA)6(MBISA= 2-mercapto-5-benzimidazolesulfonic acid sodium salt) NCs with highly efficient 1 O2 generation ability under the irradiation of white light emitting diodes(LEDs). The molecular formula and purity were determined by electrospray ionization mass spectrometry and gel electrophoresis. To the best of our knowledge, this is the first report on atomically precise thiolate silver clusters(Agn(SR)m) for efficient 1 O2 generation under visible light irradiation. The 1 O2 generation efficiency of Ag7(MBISA)6 NCs was higher than those of the following known water-soluble metal NCs: bovine serum albumin(BSA)-Au25 NCs,BSA-Ag8 NCs, BSA-Ag14 NCs,Ag25(dihydrolipoic acid)14 NCs,Ag35(glutathione)18 NCs,and Ag75(glutathione)40 NCs. The metal NCs examined in this study showed the following order of 1 O2 generation efficiency under white light irradiation: Ag7(MBISA)6 > BSA-Ag14 > Ag75(SG)40 > Ag35(SG)18 >BSA-Au25 >>BSA-Ags(not detected) and Ag2 s(DHLA)14(not detected). For further improving the 1 O2 generation of Ag7(MBISA)6 NCs, we developed a novel fluorescence resonance energy transfer(FRET) system by conjugating Ag7(MBISA)6 NCs with quinacrine(QC)(molar ratio of Ag NCs to QC is 1 : 0.5). We observed the FRET process,from QC to Ag7(MBISA)6 NCs,occurring in the conjugate. That is,the QC works as a donor chromophore,while the Ag NCs work as an acceptor chromophore in the FRET process. The FRET-mediated process caused a 2.3-fold increase in 1 O2 generation compared to that obtained with Ag7(MBISA)6 NCs alone. This study establishes a general and simple strategy for improving the PDT activity of metal NC-based photosensitizers.展开更多
The photocatalytic performances of water oxidation were usually carried out in two different systems,photosensitizer and non-photosensitizer systems.There is few report about the same catalyst used in two systems and ...The photocatalytic performances of water oxidation were usually carried out in two different systems,photosensitizer and non-photosensitizer systems.There is few report about the same catalyst used in two systems and therefore it is of great significant to compare its role of the same catalyst in two systems and explore its different reaction mechanisms.In this work,first 4 kinds of metallic Co microparticles were obtained by different reduction methods through hydrothermal processes,and Co@Co_(3)O_(4) coreshell microparticles(1-4)were obtained from these metallic Co microparticles oxidized in air or in the reacting solution in situ.The core-shell structure of 1 was characterized by a series of analytical techniques.1-4 exhibited excellent activities and stabilities in the[Ru(bpy)3]^(2+)/S_(2) O_(8)^(2-)/light system when they were used as catalysts for the photocata lytic water oxidation.The maximum O2 evolution of 1 after 20 min’s illumination was 98.2 pmol,the O_(2) yield was 65.5%,the initial turnover frequency was 6.6×10^(-3),the initial quantum efficiency(ΦQYinitial)was 15.0%higher than Co(8.3%),CoO(11.7%),Co_(2)O_(3)(1.2%),Co_(3)O_(4)(2.8%)and 5(2.2%).Even after the sixth run,the catalytic activity of recovered 1 still remained 85.1%of initial activity.In addition,the photocatalytic performances of 1 in the[Ru(bpy)_(3)]^(2+)/S_(2)O_(8)2-/light system and S_(2) O_(8)^(2-)/light system were compared for the first time.In the nonphotosensitizer system,1 shows bifunctional roles and acts as optical absorption center and active catalytic site,and oxygen evolution rate is lower and it takes longer time.In the photosensitizer system,1 only acts as a catalyst,the photosensitizer enhances the light absorption and promotes water oxidation reaction with higher O_(2) yield and QE,meanwhile the photosensitizer brings the defect of high cost and instability into the system.Based on the results the two different reaction mechanisms were deeply discussed.展开更多
The redox active ionic liquid, 1-ethyl-4-(methoxycarbonyl)pyridinium bis(trifluoromethanesulfonyl)amide(RIL), was synthesized from its iodide form by an anion exchange reaction of Li(NTf_2) with viscos liquid(η= 122 ...The redox active ionic liquid, 1-ethyl-4-(methoxycarbonyl)pyridinium bis(trifluoromethanesulfonyl)amide(RIL), was synthesized from its iodide form by an anion exchange reaction of Li(NTf_2) with viscos liquid(η= 122 cP at 25C) and characterized by NMR, IR, and elemental analysis. The compound showed reversible redox couples at -0.65 V and -1.48 V vs. Ag/AgCl and worked as an electron mediator in the B_(12) complex/[Ru(bpy)_3]Cl_2 photosensitizer catalytic system under visible light irradiation. The catalytic efficiency in the RIL was higher than those in DMF, MeOH, and the redox inactive ionic liquid, 1-butyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)amide.展开更多
Hydrogenated amorphous silicon （a-Si：H） films with high and same order of magnitude photosensitivity （-10^5） but different stability were prepared by using microwave electron cyclotron resonance chemical vapour d...Hydrogenated amorphous silicon （a-Si：H） films with high and same order of magnitude photosensitivity （-10^5） but different stability were prepared by using microwave electron cyclotron resonance chemical vapour deposition system under the different deposition conditions. It was proposed that there was no direct correlation between the photosensitivity and the hydrogen content （CH） as well as H-Si bonding configurations, but for the stability, they were the critical factors. The experimental results indicated that higher substrate temperature, hydrogen dilution ratio and lower deposition rate played an important role in improving the microstructure of a-Si：H films. We used hydrogen elimination model to explain our experimental results.展开更多
Polymer thin-film transistors （PTFTs） based on poly（3-hexylthiophene） are fabricated by the spin-coating process, and their photo-sensing characteristics are investigated under steady-state visible-light illuminat...Polymer thin-film transistors （PTFTs） based on poly（3-hexylthiophene） are fabricated by the spin-coating process, and their photo-sensing characteristics are investigated under steady-state visible-light illumination. The photosensitivity of the device is strongly modulated by gate voltage under various illuminations. When the device is in the subthreshold operating mode, a significant increase in its drain current is observed with a maximum photosensitivity of 1.7×10^3 at an illumination intensity of 1200 lx, and even with a relatively high photosensitivity of 611 at a low illumination intensity of 100 lx. However, when the device is in the on-state operating mode, the photosensitivity is very low： only 1.88 at an illumination intensity of 1200 lx for a gate voltage of -20 V and a drain voltage of -20 V. The results indicate that the devices could be used as photo-detectors or sensors in the range of visible light. The modulation mechanism of the photosensitivity in the PTFT is discussed in detail.展开更多
Phototoxic treatments of pathogenic bacteria and fungi of trees induce oxidative damage that is preferable to toxic chemical treatment.Here,we used green methods to synthesize Chlorin e6 from chlorophyll a,which was e...Phototoxic treatments of pathogenic bacteria and fungi of trees induce oxidative damage that is preferable to toxic chemical treatment.Here,we used green methods to synthesize Chlorin e6 from chlorophyll a,which was extracted from crude silkworm excrement using concentrated(strong)alkali hydrolysis and acidification.The photosensitive bactericidal activities of the new chlorin were tested in vitro,and possible mechanisms of action are discussed.The results showed that Chlorin e6 can be lightactivated to have bactericidal activity against Escherichia coli,Bacillus subtilis and Fusarium oxysporum,but it had little bactericidal effect in the dark.This kind of chlorin compounds has great potential as a natural phototoxic antimicrobial compound to control harmful bacteria on the leaves in forestry systems.展开更多
Seawater photoelectrolysis is showing huge potential in green energy conversion field,yet it is still a formidable challenge to develop one catalyst that can drive the electrolysis reaction stably,economically and eff...Seawater photoelectrolysis is showing huge potential in green energy conversion field,yet it is still a formidable challenge to develop one catalyst that can drive the electrolysis reaction stably,economically and efficiently.Motivated by this point,the inorganic–organic hybridization strategy is proposed to insitu construct one hierarchical electrode via concurrent electroless plating and polymerization,which assures the growth of boron-modulated nickel–cobalt oxyhydroxide nanoballs and photosensitive polyaniline nanochains on the self-supporting Ti-based foil(B-Co Ni OOH/PANI@TiO_(2)/Ti).Upon inducing photoelectric effect(PEE),the designed target electrode delivers overpotentials as low as 196 and 398 mV at 100 mA cm^(-2)for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),respectively,corresponding to an activity enhancement by about 15%as compared to those without PEE.Inspiringly,when served as bifunctional electrocatalysts for overall seawater electrolysis,it can stably maintain at 200 mA cm^(-2)with negligible decay over 72 h.Further analysis reveals that the exceptional catalytic performance can be credit to the B-CoNiOOH,polyaniline(PANI)and TiO_(2)subunit coupling-induced physically and chemically synergistic catalysis effect such as admirable composition stability,photoelectric function and adhesion capability.The finding in this contribution may trigger much more broad interest to the novel hybrid catalysts consisting of photosensitive polymer and transition metal-based electrocatalysts.展开更多
We report a novel technique to enhance the ultraviolet （UV） photosensitivity of a ZnO nanosensor with ZnO nanowires bridged on micromachined metallic electrodes. The experimental results reveal that the photoconduct...We report a novel technique to enhance the ultraviolet （UV） photosensitivity of a ZnO nanosensor with ZnO nanowires bridged on micromachined metallic electrodes. The experimental results reveal that the photoconductivity and the time response of the ZnO nanowire sensor with either Schottky or Ohmic contacts are significantly improved by electrifying the nanowire sensors using an alternating current at the frequency of megahertz. An integrated UV sensor incorporating ZnO nanowires with a constant current mode driving circuit is developed, which demonstrates promising sensitivity and time response to UV illumination with a low power consumption.展开更多
It has been shown by the results-of HPLC analysis in combination with spectrographicdeterminations that PsD-007 is composed of 7 different porphyrins,In order of the proportion inPsD-007,they are:3 （or 8）-（l-methox...It has been shown by the results-of HPLC analysis in combination with spectrographicdeterminations that PsD-007 is composed of 7 different porphyrins,In order of the proportion inPsD-007,they are:3 （or 8）-（l-methoxyethyl）-8 （or 3）-（l-hydroxyethyl）-deuteroporphyrin Ⅸ（MHD）;3,8-di-（l-methoxyethyl）-deuteroporphyrin Ⅸ（DMD）;3（or 8）-（l-methoxyethyl）-8 （or3）-vinyl-deuteroporphyrin Ⅸ（MVD）;3（or 8）-（l-hydroxyethyl）-8（or 3）-vinyl-deuteroporphyrin Ⅸ（HVD）;hernatoporphyrin Ⅸ （Hp）;protoporphyrin Ⅸ （Pp） and 3（or 8）-（O-aceylethyl）-8（or 3）-（l-hydroxyethyl）-deuteroporphrin Ⅸ （AHD）,which presented only in crude PsD-007 and hasbeen transformed into MHD and Hp,respectively during the separation and preparing the clinicalpreparation of PsD-007.Structures of these porphyrins were further eonfirmed by the corre-sponding anthentic samples obtained by synthetic method.It was found on the basis of the experi-mental data of photosensitizing ability in cell-free systems and photoinactivation of human cancercells in vitro as well as efficacy of photodynamic therapy for sarcoma.S<sub>180</sub> in mice of the ma-jor components MILD,DMD and MVD composed of which more over 85% of the totalamount of PsD-007,that they all exhibited comparatively high photosensitizing ability andphotodynamic effects on cancer cells and tram-planted animal tumor.展开更多
This paper studies the photosensitive effect of cerium oxide on the precipitation of Ag nanoparticles after femtosecond laser irradiating into silicate glass and successive annealing.Spectroscopy analysis and diffract...This paper studies the photosensitive effect of cerium oxide on the precipitation of Ag nanoparticles after femtosecond laser irradiating into silicate glass and successive annealing.Spectroscopy analysis and diffraction efficiency measurements show that the introduction of cerium oxide may increase the concentration of Ag atoms in the femtosecond laser-irradiated regions resulting from the photoreduction reaction Ce^3＋ ＋ Ag^＋ → Ce^4＋ ＋ Ag^0 via multiphoton excitation.These results promote the aggregation of Ag nanopartieles during the annealing process. It is also found that different concentrations of cerium oxide may influence the Ag nanoparticle precipitation in the corresponding glass.展开更多
Photocarcinorin was prepared in our Lab and its composition was differentfrom that of any other hematoporphyrin photosensitizers by TLC and HPLC analyses.The 95% fiducial limits of iv LD in mice were 176-236 mg·k...Photocarcinorin was prepared in our Lab and its composition was differentfrom that of any other hematoporphyrin photosensitizers by TLC and HPLC analyses.The 95% fiducial limits of iv LD in mice were 176-236 mg·kg<sup>-1</sup>.The iv MLD indogs was 171 mg·kg<sup>-1</sup>.The acute and subacutc toxic tests in 37 dogs showed that theintoxicated manifestations were characterized by a complex syndrome always seen inporphyrias.The biological,laboratory and histopathologic findings revealed that theliver,kidney and erythroeytic series were the target organs.The damages were dose-related and reversible within 2 wk.he phototoxicity was determined in mice with UV ra-diation and compared with that of HpD.The extent of its phototoxic reactions waslower than that of HpD’s.展开更多
Abstract--With the development of clean energy, switching and distribution issues in a photovoltaic system are getting much attention in recent years. This paper designs a DC to AC inverter and power switching and dis...Abstract--With the development of clean energy, switching and distribution issues in a photovoltaic system are getting much attention in recent years. This paper designs a DC to AC inverter and power switching and distribution system between a solar power system and the municipal system by using the Darlington amplifier structure with the photosensitive resistor and accompanying relays, and details the system circuits. The proposed system can achieve a stable output of IIOV AC, as well as self-generating driving voltage and switching between the municipal electrical system and the solar power system. The mathematic analysis and actually test results demonstrate that the proposed method is an easy, inexpensive, and low cost way to build a solar power switching and distribution system.展开更多
基金financially supported by Beijing Natural Science Foundation,Haidian,original innovation joint fund(No.17L20170)National Key Research and Development Program of China(No.2016YFA0201400)+3 种基金State Key Program of National Natural Science of China(No.81930047)Projects of International Cooperation and Exchanges NSFC-PSF(No.31961143003)National Project for Research and Development of Major Scientific Instruments(No.81727803)the Foundation for Innovative Research Groups of the National Natural Science Foundation of China(No.81421004).
文摘Patients with pancreatic cancer(PCa)have a poor prognosis apart from the few suitable for surgery.Photodynamic therapy(PDT)is a minimally invasive treatment modality whose efficacy and safety in treating unresectable localized PCa have been corroborated in clinic.Yet,it suffers from certain limitations during clinical exploitation,including insufficient photosensitizers(PSs)delivery,tumor-oxygenation dependency,and treatment escape of aggressive tumors.To overcome these obstacles,an increasing number of researchers are currently on a quest to develop photosensitizer nanoparticles(NPs)by the use of a variety of nanocarrier systems to improve cellular uptake and biodistribution of photosensitizers.Encapsulation of PSs with NPs endows them significantly higher accumulation within PCa tumors due to the increased solubility and stability in blood circulation.A number of approaches have been explored to produce NPs co-delivering multi-agents affording PDT-based synergistic therapies for improved response rates and durability of response after treatment.This review provides an overview of available data regarding the design,methodology,and oncological outcome of the innovative NPs-based PDT of PCa.
基金financial support from the National Natural Science Foundation of China (U1862111 and 21702213)Cheung Kong Scholars Programme of China+3 种基金Chinese Academic of Science “light of west China” ProgramProvincial International Cooperation Project 2020YFH0118, Sichuan, ChinaOpen Fund (PLN201802 and 201928) of State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation (Southwest Petroleum University)Open Fund of State Key Laboratory of Industrial Vent Gas Reuse (SKLIVGR-SWPU-2020-05)。
文摘Photocatalytic splitting of hydrogen sulfide(H2S) for hydrogen evolution is a promising method to solve the energy and environmental issues.In this work,S,N-codoped carbon dots(S,N-CDs)/graphitic carbon nitride(g-C3N4) nanosheet is synthesized by hydrothermal method as an efficient photocatalyst for the decomposition of H2S.In addition to the characterization of the morphology and structure,chemical state,optical and electrochemical performances of S,N-CDs/g-C3N4,hydrogen evolution tests show that the activity of g-C3N4 is improved by introducing S,N-CDs,and the enhancement depends strongly on the wavelength of incident light.The photocatalytic hydrogen production rate of S,N-CDs/g-C3N4 composite reaches 832 μmol g-1h-1, which is 38 times to that of g-C3N4 under irradiation at 460 nm.Density functional theory calculations and electron paramagnetic resonance as well as photoluminescence technologies have altogether authenticated that the unique wavelength-dependent photosensitization of S,N-CDs on g-C3N4;meanwhile,a good match between the energy level of S,N-CDs and g-C3N4 is pivotal for the effective photocatalytic activity.Our work has unveiled the detailed mechanism of the photocatalytic activity enhancement in S,N-CDs/g-C3N4 composite and showed its potential in photocatalytic splitting of H2S for hydrogen evolution.
文摘A nanomicelle(denoted as TPGS/Ppa)was fabricated via the coassembly of the amphiphilic D-α-tocopheryl polyethylene glycol 1000 succinate(TPGS)and the hydrophobic photosensitizer pyropheophorbide a(Ppa)for photodynamic therapy(PDT).The obtained nanomicelle possessed a spherical structure with a diameter of(18.0±2.2)nm and a zeta potential of approximately -18 mV.Besides,the nanomicelle exhibited excellent photostability,biocompatibility,and phototoxicity,and could effectively reach the tumor region via the enhanced permeability and retention effect.Additionally,it could be found that the TPGS/Ppa nanomicelle exhibited higher phototoxicity against 4T1 murine mammary cancer cells than free Ppa.In the 4T1 tumor-bearing mouse model,the nanomicelle showed an excellent antitumor therapeutic effect.This study develops a new type of photodynamic nanomicelle TPGS/Ppa,which can increase the accumulation of drugs and prolong their tumor retention time,providing a feasible strategy for realizing the delivery of small-molecule hydrophobic drugs and tumor PDT.
基金supported by the Institute of Materials Research and Engineering under Biomimetic and Biomedical Materials program(IMRE/00-1P1400)Newcastle University(RSA/CCEAMD5010)+1 种基金National University of Singapore(R279-000-482-133)The funding from NRF Investigatorship(R279-000-444-281)is also appreciated。
文摘Dual-functional aggregation-induced photosensitizers(AIE-PSs)with singlet oxygen generation(SOG)ability and bright fluorescence in aggregated state have received much attention in image-guided photodynamic therapy(PDT).However,designing an AIE-PS with both high SOG and intense fluorescence via molecular design is still challenging.In this work,we report a new nanohybrid consisting of gold nanostar(AuNS)and AIE-PS dots with enhanced fluorescence and photosensitization for theranostic applications.The spectral overlap between the extinction of AuNS and fluorescence emission of AIE-PS dots(665 nm)is carefully selected using five different AuNSs with distinct localized surface plasmon(LSPR)peaks.Results show that all the AuNS s can enhance the 1 O2 production of AIE-PS dots,among which the AuNS with LSPR peak at 585 nm exhibited the highest 1 O2 enhancement factor of15-fold with increased fluorescence brightness.To the best of our knowledge,this is the highest enhancement factor reported for the metalenhanced singlet oxygen generation systems.The Au585@AIE-PS nanodots were applied for simultaneous fluorescence imaging and photodynamic ablation of HeLa cancer cells with strongly enhanced PDT efficiency in vitro.This study provides a better understanding of the metal-enhanced AIE-PS nanohybrid systems,opening up new avenue towards advanced image-guided PDT with greatly improved efficacy.
基金The project was supported by the JSPS KAKENH1, Japan (15H03520, 15H03526, and 26107719), and the MEXT-Supported Program for the Strategic Research Foundation at Private Universities, Japan.
文摘Singlet oxygen(1 O2) plays an important role in various applications, such as in the photodynamic therapy(PDT) of cancers,photodynamic inactivation of microorganisms, photo-degradation of toxic compounds, and photo-oxidation in synthetic chemistry. Recently,water-soluble metal nanoclusters(NCs) have been utilized as photosensitizers for the generation of highly reactive 1 O2 because of their high water solubility, low toxicity, and surface functionalizability for targeted substances. In the case of metal NC-based photosensitizers, the photo-physical properties depend on the core size of the NCs and the core/ligand interfacial structures. A wide range of atomically precise gold NCs have been reported; however, reports on the synthesis of atomically precise silver NCs are limited due to the high reactivity and low photostability(i.e., easy oxidation) of Ag NCs. In addition, there have been few reports on what kinds of metal NCs can generate large amounts of 1 O2. In this study, we developed a new one-pot synthesis method of water-soluble Ag7(MBISA)6(MBISA= 2-mercapto-5-benzimidazolesulfonic acid sodium salt) NCs with highly efficient 1 O2 generation ability under the irradiation of white light emitting diodes(LEDs). The molecular formula and purity were determined by electrospray ionization mass spectrometry and gel electrophoresis. To the best of our knowledge, this is the first report on atomically precise thiolate silver clusters(Agn(SR)m) for efficient 1 O2 generation under visible light irradiation. The 1 O2 generation efficiency of Ag7(MBISA)6 NCs was higher than those of the following known water-soluble metal NCs: bovine serum albumin(BSA)-Au25 NCs,BSA-Ag8 NCs, BSA-Ag14 NCs,Ag25(dihydrolipoic acid)14 NCs,Ag35(glutathione)18 NCs,and Ag75(glutathione)40 NCs. The metal NCs examined in this study showed the following order of 1 O2 generation efficiency under white light irradiation: Ag7(MBISA)6 > BSA-Ag14 > Ag75(SG)40 > Ag35(SG)18 >BSA-Au25 >>BSA-Ags(not detected) and Ag2 s(DHLA)14(not detected). For further improving the 1 O2 generation of Ag7(MBISA)6 NCs, we developed a novel fluorescence resonance energy transfer(FRET) system by conjugating Ag7(MBISA)6 NCs with quinacrine(QC)(molar ratio of Ag NCs to QC is 1 : 0.5). We observed the FRET process,from QC to Ag7(MBISA)6 NCs,occurring in the conjugate. That is,the QC works as a donor chromophore,while the Ag NCs work as an acceptor chromophore in the FRET process. The FRET-mediated process caused a 2.3-fold increase in 1 O2 generation compared to that obtained with Ag7(MBISA)6 NCs alone. This study establishes a general and simple strategy for improving the PDT activity of metal NC-based photosensitizers.
基金the funding support from the National Natural Science Foundation of China(No.21861035)the University Scientific Research Project of Xinjiang Uyghur Autonomous Region(No.XJEDU2017I001)。
文摘The photocatalytic performances of water oxidation were usually carried out in two different systems,photosensitizer and non-photosensitizer systems.There is few report about the same catalyst used in two systems and therefore it is of great significant to compare its role of the same catalyst in two systems and explore its different reaction mechanisms.In this work,first 4 kinds of metallic Co microparticles were obtained by different reduction methods through hydrothermal processes,and Co@Co_(3)O_(4) coreshell microparticles(1-4)were obtained from these metallic Co microparticles oxidized in air or in the reacting solution in situ.The core-shell structure of 1 was characterized by a series of analytical techniques.1-4 exhibited excellent activities and stabilities in the[Ru(bpy)3]^(2+)/S_(2) O_(8)^(2-)/light system when they were used as catalysts for the photocata lytic water oxidation.The maximum O2 evolution of 1 after 20 min’s illumination was 98.2 pmol,the O_(2) yield was 65.5%,the initial turnover frequency was 6.6×10^(-3),the initial quantum efficiency(ΦQYinitial)was 15.0%higher than Co(8.3%),CoO(11.7%),Co_(2)O_(3)(1.2%),Co_(3)O_(4)(2.8%)and 5(2.2%).Even after the sixth run,the catalytic activity of recovered 1 still remained 85.1%of initial activity.In addition,the photocatalytic performances of 1 in the[Ru(bpy)_(3)]^(2+)/S_(2)O_(8)2-/light system and S_(2) O_(8)^(2-)/light system were compared for the first time.In the nonphotosensitizer system,1 shows bifunctional roles and acts as optical absorption center and active catalytic site,and oxygen evolution rate is lower and it takes longer time.In the photosensitizer system,1 only acts as a catalyst,the photosensitizer enhances the light absorption and promotes water oxidation reaction with higher O_(2) yield and QE,meanwhile the photosensitizer brings the defect of high cost and instability into the system.Based on the results the two different reaction mechanisms were deeply discussed.
基金partially supported by JSPS KAKENHI Grant Number 18H04265 in Precisely Designed Catalysts with Customized Scaffolding and Grant Number JP16H04119by JSPS and PAN under the Research Cooperative Program Grant Number AJ180081 (30-0004-04)a Grant from the Nippon Sheet Glass Foundation (HAKF541800)
文摘The redox active ionic liquid, 1-ethyl-4-(methoxycarbonyl)pyridinium bis(trifluoromethanesulfonyl)amide(RIL), was synthesized from its iodide form by an anion exchange reaction of Li(NTf_2) with viscos liquid(η= 122 cP at 25C) and characterized by NMR, IR, and elemental analysis. The compound showed reversible redox couples at -0.65 V and -1.48 V vs. Ag/AgCl and worked as an electron mediator in the B_(12) complex/[Ru(bpy)_3]Cl_2 photosensitizer catalytic system under visible light irradiation. The catalytic efficiency in the RIL was higher than those in DMF, MeOH, and the redox inactive ionic liquid, 1-butyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)amide.
文摘Hydrogenated amorphous silicon （a-Si：H） films with high and same order of magnitude photosensitivity （-10^5） but different stability were prepared by using microwave electron cyclotron resonance chemical vapour deposition system under the different deposition conditions. It was proposed that there was no direct correlation between the photosensitivity and the hydrogen content （CH） as well as H-Si bonding configurations, but for the stability, they were the critical factors. The experimental results indicated that higher substrate temperature, hydrogen dilution ratio and lower deposition rate played an important role in improving the microstructure of a-Si：H films. We used hydrogen elimination model to explain our experimental results.
基金Projected supported by the National Natural Science Foundation of China (Grant No. 61076113)the Natural Science Foundation of Guangdong Province,China (Grant No. 8451064101000257)the Research Grants Council (RGC) of Hong Kong Special Administrative Region (HKSAR),China (Grant No. HKU 7133/07E)
文摘Polymer thin-film transistors （PTFTs） based on poly（3-hexylthiophene） are fabricated by the spin-coating process, and their photo-sensing characteristics are investigated under steady-state visible-light illumination. The photosensitivity of the device is strongly modulated by gate voltage under various illuminations. When the device is in the subthreshold operating mode, a significant increase in its drain current is observed with a maximum photosensitivity of 1.7×10^3 at an illumination intensity of 1200 lx, and even with a relatively high photosensitivity of 611 at a low illumination intensity of 100 lx. However, when the device is in the on-state operating mode, the photosensitivity is very low： only 1.88 at an illumination intensity of 1200 lx for a gate voltage of -20 V and a drain voltage of -20 V. The results indicate that the devices could be used as photo-detectors or sensors in the range of visible light. The modulation mechanism of the photosensitivity in the PTFT is discussed in detail.
基金supported by Fundamental Research Funds for the Central Universities(No.DL12BA06)Harbin Science and Technology Innovation Talent Research Special Funds(2015RAQXJ002)
文摘Phototoxic treatments of pathogenic bacteria and fungi of trees induce oxidative damage that is preferable to toxic chemical treatment.Here,we used green methods to synthesize Chlorin e6 from chlorophyll a,which was extracted from crude silkworm excrement using concentrated(strong)alkali hydrolysis and acidification.The photosensitive bactericidal activities of the new chlorin were tested in vitro,and possible mechanisms of action are discussed.The results showed that Chlorin e6 can be lightactivated to have bactericidal activity against Escherichia coli,Bacillus subtilis and Fusarium oxysporum,but it had little bactericidal effect in the dark.This kind of chlorin compounds has great potential as a natural phototoxic antimicrobial compound to control harmful bacteria on the leaves in forestry systems.
基金supported by the National Natural Science Foundation of China(22109098)the Shanghai Sailing Program(20YF1432300)+4 种基金the Shanghai Engineering Research Center for Food Rapid Detection(19DZ2251300)the Natural Science Foundation of Jiangsu Province(BK20210735)the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province(21KJB430043)the Collaborative Innovation Center of Suzhou Nano Science&Technology,the 111 Projectthe Suzhou Key Laboratory of Functional Nano&Soft Materials。
文摘Seawater photoelectrolysis is showing huge potential in green energy conversion field,yet it is still a formidable challenge to develop one catalyst that can drive the electrolysis reaction stably,economically and efficiently.Motivated by this point,the inorganic–organic hybridization strategy is proposed to insitu construct one hierarchical electrode via concurrent electroless plating and polymerization,which assures the growth of boron-modulated nickel–cobalt oxyhydroxide nanoballs and photosensitive polyaniline nanochains on the self-supporting Ti-based foil(B-Co Ni OOH/PANI@TiO_(2)/Ti).Upon inducing photoelectric effect(PEE),the designed target electrode delivers overpotentials as low as 196 and 398 mV at 100 mA cm^(-2)for hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),respectively,corresponding to an activity enhancement by about 15%as compared to those without PEE.Inspiringly,when served as bifunctional electrocatalysts for overall seawater electrolysis,it can stably maintain at 200 mA cm^(-2)with negligible decay over 72 h.Further analysis reveals that the exceptional catalytic performance can be credit to the B-CoNiOOH,polyaniline(PANI)and TiO_(2)subunit coupling-induced physically and chemically synergistic catalysis effect such as admirable composition stability,photoelectric function and adhesion capability.The finding in this contribution may trigger much more broad interest to the novel hybrid catalysts consisting of photosensitive polymer and transition metal-based electrocatalysts.
基金Project supported by the National Natural Science Foundation of China (Grant No. 91123017)
文摘We report a novel technique to enhance the ultraviolet （UV） photosensitivity of a ZnO nanosensor with ZnO nanowires bridged on micromachined metallic electrodes. The experimental results reveal that the photoconductivity and the time response of the ZnO nanowire sensor with either Schottky or Ohmic contacts are significantly improved by electrifying the nanowire sensors using an alternating current at the frequency of megahertz. An integrated UV sensor incorporating ZnO nanowires with a constant current mode driving circuit is developed, which demonstrates promising sensitivity and time response to UV illumination with a low power consumption.
文摘It has been shown by the results-of HPLC analysis in combination with spectrographicdeterminations that PsD-007 is composed of 7 different porphyrins,In order of the proportion inPsD-007,they are:3 （or 8）-（l-methoxyethyl）-8 （or 3）-（l-hydroxyethyl）-deuteroporphyrin Ⅸ（MHD）;3,8-di-（l-methoxyethyl）-deuteroporphyrin Ⅸ（DMD）;3（or 8）-（l-methoxyethyl）-8 （or3）-vinyl-deuteroporphyrin Ⅸ（MVD）;3（or 8）-（l-hydroxyethyl）-8（or 3）-vinyl-deuteroporphyrin Ⅸ（HVD）;hernatoporphyrin Ⅸ （Hp）;protoporphyrin Ⅸ （Pp） and 3（or 8）-（O-aceylethyl）-8（or 3）-（l-hydroxyethyl）-deuteroporphrin Ⅸ （AHD）,which presented only in crude PsD-007 and hasbeen transformed into MHD and Hp,respectively during the separation and preparing the clinicalpreparation of PsD-007.Structures of these porphyrins were further eonfirmed by the corre-sponding anthentic samples obtained by synthetic method.It was found on the basis of the experi-mental data of photosensitizing ability in cell-free systems and photoinactivation of human cancercells in vitro as well as efficacy of photodynamic therapy for sarcoma.S<sub>180</sub> in mice of the ma-jor components MILD,DMD and MVD composed of which more over 85% of the totalamount of PsD-007,that they all exhibited comparatively high photosensitizing ability andphotodynamic effects on cancer cells and tram-planted animal tumor.
基金Project supported by the National Basic Research Program of China (Grant No 2006CB806000b)the Shanghai Leading Academic Discipline Project (Grant No S30105)
文摘This paper studies the photosensitive effect of cerium oxide on the precipitation of Ag nanoparticles after femtosecond laser irradiating into silicate glass and successive annealing.Spectroscopy analysis and diffraction efficiency measurements show that the introduction of cerium oxide may increase the concentration of Ag atoms in the femtosecond laser-irradiated regions resulting from the photoreduction reaction Ce^3＋ ＋ Ag^＋ → Ce^4＋ ＋ Ag^0 via multiphoton excitation.These results promote the aggregation of Ag nanopartieles during the annealing process. It is also found that different concentrations of cerium oxide may influence the Ag nanoparticle precipitation in the corresponding glass.
文摘Photocarcinorin was prepared in our Lab and its composition was differentfrom that of any other hematoporphyrin photosensitizers by TLC and HPLC analyses.The 95% fiducial limits of iv LD in mice were 176-236 mg·kg<sup>-1</sup>.The iv MLD indogs was 171 mg·kg<sup>-1</sup>.The acute and subacutc toxic tests in 37 dogs showed that theintoxicated manifestations were characterized by a complex syndrome always seen inporphyrias.The biological,laboratory and histopathologic findings revealed that theliver,kidney and erythroeytic series were the target organs.The damages were dose-related and reversible within 2 wk.he phototoxicity was determined in mice with UV ra-diation and compared with that of HpD.The extent of its phototoxic reactions waslower than that of HpD’s.
文摘Abstract--With the development of clean energy, switching and distribution issues in a photovoltaic system are getting much attention in recent years. This paper designs a DC to AC inverter and power switching and distribution system between a solar power system and the municipal system by using the Darlington amplifier structure with the photosensitive resistor and accompanying relays, and details the system circuits. The proposed system can achieve a stable output of IIOV AC, as well as self-generating driving voltage and switching between the municipal electrical system and the solar power system. The mathematic analysis and actually test results demonstrate that the proposed method is an easy, inexpensive, and low cost way to build a solar power switching and distribution system.
