Room-temperature gas sensors have aroused great attention in current gas sensor technology because of deemed demand of cheap,low power consumption and portable sensors for rapidly growing Internet of things applicatio...Room-temperature gas sensors have aroused great attention in current gas sensor technology because of deemed demand of cheap,low power consumption and portable sensors for rapidly growing Internet of things applications.As an important approach,light illumination has been exploited for room-temperature operation with improving gas sensor's attributes including sensitivity,speed and selectivity.This review provides an overview of the utilization of photoactivated nanomaterials in gas sensing field.First,recent advances in gas sensing of some exciting different nanostructures and hybrids of metal oxide semiconductors under light illumination are highlighted.Later,excellent gas sensing performance of emerging two-dimensional materialsbased sensors under light illumination is discussed in details with proposed gas sensing mechanism.Originated impressive features from the interaction of photons with sensing materials are elucidated in the context of modulating sensing characteristics.Finally,the review concludes with key and constructive insights into current and future perspectives in the light-activated nanomaterials for optoelectronic gas sensor applications.展开更多
Despite extensive investigations into photophysics at the molecular level,the complex interplays between intermolecular interactions,hierarchical assembly,and photoluminescence properties remain a fundamental challeng...Despite extensive investigations into photophysics at the molecular level,the complex interplays between intermolecular interactions,hierarchical assembly,and photoluminescence properties remain a fundamental challenge in materials science,particularly concerning emergent phenomena in molecular aggregates.Herein,we construct different dimeric structures in both solution and aggregate states through cycloreversion upon photoirradiation from a series of nonemissive phenanthrene cycloadducts,exhibiting state-dependent photoactivatable luminescence.Specifically,the excimer in solution is nonemissive due to its antiparallel cofacial structure.In contrast,the dimer in the crystal exhibits nonclassical excimer emission according to its cross-stacked stacking within the restriction of the crystal lattice.Prominently,the luminescent behavior in aggregate is uniquely accessible through photocycloreversion and cannot be achieved through spontaneous crystallization of their parent phenanthrene molecules.Moreover,the photoactivatable nature of these materials is successfully demonstrated in thin films,showcasing their potential applications in information encryption.This work expands the possibilities for constructing new functional aggregate materials by photochemistry and deepens our understanding of dimer-luminescence relationships in different states.展开更多
Phenols are extremely difficult to release the hydrogen radical(H^(·))due to the disfavored O-H bond dissociation energy(BDE)and undergo O-H homolysis under strong ultraviolet-C(UVC)light.In this work,we provided...Phenols are extremely difficult to release the hydrogen radical(H^(·))due to the disfavored O-H bond dissociation energy(BDE)and undergo O-H homolysis under strong ultraviolet-C(UVC)light.In this work,we provided a method to modulate the O-H BDE of phenols byπ-conjugation to electron-donating heteroaromatics.Calculations on a phenol-cored photosensitizer(BTP-1)revealed drastic declines of O-H BDE(80.5 vs.28.1 kcal mol^(-1))by comparing the ground state(S_(0))and triplet excited state(T_(1)).Consequently,BTP-1 was sensitive to visible light and generated H^(·)after O-H scission.With glutathione(GSH)serving as an ultimate H^(·)donor,the BTP-1-based photosystem was efficient in catalyzing H^(·)generation under physiological conditions.This kind of hydrogen atom-based photochemistry is distinct from traditional typeⅠ/Ⅱphotosensitizing pathways that are electron or energy transfer-based.We applied the photosystem to solve the obstacle in hypoxia-activated prodrugs(HAPs)that face a dilemma with the heterogeneously hypoxic level of tumors.In vitro studies demonstrated that the photosystem boosted the chemotherapy performance of TH-302(a representative HAP)under moderate hypoxia.With the capability to target redox bonds in HAPs and good compatibility with near-infrared two-photon laser,the photosystem is promising for cancer precision therapy.展开更多
Ion-exchangable trititanate nanotubes synthesized by the alkali treatment of TiO_(2)(anatase)are modified by MS(M=Cd,Zn)nanoparticles via a simple wet chemical process.The obtained samples are characterized by X-ray d...Ion-exchangable trititanate nanotubes synthesized by the alkali treatment of TiO_(2)(anatase)are modified by MS(M=Cd,Zn)nanoparticles via a simple wet chemical process.The obtained samples are characterized by X-ray diffraction(XRD),high-resolution transmission electron microscopy(HRTEM),and Raman spectroscopy.The photocatalytic activities of the samples are evaluated upon the oxidation of methyl orange under UV light illumination.Results show that the photoactivation may be caused by the strong coupling between the nanotube and the nanoparticles,which is a direct consequence of the ion exchange property of the trititanate wall structure during the formation of TiO_(2)/MS.展开更多
Bottle-brush polymers possessing densely grafted side chains have special properties that are distinct from linear macromolecules.Herein,an efficient method for preparing bottle-brush polymers based on a selective pho...Bottle-brush polymers possessing densely grafted side chains have special properties that are distinct from linear macromolecules.Herein,an efficient method for preparing bottle-brush polymers based on a selective photoactivation strategy in the photoinduced electron/energy transfer reversible addition-fragmentation chain transfer(PET-RAFT)polymerization was developed.A methacrylate monomer 2-(2-(dodecylthiocarbonothioylthio)propionate)ethyl methacrylate(DTPEMA)containing a 2-(dodecylthiocarbonothioylthio)propionate(DTP)unit with a secondary R group was designed.Utilizing the unique selectivity of metal naphthalocyanine photocatalyst zinc 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine(ZnTtBNc)toward trithiocarbonate with tertiary R group,the PET-RAFT polymerization of DTPEMA catalyzed by ZnTtBNc was performed under near infrared(NIR)light(λ_(max)=760 nm)irradiation at room temperature,using 4-cyano-4-[(dodecylsulfanylthiocarbonyl)-sulfanyl]pentanoic acid(CDTPA)with a tertiary R group as a chain transfer agent(CTA).Proton nuclear magnetic resonance(1H NMR)and gel permeation chromatography(GPC)results demonstrated that the DTP units in the side chains were inert during the polymerization.By grafting poly(methyl acrylate)(PMA)from PDTPEMA via thermal-initiated RAFT polymerization,welldefined P(DTPEMA-g-PMA)bottle-brush polymers could be afforded.Furthermore,the film prepared from the bottle-brush polymer exhibited excellent scratch self-healing property due to the interlocking of side chains.展开更多
The retrospective study by Edwar et al reinforces the role of therapeutic penetrating keratoplasty(PK)as a vital intervention in severe,treatment-resistant infectious keratitis.In advanced cases—often complicated by ...The retrospective study by Edwar et al reinforces the role of therapeutic penetrating keratoplasty(PK)as a vital intervention in severe,treatment-resistant infectious keratitis.In advanced cases—often complicated by trauma,delayed presentation,and corneal perforation—PK restores globe integrity and provides limited visual recovery.However,its application is constrained by graft-related complications and donor shortages,particularly in low-resource settings.These limitations highlight the need for earlier,globe-sparing strategies to prevent progression and reduce surgical demand.Photoactivated chromophore for infectious keratitis-corneal collagen cross-linking(PACK-CXL)has emerged as a promising adjunct or alternative.With both antimicrobial and tissue-stabilizing effects,PACK-CXL may control infection and preserve corneal structure in earlier stages.A layered treatment framework that incorporates PACK-CXL as an initial intervention and reserves PK for refractory cases may help improve clinical outcomes.Further studies are needed to define their best use in practice.展开更多
Great success has been witnessed in last decades,some new techniques and strategies have been widely used in drug discovery.In this roadmap,several representative techniques and strategies are highlighted to show rece...Great success has been witnessed in last decades,some new techniques and strategies have been widely used in drug discovery.In this roadmap,several representative techniques and strategies are highlighted to show recent advances in this filed.(A)A DOX protocol has been developed for accurate protein-ligand binding structure prediction,in which first principle method was used to rank the binding poses.Validation against crystal structures have found that DOX prediction achieved an impressive success rate of 99%,indicating significant improvement over molecular docking method.(B)Virtual target profiling is a compound-centric strategy enabling a parallel implementation of interrogating compounds against various targets in a single screen,which has been used in hit/lead identification,drug repositioning,and mechanism-of-action studies.Current and emerging methods for virtual target profiling are briefly summarized herein.(C)Research on targeted autophagy to treat diseases has received encouraging progress.However,due to the complexity of autophagy and disease,experimental and in silico methods should be performed synergistically for the entire process.This part focuses on in silico methods in autophagy research to promote their use in medicinal research.(D)Histone deacetylases(HDACs)play important roles in various biological functions through the deacetylation of lysine residues.Recent studies demonstrated that HDACs,which possess low deacetylase activities,exhibited more efficient defatty-acylase activities.Here,we review the defatty-acylase activity of HDACs and describe examples for the design of isoform selective HDAC inhibitor.(E)The FDA approval of three kinase allosteric inhibitors and some others entering clinical study has spurred considerable interests in this targeted drug discovery area.(F)Recent advances are reviewed in structure-based design of novel antiviral agents to combat drug resistance.(G)Since nitric oxide(NO)exerts anticancer activity depending on its concentration,optimal levels of NO in cancer cells is desirable.In this minireview,we briefly describe recent advances in the research of NO-based anticancer agents by our group and present some opinions on the future development of these agents.(H)The field of photoactivation strategies have been extensively developed for controlling chemical and biological processes with light.This review will summarize and provide insight into recent research advances in the understanding of photoactivatable molecules including photoactivatable caged prodrugs and photoswitchable molecules.展开更多
[Objective ]The aim of this study was to improve the photostability of pho-tosensitizers. [Method] 2,5-Diphenylthiophene and 2,5-dithienylethynylthiophene were synthesized by replacing thiophene rings of α-terthienyl...[Objective ]The aim of this study was to improve the photostability of pho-tosensitizers. [Method] 2,5-Diphenylthiophene and 2,5-dithienylethynylthiophene were synthesized by replacing thiophene rings of α-terthienyl （α-T） with benzene rings. Photoactivated activities on Spodoptera litura （SL） cells, singlet oxygen with UV and photostability of photosensitizers were investigated. [Result] The cytotoxicity of pho-tosensitizer 2,5-diphenylthiophene on SL cells was 0.22 and 0.16 μg/ml after treat-ment for 24 and 48 h, respectively, while that of 2,5-dithienylethynylthiophene on SL cells was 0.06 and 0.04 μg/ml. Singlet oxygen of 2,5-diphenylthiophene and 2,5-dithienylethynylthiophene was 1.047 5, 1.529 4 μg/mmol under UV, respectively. Degradation dynamic equations of 2,5-diphenylthiophene and 2,5-dithienylethynylthio-phene in methanol were Ct= 5.227 1e-0.006 1t, Ct= 5.084 2e-0.097 3t and half life was 111.79, 7.12 h. [Conclusion] Photosensitizer 2,5-diphenylthiophene has high singlet oxygen production ability, and high photoactivated cytotoxicity on SL cells under UV. Moreover, 2,5-diphenylthiophene has overcome the deficiency of photoactivated in-secticides, which is not applied directly in field because it degrades quickly in the environment.展开更多
CO_(2)reduction by CH4(CRM)to produce fuel is of great significance for solar energy storage and eliminating greenhouse gas.Herein,the catalyst of ultrafine Ni nanoparticles supported on CeZrNiO_(2)solid solution(Ni@C...CO_(2)reduction by CH4(CRM)to produce fuel is of great significance for solar energy storage and eliminating greenhouse gas.Herein,the catalyst of ultrafine Ni nanoparticles supported on CeZrNiO_(2)solid solution(Ni@CZNO)was synthesized by the sol-gel method.High yield of H_(2)and CO(58.0 and 69.8 mmol min^(-1)g^(-1))and excellent durability(50 h)were achieved by photothermal catalytic CRM merely under focused light irradiation.Structural characterization and DFT calculations reveal that CZNO has rich oxygen vacancies that can adsorb and activate CO_(2)to produce reactive oxygen species.Oxygen species are transferred to ultrafine Ni nanoparticles through the rich Ni-CZNO interface to accelerate carbon oxidation,thereby maintaining the excellent catalytic stability of the catalyst.Moreover,the experimental results reveal that light irradiation can not only enhance the photothermal catalytic CRM activity through photothermal conversion and molecular activation,but also improve the stability by increasing the concentration of oxygen vacancies and inhibiting CO disproportionation.展开更多
Optical microscopy promises researchers to soe most tiny substances directly.However,the resolution of conventional microscopy is resticted by the diffraction limit.This makes it a challenge to observe subcellular pro...Optical microscopy promises researchers to soe most tiny substances directly.However,the resolution of conventional microscopy is resticted by the diffraction limit.This makes it a challenge to observe subcellular processes happened in nanoscale.The development of super-resolution microscopy provides a solution to this challenge.Here,we briefly review several commonly used super-resolution techniques,explicating their basic principles and applications in biological science,especially in neuroscience.In addition,characteristics and limitations of each techrique are compared to provide a guidance for biologists to choose the most suitable tool.展开更多
AIM: To assess the effect of photoactivated chromophore for keratitis crosslinking(PACK-CXL) in case of severe keratitis with melting on the electrophysiological function of the retina and the optic nerve.METHODS: The...AIM: To assess the effect of photoactivated chromophore for keratitis crosslinking(PACK-CXL) in case of severe keratitis with melting on the electrophysiological function of the retina and the optic nerve.METHODS: The study included 32 eyes of 32 patients with smear positive severe infectious keratitis with corneal melting. The patients were randomly divided into two groups. Group I(control group) included 16 eyes received systemic and topical antimicrobial drugs guarded by culture and sensitivity test. Group II underwent CXL and then continued their antimicrobial treatment. Full field electroretinogram(ERG) and flash visual evoked potential(VEP) were done for each patient in both groups basically and then 1 wk, 1 and 3 mo post-treatment to assess the changes in the electrophysiological function of the retina and optic nerve.RESULTS: Healing of 10 eyes in group I in comparison to 14 eyes in group II was recorded. The mean duration of healing was 36.56±5.21 d in group I vs 20.2±4.4 d in group II(P<0.005). In group II, ERG showed an insignificant reduction of all parameters of ERG and VEP after CXL. The amplitude of scotopic rod response, oscillatory potential amplitude, flicker amplitude and photopic cone response were insignificantly decreased(P=0.4, 0.8, 0.1, and 0.3 respectively). There were insignificant prolongation of latencies of scotopic rod, oscillatory potential, flicker and photopic cone response(P=0.2, 0.7, 0.5 and 0.1). There was slight delay in latency of VEP without a significant reduction in amplitude.CONCLUSION: CXL is an effective technique in treatment of severe infectious keratitis with melting as it halts the melting process with acceptable safety on the retinal and optic nerve function.展开更多
Diazido Pt(Ⅳ)complexes with a general formula[Pt(N_(3))_(2)(L)(L’)(OR)(OR’)]are a new generation of anticancer prodrugs designed for use in photoactivated chemotherapy.The potencies of these complexes are affected ...Diazido Pt(Ⅳ)complexes with a general formula[Pt(N_(3))_(2)(L)(L’)(OR)(OR’)]are a new generation of anticancer prodrugs designed for use in photoactivated chemotherapy.The potencies of these complexes are affected by the cis/trans geometry configuration,the non-leaving ligand L/L’and derivatisation of the axial ligand OR/OR’.展开更多
In the search for new and more active anticancer drugs,light-activated compounds are emerging as effective drugs to be used in photodynamic therapy(PDT)and photoactivated chemotherapy(PACT).These clinical treatments a...In the search for new and more active anticancer drugs,light-activated compounds are emerging as effective drugs to be used in photodynamic therapy(PDT)and photoactivated chemotherapy(PACT).These clinical treatments are able to overcome severe side effects caused by the conventional Pt(Ⅱ)com plexes in chemotherapy,since the cytotoxic species are released directly into the target regions,reducing toxicity in healthy tissues.The curcumin cis-diammineplatinum(Ⅱ)complex has been proposed for PACT as it allows the controlled release of aquated diammine–platinum(Ⅱ)species as a DNA cross-linking agent and curcumin as a potential photosensitizer,thus working as a dual action anticancer agent.The curcu min ligand dissociation upon irradiation with visible light was examined by means of DFT and TD-DFT cal culations.The outcomes clearly unraveled the metal-centered triplet states 3MC as active species involved in the photocleavage of curcumin that lead to the formation of aquated platinum species and ruled out the potential activity of such a complex in the dark.展开更多
By virtue of their rich photophysical and photochemical properties,transition metal complexes(TMCs)have been extensively studied in multidisciplinary research.In this review,recent studies on TMCs for biological appli...By virtue of their rich photophysical and photochemical properties,transition metal complexes(TMCs)have been extensively studied in multidisciplinary research.In this review,recent studies on TMCs for biological applications are described with a focus on the behaviour of TMCs as specific intracellular sensors and organelle-targeting imaging reagents.Some prominent examples of TMCs as photosensitisers for in vitro and in vivo phototherapies,such as photodynamic therapy and photoactivated chemotherapy,are highlighted.Also,future development of TMCs for new diagnostic and therapeutic applications is discussed.展开更多
The insertion of metal complexes in biologically active systems is of great interest in view of diagnostic and therapeutic applications as well as a precious tool to unveil biological mechanisms. Optimization of safe ...The insertion of metal complexes in biologically active systems is of great interest in view of diagnostic and therapeutic applications as well as a precious tool to unveil biological mechanisms. Optimization of safe and biocompatible reactions is critical to achieve high functionalization efficiency. Herein we present the application of two modified versions of copper-catalyzed azide–alkyne cycloaddition (click) chemistry, namely a one-pot diazotransfer + azide–alkyne cycloaddition (one-pot click) and a copper-free photoactivated tetrazole–alkene cycloaddition (photoclick), for derivatization of peptides and peptide nucleic acids (PNAs) with ferrocene and cymantrene moieties. These metal fragments were chosen for their possible exploitation as redox and IR probes. We could demonstrate that one-pot click enables for efficient functionalization of propargyl-glycine and an alkyne-containing peptide with an amino-containing cymantrene precursor. In addition, we could show that photoclick allows for the insertion of maleimido-ferrocene into a peptide and a PNA sequence containing a tetrazole moiety.展开更多
Achieving photochromism,photodeformation,and photoinduced room-temperature phosphorescence(RTP)simultaneously in a single type of moleculedoped film is a complex and challenging task.Here,we introduce an efficient des...Achieving photochromism,photodeformation,and photoinduced room-temperature phosphorescence(RTP)simultaneously in a single type of moleculedoped film is a complex and challenging task.Here,we introduce an efficient design strategy that utilizes dicarbonyl as a bridge linking between phenothiazine(PTZ)units,thereby enabling a synergistic multi-photoresponse upon photoactivation.Our study reveals that thin films of polyvinyl alcohol(PVA)doped with five PTZ derivatives(DPTZCn:n=1–5)show photoactivated RTP.Notably,the DPTZC1 variant in PVA film uniquely undergoes photoactivated macroscopic deformation and displays enhanced photoluminescence efficiency compared to its PTZ counterparts(DPTZCn:n=2–5)in PVA films.Further photophysical analysis indicates that the exceptional performance of DPTZC1 stems from the combined effects of keto-enol tautomerism and matrix rigidification,which also facilitate the generation of photoinduced radicals in DPTZC1 in the PVA film.We investigate the potential bionic applications of the versatile DPTZC1,providing insights into the design of intelligent,photodriven materials based on RTP.展开更多
Arabidopsis phytochromes （phyA-phyE） are photoreceptors dedicated to sensing red/far-red light. Phyto- chromes promote photomorphogenic developments upon light irradiation via a signaling pathway that involves rapid...Arabidopsis phytochromes （phyA-phyE） are photoreceptors dedicated to sensing red/far-red light. Phyto- chromes promote photomorphogenic developments upon light irradiation via a signaling pathway that involves rapid degradation of PIFs （PHYTOCHROME INTERACTING FACTORS） and suppression of COP1 （CONSTITUTIVE PHOTOMORPHOGENIC 1） nuclear accumulation, through physical interactions with PIFs and COP1, respectively. Both phyA and phyB, the two best characterized phytochromes, regulate plant photomorphogenesis predominantly under far-red light and red light, respectively. It has been demonstrated that SPA1 （SUPPRESSOR OF PHYTOCHROME A 1） associates with COP1 to promote COP1 activity and suppress photomorphogenesis. Here, we report that the mechanism underlying phyB- promoted photomorphogenesis in red light involves direct physical and functional interactions between red-light-activated phyB and SPA1. We found that SPA1 acts genetically downstream of PHYB to repress photomorphogenesis in red light. Protein interaction studies in both yeast and Arabidopsis demonstrated that the photoactivated phyB represses the association of SPA1 with COP1, which is mediated, at least in part, through red-light-dependent interaction of phyB with SPA1. Moreover, we show that phyA physically interacts with SPA1 in a Pfr-form-dependent manner, and that SPA1 acts downstream of PHYA to regulate photomorphogenesis in far-red light. This study provides a genetic and biochemical model of how photo- activated phyB represses the activity of COP1-SPA1 complex through direct interaction with SPA1 to promote photomorphogenesis in red light.展开更多
Comprehensive Summary,The Haber-Bosch process,which is used for ammonia(NH3)synthesis,requires vast amounts of energy,accounting for approximately 1%—2%of the world's annual energy consumption.Therefore,researche...Comprehensive Summary,The Haber-Bosch process,which is used for ammonia(NH3)synthesis,requires vast amounts of energy,accounting for approximately 1%—2%of the world's annual energy consumption.Therefore,researchers in both industry and academia are interested in developing sustainable and environmentally friendly methods for synthesizing nitrogenous compounds at ambient conditions using renewable energy sources such as visible light.While several examples of thermal activation of dinitrogen molecules have been demonstrated using various transition metals and ligand frameworks,the use of light to weaken or split the strong N—N bond has been less explored.This article presents an overview of molecular complexes capable of dinitrogen photocleavage and provides mechanistic insights into the photoactivation process through experimental and theoretical studies.We believe this review will provide readers with an in-depth understanding of the current state-of-the-art and future research perspectives,particularly in the use of visible light for dinitrogen activation and transformation.展开更多
Ce/Sm ions are covalently grafted to a Keggin polyoxomolybdate cluster[PMo12O40]3-to yield interesting fluorescent-photodarkening molecular systems.Their photoresponce processes are observed to be activated via energy...Ce/Sm ions are covalently grafted to a Keggin polyoxomolybdate cluster[PMo12O40]3-to yield interesting fluorescent-photodarkening molecular systems.Their photoresponce processes are observed to be activated via energy transfer from luminescent fragments to photocoloration components.展开更多
The formation of molecular oxygen from water by PSⅡ is supposed to occur by meansof a linear, four-electron oxidation process involving five so-called S-state intermediates（S<sub>0</sub>→S<sub>4&l...The formation of molecular oxygen from water by PSⅡ is supposed to occur by meansof a linear, four-electron oxidation process involving five so-called S-state intermediates（S<sub>0</sub>→S<sub>4</sub>）. The Mn-cluster is considered to be ligated to the PSⅡ reaction centerpolypeptides, but for its functioning, 43 and 47ku chlorophyll proteins, three peripheralproteins of 17, 23 and 33 ku need to be associated with the lumenal surface of thylakoidmembranes. These proteins, together with Ca<sup>2+</sup> and Cl<sup>-</sup>, play a regulatory role in the effi-展开更多
基金the financial support of the Department of Science and Engineering Research Board (SERB) (Sanction Order No. CRG/2019/000112)。
文摘Room-temperature gas sensors have aroused great attention in current gas sensor technology because of deemed demand of cheap,low power consumption and portable sensors for rapidly growing Internet of things applications.As an important approach,light illumination has been exploited for room-temperature operation with improving gas sensor's attributes including sensitivity,speed and selectivity.This review provides an overview of the utilization of photoactivated nanomaterials in gas sensing field.First,recent advances in gas sensing of some exciting different nanostructures and hybrids of metal oxide semiconductors under light illumination are highlighted.Later,excellent gas sensing performance of emerging two-dimensional materialsbased sensors under light illumination is discussed in details with proposed gas sensing mechanism.Originated impressive features from the interaction of photons with sensing materials are elucidated in the context of modulating sensing characteristics.Finally,the review concludes with key and constructive insights into current and future perspectives in the light-activated nanomaterials for optoelectronic gas sensor applications.
基金supported by the National Natural Science Foundation of China(52303382,52333007)Shenzhen Key Laboratory of Functional Aggregate Materials(ZDSYS20211021111400001)+2 种基金the Science Technology Innovation Commission of Shenzhen Municipality(KQTD20210811090142053,JCYJ20220530143805012)Shenzhen Science and Technology Program(grant no.2024SC0019)the 2022 Joint Fund Project between the Second Affiliated Hospital and the Chinese University of Hong Kong,Shenzhen(Special project of AIE Center).
文摘Despite extensive investigations into photophysics at the molecular level,the complex interplays between intermolecular interactions,hierarchical assembly,and photoluminescence properties remain a fundamental challenge in materials science,particularly concerning emergent phenomena in molecular aggregates.Herein,we construct different dimeric structures in both solution and aggregate states through cycloreversion upon photoirradiation from a series of nonemissive phenanthrene cycloadducts,exhibiting state-dependent photoactivatable luminescence.Specifically,the excimer in solution is nonemissive due to its antiparallel cofacial structure.In contrast,the dimer in the crystal exhibits nonclassical excimer emission according to its cross-stacked stacking within the restriction of the crystal lattice.Prominently,the luminescent behavior in aggregate is uniquely accessible through photocycloreversion and cannot be achieved through spontaneous crystallization of their parent phenanthrene molecules.Moreover,the photoactivatable nature of these materials is successfully demonstrated in thin films,showcasing their potential applications in information encryption.This work expands the possibilities for constructing new functional aggregate materials by photochemistry and deepens our understanding of dimer-luminescence relationships in different states.
基金supported by the National Natural Science Foundation of China(22277054,22077065,21973041,22173045)the CAS-Croucher Funding Scheme for Joint Laboratories。
文摘Phenols are extremely difficult to release the hydrogen radical(H^(·))due to the disfavored O-H bond dissociation energy(BDE)and undergo O-H homolysis under strong ultraviolet-C(UVC)light.In this work,we provided a method to modulate the O-H BDE of phenols byπ-conjugation to electron-donating heteroaromatics.Calculations on a phenol-cored photosensitizer(BTP-1)revealed drastic declines of O-H BDE(80.5 vs.28.1 kcal mol^(-1))by comparing the ground state(S_(0))and triplet excited state(T_(1)).Consequently,BTP-1 was sensitive to visible light and generated H^(·)after O-H scission.With glutathione(GSH)serving as an ultimate H^(·)donor,the BTP-1-based photosystem was efficient in catalyzing H^(·)generation under physiological conditions.This kind of hydrogen atom-based photochemistry is distinct from traditional typeⅠ/Ⅱphotosensitizing pathways that are electron or energy transfer-based.We applied the photosystem to solve the obstacle in hypoxia-activated prodrugs(HAPs)that face a dilemma with the heterogeneously hypoxic level of tumors.In vitro studies demonstrated that the photosystem boosted the chemotherapy performance of TH-302(a representative HAP)under moderate hypoxia.With the capability to target redox bonds in HAPs and good compatibility with near-infrared two-photon laser,the photosystem is promising for cancer precision therapy.
基金supported by National Basic Re-search Program of China(No.2006CB933304,2006CB705602-7 and 2010CB933904)the Na-tional High Technology Research and Development Program of China(No.2007AA021803).
文摘Ion-exchangable trititanate nanotubes synthesized by the alkali treatment of TiO_(2)(anatase)are modified by MS(M=Cd,Zn)nanoparticles via a simple wet chemical process.The obtained samples are characterized by X-ray diffraction(XRD),high-resolution transmission electron microscopy(HRTEM),and Raman spectroscopy.The photocatalytic activities of the samples are evaluated upon the oxidation of methyl orange under UV light illumination.Results show that the photoactivation may be caused by the strong coupling between the nanotube and the nanoparticles,which is a direct consequence of the ion exchange property of the trititanate wall structure during the formation of TiO_(2)/MS.
基金supported by the National Natural Science Foundation of China(22201276,22131010,52021002)。
文摘Bottle-brush polymers possessing densely grafted side chains have special properties that are distinct from linear macromolecules.Herein,an efficient method for preparing bottle-brush polymers based on a selective photoactivation strategy in the photoinduced electron/energy transfer reversible addition-fragmentation chain transfer(PET-RAFT)polymerization was developed.A methacrylate monomer 2-(2-(dodecylthiocarbonothioylthio)propionate)ethyl methacrylate(DTPEMA)containing a 2-(dodecylthiocarbonothioylthio)propionate(DTP)unit with a secondary R group was designed.Utilizing the unique selectivity of metal naphthalocyanine photocatalyst zinc 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine(ZnTtBNc)toward trithiocarbonate with tertiary R group,the PET-RAFT polymerization of DTPEMA catalyzed by ZnTtBNc was performed under near infrared(NIR)light(λ_(max)=760 nm)irradiation at room temperature,using 4-cyano-4-[(dodecylsulfanylthiocarbonyl)-sulfanyl]pentanoic acid(CDTPA)with a tertiary R group as a chain transfer agent(CTA).Proton nuclear magnetic resonance(1H NMR)and gel permeation chromatography(GPC)results demonstrated that the DTP units in the side chains were inert during the polymerization.By grafting poly(methyl acrylate)(PMA)from PDTPEMA via thermal-initiated RAFT polymerization,welldefined P(DTPEMA-g-PMA)bottle-brush polymers could be afforded.Furthermore,the film prepared from the bottle-brush polymer exhibited excellent scratch self-healing property due to the interlocking of side chains.
文摘The retrospective study by Edwar et al reinforces the role of therapeutic penetrating keratoplasty(PK)as a vital intervention in severe,treatment-resistant infectious keratitis.In advanced cases—often complicated by trauma,delayed presentation,and corneal perforation—PK restores globe integrity and provides limited visual recovery.However,its application is constrained by graft-related complications and donor shortages,particularly in low-resource settings.These limitations highlight the need for earlier,globe-sparing strategies to prevent progression and reduce surgical demand.Photoactivated chromophore for infectious keratitis-corneal collagen cross-linking(PACK-CXL)has emerged as a promising adjunct or alternative.With both antimicrobial and tissue-stabilizing effects,PACK-CXL may control infection and preserve corneal structure in earlier stages.A layered treatment framework that incorporates PACK-CXL as an initial intervention and reserves PK for refractory cases may help improve clinical outcomes.Further studies are needed to define their best use in practice.
基金This work was supported by grants from the National Natural Science Foundation of China(Nos.81973173 and 81773571),Jiangsu Province Funds for Excellent Young Scientists(No.BK20170088),the Six Talent Peaks Project(No.YY-023)and the 333 Project of Jiangsu Province.
文摘Great success has been witnessed in last decades,some new techniques and strategies have been widely used in drug discovery.In this roadmap,several representative techniques and strategies are highlighted to show recent advances in this filed.(A)A DOX protocol has been developed for accurate protein-ligand binding structure prediction,in which first principle method was used to rank the binding poses.Validation against crystal structures have found that DOX prediction achieved an impressive success rate of 99%,indicating significant improvement over molecular docking method.(B)Virtual target profiling is a compound-centric strategy enabling a parallel implementation of interrogating compounds against various targets in a single screen,which has been used in hit/lead identification,drug repositioning,and mechanism-of-action studies.Current and emerging methods for virtual target profiling are briefly summarized herein.(C)Research on targeted autophagy to treat diseases has received encouraging progress.However,due to the complexity of autophagy and disease,experimental and in silico methods should be performed synergistically for the entire process.This part focuses on in silico methods in autophagy research to promote their use in medicinal research.(D)Histone deacetylases(HDACs)play important roles in various biological functions through the deacetylation of lysine residues.Recent studies demonstrated that HDACs,which possess low deacetylase activities,exhibited more efficient defatty-acylase activities.Here,we review the defatty-acylase activity of HDACs and describe examples for the design of isoform selective HDAC inhibitor.(E)The FDA approval of three kinase allosteric inhibitors and some others entering clinical study has spurred considerable interests in this targeted drug discovery area.(F)Recent advances are reviewed in structure-based design of novel antiviral agents to combat drug resistance.(G)Since nitric oxide(NO)exerts anticancer activity depending on its concentration,optimal levels of NO in cancer cells is desirable.In this minireview,we briefly describe recent advances in the research of NO-based anticancer agents by our group and present some opinions on the future development of these agents.(H)The field of photoactivation strategies have been extensively developed for controlling chemical and biological processes with light.This review will summarize and provide insight into recent research advances in the understanding of photoactivatable molecules including photoactivatable caged prodrugs and photoswitchable molecules.
基金Supported by Science and Technology Support Program of Jiangsu Province(Agricultural Project)(BE2012346)Science and Technology Projects for Social Development of Yangzhou City,China(2012110)Natural Science Foundation of the Jiangsu Higher Education Institutions of China(13KJB210010)~~
文摘[Objective ]The aim of this study was to improve the photostability of pho-tosensitizers. [Method] 2,5-Diphenylthiophene and 2,5-dithienylethynylthiophene were synthesized by replacing thiophene rings of α-terthienyl （α-T） with benzene rings. Photoactivated activities on Spodoptera litura （SL） cells, singlet oxygen with UV and photostability of photosensitizers were investigated. [Result] The cytotoxicity of pho-tosensitizer 2,5-diphenylthiophene on SL cells was 0.22 and 0.16 μg/ml after treat-ment for 24 and 48 h, respectively, while that of 2,5-dithienylethynylthiophene on SL cells was 0.06 and 0.04 μg/ml. Singlet oxygen of 2,5-diphenylthiophene and 2,5-dithienylethynylthiophene was 1.047 5, 1.529 4 μg/mmol under UV, respectively. Degradation dynamic equations of 2,5-diphenylthiophene and 2,5-dithienylethynylthio-phene in methanol were Ct= 5.227 1e-0.006 1t, Ct= 5.084 2e-0.097 3t and half life was 111.79, 7.12 h. [Conclusion] Photosensitizer 2,5-diphenylthiophene has high singlet oxygen production ability, and high photoactivated cytotoxicity on SL cells under UV. Moreover, 2,5-diphenylthiophene has overcome the deficiency of photoactivated in-secticides, which is not applied directly in field because it degrades quickly in the environment.
基金supported by the National Natural Science Foundation of China(22202121,22005340)Shandong Provincial Natural Science Foundation(ZR2021QB079).
文摘CO_(2)reduction by CH4(CRM)to produce fuel is of great significance for solar energy storage and eliminating greenhouse gas.Herein,the catalyst of ultrafine Ni nanoparticles supported on CeZrNiO_(2)solid solution(Ni@CZNO)was synthesized by the sol-gel method.High yield of H_(2)and CO(58.0 and 69.8 mmol min^(-1)g^(-1))and excellent durability(50 h)were achieved by photothermal catalytic CRM merely under focused light irradiation.Structural characterization and DFT calculations reveal that CZNO has rich oxygen vacancies that can adsorb and activate CO_(2)to produce reactive oxygen species.Oxygen species are transferred to ultrafine Ni nanoparticles through the rich Ni-CZNO interface to accelerate carbon oxidation,thereby maintaining the excellent catalytic stability of the catalyst.Moreover,the experimental results reveal that light irradiation can not only enhance the photothermal catalytic CRM activity through photothermal conversion and molecular activation,but also improve the stability by increasing the concentration of oxygen vacancies and inhibiting CO disproportionation.
基金support from National Basic Research Program of China (973 Program) (2015CB352005)National Natural Science Foundation of China (No.6142780065,31571110,81527901)+1 种基金Natural Science Foundation of Zhejiang Province of China (No.Y16F050002)the Fundamental Research Funds for the Central Universities.
文摘Optical microscopy promises researchers to soe most tiny substances directly.However,the resolution of conventional microscopy is resticted by the diffraction limit.This makes it a challenge to observe subcellular processes happened in nanoscale.The development of super-resolution microscopy provides a solution to this challenge.Here,we briefly review several commonly used super-resolution techniques,explicating their basic principles and applications in biological science,especially in neuroscience.In addition,characteristics and limitations of each techrique are compared to provide a guidance for biologists to choose the most suitable tool.
文摘AIM: To assess the effect of photoactivated chromophore for keratitis crosslinking(PACK-CXL) in case of severe keratitis with melting on the electrophysiological function of the retina and the optic nerve.METHODS: The study included 32 eyes of 32 patients with smear positive severe infectious keratitis with corneal melting. The patients were randomly divided into two groups. Group I(control group) included 16 eyes received systemic and topical antimicrobial drugs guarded by culture and sensitivity test. Group II underwent CXL and then continued their antimicrobial treatment. Full field electroretinogram(ERG) and flash visual evoked potential(VEP) were done for each patient in both groups basically and then 1 wk, 1 and 3 mo post-treatment to assess the changes in the electrophysiological function of the retina and optic nerve.RESULTS: Healing of 10 eyes in group I in comparison to 14 eyes in group II was recorded. The mean duration of healing was 36.56±5.21 d in group I vs 20.2±4.4 d in group II(P<0.005). In group II, ERG showed an insignificant reduction of all parameters of ERG and VEP after CXL. The amplitude of scotopic rod response, oscillatory potential amplitude, flicker amplitude and photopic cone response were insignificantly decreased(P=0.4, 0.8, 0.1, and 0.3 respectively). There were insignificant prolongation of latencies of scotopic rod, oscillatory potential, flicker and photopic cone response(P=0.2, 0.7, 0.5 and 0.1). There was slight delay in latency of VEP without a significant reduction in amplitude.CONCLUSION: CXL is an effective technique in treatment of severe infectious keratitis with melting as it halts the melting process with acceptable safety on the retinal and optic nerve function.
基金supported by the MRC(grant G0701062)EPSRC(grants EP/G006792,EP/F034210/1,EP/P030572/1 to PJS),ERC(grant 247450 to PJS)a Chancellor’s International PhD Scholarship from the University of Warwick(for HS),and the Wellcome Trust(209173/Z/17/Z,Sir Henry Wellcome Fellowship for CI).
文摘Diazido Pt(Ⅳ)complexes with a general formula[Pt(N_(3))_(2)(L)(L’)(OR)(OR’)]are a new generation of anticancer prodrugs designed for use in photoactivated chemotherapy.The potencies of these complexes are affected by the cis/trans geometry configuration,the non-leaving ligand L/L’and derivatisation of the axial ligand OR/OR’.
文摘In the search for new and more active anticancer drugs,light-activated compounds are emerging as effective drugs to be used in photodynamic therapy(PDT)and photoactivated chemotherapy(PACT).These clinical treatments are able to overcome severe side effects caused by the conventional Pt(Ⅱ)com plexes in chemotherapy,since the cytotoxic species are released directly into the target regions,reducing toxicity in healthy tissues.The curcumin cis-diammineplatinum(Ⅱ)complex has been proposed for PACT as it allows the controlled release of aquated diammine–platinum(Ⅱ)species as a DNA cross-linking agent and curcumin as a potential photosensitizer,thus working as a dual action anticancer agent.The curcu min ligand dissociation upon irradiation with visible light was examined by means of DFT and TD-DFT cal culations.The outcomes clearly unraveled the metal-centered triplet states 3MC as active species involved in the photocleavage of curcumin that lead to the formation of aquated platinum species and ruled out the potential activity of such a complex in the dark.
基金funding support from the Hong Kong Research Grants Council(Project No.CityU 11300017,CityU 11300318,CityU 11300019,CityU 11302820 and T42-103/16-N)“Laboratory for Synthetic Chemistry and Chemical Biology”under the Health@InnoHK Program launched by Innovation and Technology Commission,The Government of Hong Kong Special Administrative Region of the People’s Republic of China+1 种基金the receipt of a Postgraduate Studentship administered by City University of Hong Kongthe receipt of a Hong Kong PhD Fellowship administered by the Research Grants Council of Hong Kong Special Administrative Region of the People’s Republic of China.
文摘By virtue of their rich photophysical and photochemical properties,transition metal complexes(TMCs)have been extensively studied in multidisciplinary research.In this review,recent studies on TMCs for biological applications are described with a focus on the behaviour of TMCs as specific intracellular sensors and organelle-targeting imaging reagents.Some prominent examples of TMCs as photosensitisers for in vitro and in vivo phototherapies,such as photodynamic therapy and photoactivated chemotherapy,are highlighted.Also,future development of TMCs for new diagnostic and therapeutic applications is discussed.
基金supported by the Swiss National Science Foundation(Ambizione Fellowship No.PZ00P2_126404 as well as Professorships No.PP00P2_133568 and PP00P2_157545 to G.G)the University of Zurich(G.G)+1 种基金the Stiftung für wissenschaftliche Forschung of the University of Zurich(G.G.)the Forschungskredit of the University of Zurich(Grant K-73532-01-01 to C.M).
文摘The insertion of metal complexes in biologically active systems is of great interest in view of diagnostic and therapeutic applications as well as a precious tool to unveil biological mechanisms. Optimization of safe and biocompatible reactions is critical to achieve high functionalization efficiency. Herein we present the application of two modified versions of copper-catalyzed azide–alkyne cycloaddition (click) chemistry, namely a one-pot diazotransfer + azide–alkyne cycloaddition (one-pot click) and a copper-free photoactivated tetrazole–alkene cycloaddition (photoclick), for derivatization of peptides and peptide nucleic acids (PNAs) with ferrocene and cymantrene moieties. These metal fragments were chosen for their possible exploitation as redox and IR probes. We could demonstrate that one-pot click enables for efficient functionalization of propargyl-glycine and an alkyne-containing peptide with an amino-containing cymantrene precursor. In addition, we could show that photoclick allows for the insertion of maleimido-ferrocene into a peptide and a PNA sequence containing a tetrazole moiety.
基金the National Natural Science Foundation of China(grant no.22235006)the RIE2025 Manufacturing,Trade,and Connectivity Programmatic Fund(award no.M21J9b0085)+2 种基金the National Research Foundationthe Prime Minister’s Office of Singapore under its Competitive Research Program(award no.NRF-CRP23-2019-0002)the National Research Foundation(NRF)Investigatorship Programme(award no.NRF-NRFI05-2019-0003).
文摘Achieving photochromism,photodeformation,and photoinduced room-temperature phosphorescence(RTP)simultaneously in a single type of moleculedoped film is a complex and challenging task.Here,we introduce an efficient design strategy that utilizes dicarbonyl as a bridge linking between phenothiazine(PTZ)units,thereby enabling a synergistic multi-photoresponse upon photoactivation.Our study reveals that thin films of polyvinyl alcohol(PVA)doped with five PTZ derivatives(DPTZCn:n=1–5)show photoactivated RTP.Notably,the DPTZC1 variant in PVA film uniquely undergoes photoactivated macroscopic deformation and displays enhanced photoluminescence efficiency compared to its PTZ counterparts(DPTZCn:n=2–5)in PVA films.Further photophysical analysis indicates that the exceptional performance of DPTZC1 stems from the combined effects of keto-enol tautomerism and matrix rigidification,which also facilitate the generation of photoinduced radicals in DPTZC1 in the PVA film.We investigate the potential bionic applications of the versatile DPTZC1,providing insights into the design of intelligent,photodriven materials based on RTP.
文摘Arabidopsis phytochromes （phyA-phyE） are photoreceptors dedicated to sensing red/far-red light. Phyto- chromes promote photomorphogenic developments upon light irradiation via a signaling pathway that involves rapid degradation of PIFs （PHYTOCHROME INTERACTING FACTORS） and suppression of COP1 （CONSTITUTIVE PHOTOMORPHOGENIC 1） nuclear accumulation, through physical interactions with PIFs and COP1, respectively. Both phyA and phyB, the two best characterized phytochromes, regulate plant photomorphogenesis predominantly under far-red light and red light, respectively. It has been demonstrated that SPA1 （SUPPRESSOR OF PHYTOCHROME A 1） associates with COP1 to promote COP1 activity and suppress photomorphogenesis. Here, we report that the mechanism underlying phyB- promoted photomorphogenesis in red light involves direct physical and functional interactions between red-light-activated phyB and SPA1. We found that SPA1 acts genetically downstream of PHYB to repress photomorphogenesis in red light. Protein interaction studies in both yeast and Arabidopsis demonstrated that the photoactivated phyB represses the association of SPA1 with COP1, which is mediated, at least in part, through red-light-dependent interaction of phyB with SPA1. Moreover, we show that phyA physically interacts with SPA1 in a Pfr-form-dependent manner, and that SPA1 acts downstream of PHYA to regulate photomorphogenesis in far-red light. This study provides a genetic and biochemical model of how photo- activated phyB represses the activity of COP1-SPA1 complex through direct interaction with SPA1 to promote photomorphogenesis in red light.
基金the National Natural Science Foundation of China(Nos.21988101 and 22201013)Beijing Natural Science Foundation(No.2222008).
文摘Comprehensive Summary,The Haber-Bosch process,which is used for ammonia(NH3)synthesis,requires vast amounts of energy,accounting for approximately 1%—2%of the world's annual energy consumption.Therefore,researchers in both industry and academia are interested in developing sustainable and environmentally friendly methods for synthesizing nitrogenous compounds at ambient conditions using renewable energy sources such as visible light.While several examples of thermal activation of dinitrogen molecules have been demonstrated using various transition metals and ligand frameworks,the use of light to weaken or split the strong N—N bond has been less explored.This article presents an overview of molecular complexes capable of dinitrogen photocleavage and provides mechanistic insights into the photoactivation process through experimental and theoretical studies.We believe this review will provide readers with an in-depth understanding of the current state-of-the-art and future research perspectives,particularly in the use of visible light for dinitrogen activation and transformation.
基金supported by the National Natural Science Foundation of China(50971063)the Natural Science Foundation of Fujian Province of China(2003F006,2010J01042)the Scientific Research Foundation for Returned Overseas Chinese Scholars of the State Education Ministry of China
文摘Ce/Sm ions are covalently grafted to a Keggin polyoxomolybdate cluster[PMo12O40]3-to yield interesting fluorescent-photodarkening molecular systems.Their photoresponce processes are observed to be activated via energy transfer from luminescent fragments to photocoloration components.
基金Project supported by the National Natural Science Foundation of China.
文摘The formation of molecular oxygen from water by PSⅡ is supposed to occur by meansof a linear, four-electron oxidation process involving five so-called S-state intermediates（S<sub>0</sub>→S<sub>4</sub>）. The Mn-cluster is considered to be ligated to the PSⅡ reaction centerpolypeptides, but for its functioning, 43 and 47ku chlorophyll proteins, three peripheralproteins of 17, 23 and 33 ku need to be associated with the lumenal surface of thylakoidmembranes. These proteins, together with Ca<sup>2+</sup> and Cl<sup>-</sup>, play a regulatory role in the effi-
