Introduction:One of the main events that regulate a cell’s well-being is cell-to-cell communication.This intercellular mechanism of information transfer is often mediated by vesicular trafficking.Mitochondrial-derive...Introduction:One of the main events that regulate a cell’s well-being is cell-to-cell communication.This intercellular mechanism of information transfer is often mediated by vesicular trafficking.Mitochondrial-derived vesicles(MDVs)are an emerging subpopulation of extracellular vesicle(EV)first discovered in 2008 that allow mitochondria to communicate with their surroundings.展开更多
Ischemic stroke(IS)presents a major threat to human life and health due to its high disability and mortality rates.3-n-Butylphthalide(NBP),derived from celery seeds of the Apiaceae family native to the Mediterranean r...Ischemic stroke(IS)presents a major threat to human life and health due to its high disability and mortality rates.3-n-Butylphthalide(NBP),derived from celery seeds of the Apiaceae family native to the Mediterranean region,was first introduced in China for acute IS treatment in 2004.NBP demonstrates multiple therapeutic actions,including reconstruction of microcirculation in the cerebral ischemia area,inhibition of platelet aggregation,reduction of cerebral infarction volume,maintenance of blood-brain barrier(BBB)integrity,and enhancement of cerebral blood perfusion.However,its overall efficacy remains moderate,limited by poor water solubility and low bioavailability,which constrains its clinical application.To address these limitations,researchers have actively pursued the development of NBP derivatives and analogs,achieving notable progress.These efforts,including substituent introduction,ring opening derivatization,esterification,and atom substitution,have generated diverse NBP derivatives.Several of these derivatives have advanced to clinical studies.Specifically,potassium 2-(1-hydroxypentyl)-benzoate(PHPB),brozopentyl sodium(BZP),and XY-03-EA(ZONK1103)have reached phase II clinical trials,while(S)-2-(1-acetoxypentyl)benzoic acid L-arginine salt(AAPB)has received clinical trial approval for 2024.This review examines the structural modification and optimization of NBP over the past two decades from a medicinal chemistry perspective,aiming to facilitate the development of superior derivatives and advance cerebral ischemia treatment.展开更多
In this paper,we investigate the problem of describing the form of Jordan triple derivations on trivial extension algebras.We show that every Jordan triple derivation on a 2-torsion free *-type trivial extension algeb...In this paper,we investigate the problem of describing the form of Jordan triple derivations on trivial extension algebras.We show that every Jordan triple derivation on a 2-torsion free *-type trivial extension algebra is a sum of a derivation and an antiderivation.As its applications,Jordan triple derivations on triangular algebras are characterized.展开更多
Lithium(Li)is an‘emerging'environmental pollutant,especially in soil,which is a great concern because it can endanger human health through the food chain.Compared with traditional chemical analyses,hyperspectral ...Lithium(Li)is an‘emerging'environmental pollutant,especially in soil,which is a great concern because it can endanger human health through the food chain.Compared with traditional chemical analyses,hyperspectral techniques have achieved many exciting results in soil metal monitoring due to their advantages of being fast and non-destructive.However,insufficient attention has been paid to lithium in soil,and the feasibility of its estimation using hyperspectral techniques needs to be investigated.We studied 97 soil samples from claytype lithium mines in the Ertanggou area of the East Tianshan Mountains of Xinjiang to explore the effects of spectral resolution,fractional order derivatives(FOD),and characteristic band selection on the estimation accuracy of clay Li content,to obtain a fast and effective method for estimating clay Li content.Finally,we developed a new method for rapid and nondestructive estimation of soil lithium content.We have obtained some important results from the study.Spectral resolution exerts a significant impact on model performance,and its reduction usually leads to a decline in model performance.For the full band,the models constructed with low-order derivatives were superior to those with high-order derivatives,and the best model was obtained at the 0.4-order derivative(coefficient of determination(R^(2))and relative predictive deviation(RPD)of 0.777 and 2.118,respectively).In the characteristic bands,the lower order is sensitive to the visible-near-infrared range,and the higher order is sensitive to the short-wave infrared range,and the model constructed with the higher-order derivatives outperforms the lower-order derivatives.In this study,the combination of FOD and Random Forest(RF)can significantly improve the model performance,with R^(2),Relative Root Mean Squared Error(RRMSE),and RPD being 0.849,1.526,and 2.574,respectively.Therefore,this research provides a theoretical basis and technical reference for imaging hyperspectral exploration of anomalous areas of clay-type Li resources.展开更多
Background:Myeloid-derived suppressor cells(MDSCs)are important tumor microenvironment components in small cell lung cancer(SCLC).We successfully identified MDSCs expressing the surface marker CD33 in SCLC;nonetheless...Background:Myeloid-derived suppressor cells(MDSCs)are important tumor microenvironment components in small cell lung cancer(SCLC).We successfully identified MDSCs expressing the surface marker CD33 in SCLC;nonetheless,whether CD33^(+)MDSCs promote SCLC angiogenesis remains unclear.This study aims to explore the angiogenic effect and clinical significance of CD33^(+)MDSCs derived from SCLC.Method:Nineteen patients diagnosed with extensive-stage SCLC at Jilin Cancer Hospital were selected as the research subjects.CD33^(+)MDSCs were isolated from the peripheral blood of patients with SCLC using magnetic bead separation and CD33 expression was detected by flow cytometry.The angiogenic potential of CD33^(+)MDSCs derived from the peripheral blood of patients with SCLC and healthy individuals was assessed using human umbilical vein endothelial cell(HUVEC)angiogenesis assays,and the clinical significance of CD33^(+)MDSCs in promoting angiogenesis in patients with SCLC was analyzed using clinical data.Results:Compared to healthy individuals,the CD33^(+)MDSCs(CD14^(+)CD33^(+))isolated from the peripheral blood of SCLC patients exhibited a greater ability to promote HUVEC tubular growth(average vessel length:57.60 mm[47.78 mm]vs.39.07 mm[15.84 mm],p=0.000;vessel area:371,890 mm^(3)[699,927 mm^(3)]vs.334,652 mm^(3)[219,520 mm^(3)],p<0.000;total number of junctions:141[301]vs.120[94],p<0.005),and their angiogenic ability was associated with older age,female sex,high performance status scores,no systematic treatment,and treatment unresponsiveness(p<0.050).Furthermore,the enhanced angiogenic ability of CD33^(+)MDSCs may represent a risk factor for treatment unresponsiveness(average vessel length:Odds ratio=3.904,95%CI=1.812-8.409,p=0.001;vessel area:Odds ratio=2.501,95%CI=1.187-5.267,p=0.016;total number of junctions:Odds ratio=3.630,95%CI=1.686-7.815,p=0.001)and is associated with a poor SCLC prognosis(average vessel length:Hazard ratio=2.210,95%CI=1.299-3.758,p=0.003;vessel area:Hazard ratio=2.170,95%CI=1.274-3.693,p=0.004;total number of junctions:Hazard ratio=2.267,95%CI=1.333-3.853,p=0.003).Conclusion:CD33^(+)MDSCs derived from the peripheral blood of patients with SCLC promote angiogenesis,which is a risk factor for treatment unresponsiveness and is associated with poor prognosis.展开更多
Mitophagy is a well-characterized and redundant recycling system for damaged mitochondria and a marker of organelle quality(Picca et al.,2023).Yet,the assessment of mitophagy in vivo remains a challenge.The characteri...Mitophagy is a well-characterized and redundant recycling system for damaged mitochondria and a marker of organelle quality(Picca et al.,2023).Yet,the assessment of mitophagy in vivo remains a challenge.The characterization of the endosomallysosomal pathways supporting the endocytic tra fficking has provided invaluable information also into mitophagy signaling.展开更多
The thermal decomposition characteristic of ammonium perchlorate(AP)represents a critical factor in determining the performance of solid propellants,which has aroused significant interest on the structure and performa...The thermal decomposition characteristic of ammonium perchlorate(AP)represents a critical factor in determining the performance of solid propellants,which has aroused significant interest on the structure and performance improvement of kinds of catalysts.In this study,bimetallic metal-organic frameworks(MOFs),such as CuCo-BTC(BTC=1,3,5-Benzenetricarboxylic acid,H_(3)BTC),CuNi-BTC,and CoNi-BTC,were synthesized by solvothermal(ST)and spray-drying(SD)methods,and then calcined at 400℃for 2 h to form metal oxides.The catalysts as well as their catalytic effects for AP decomposition were characterized by FTIR,XRD,SEM,XPS,TG,DSC,TG-IR,EIS,CV,and LSV.It was found that the rapid coordination of metal ions with ligands during spray drying may lead to catalytic structural defects,promoting the exposure of reactive active sites and increasing the catalytic active region.The results showed that the addition of 2 wt%binary transition metal oxides(BTMOs)as catalysts significantly reduced the high-temperature decomposition(HTD)temperature of AP and enhanced its heat release.Of particular significance is the observation that SD-CoNiO_(x),prepared by spray-drying,reduced the decomposition temperature of AP from 413.26℃(pure AP)to 306℃and enhanced the heat release from 256.79 J/g(pure AP)to 1496.82 J/g,while concomitantly reducing the activation energy by 42%.By analysing the gaseous products during the decomposition of AP+SD-CoNiO_(x)and AP+ST-CoNiO_(x),it was found that SD-CoNiO_(x)could significantly increase the content of high-valent nitrogen oxides during the AP decomposition reaction,which indicates that the BTMOs prepared by spray-drying in the reaction system are more conducive to accelerating the electron transfer in the thermal decomposition process of AP,and can provide a high concentration of reactive oxygen species that oxidize AP to high-valent nitrogen oxide-containing compounds.The present study shows that the structure selectivity of the spray-drying technique influences surfactant molecular arrangement on catalyst surfaces,resulting in their ability to promote higher electron transfer during the catalytic process.Therefore,BTMOs prepared by spray drying method have higher potential for application.展开更多
Two viologen derivatives containing fluorine substituent(F)with an asymmetric structures,1,1'-bis(4-(trifluoromethyl)phenyl)-[4,4'-bipyridine]dihexafluorophosphate(DFPV)and 1-benzyl-1'-(4-(trifluoromethyl)...Two viologen derivatives containing fluorine substituent(F)with an asymmetric structures,1,1'-bis(4-(trifluoromethyl)phenyl)-[4,4'-bipyridine]dihexafluorophosphate(DFPV)and 1-benzyl-1'-(4-(trifluoromethyl)phenyl)-[4,4'-bipyridine]di-hexafluorophosphate(Bn-FPV),were synthesized.These viologen derivatives as active materials were used to assemble both flexible and rigid electrochromic devices(ECDs).ECDs based on DFPV exhibited reversible color change from colorless to deep green and ECDs based on Bn-FPV exhibited reversible color change from colorless to blue-green within applied voltage.It was found that the devices based on DFPV showed cycle stability,which could still maintain more than 90% after 1000 cycles.In addition,the modulation rate of the device to the solar irradiance is also calculated to characterize its application potential in smart windows.Among them,the rigid device(R-DFPV)based on the DFPV has a large solar irradiance modulation rate of 54.66%,which has the potential to be used as smart windows.展开更多
Sulfur dioxide(SO_(2)) and its derivatives have been recognized as harmful environmental pollutants.However,they are often produced during the processing of traditional Chinese medicines,potentially compromising the q...Sulfur dioxide(SO_(2)) and its derivatives have been recognized as harmful environmental pollutants.However,they are often produced during the processing of traditional Chinese medicines,potentially compromising the quality of these medicinal materials and contributing to various health issues.Due to a lack of effective monitoring and imaging tools,the physiological effects of excessive SO_(2) residues in traditional Chinese medicine remain unclear.Therefore,developing a rapid and effective tool for detecting SO_(2) is crucial for understanding its metabolic pathways and effects in vivo.In this study,we developed a near infrared(NIR) and ratiometric fluorescent probe,NIR-RS,which exhibits high sensitivity,selectivity,and rapid response for SO_(2) detection.Notably,NIR-RS accurately quantifies SO_(2) contents in Pinelliae rhizoma(P.rhizoma) samples,with recovery rates from 98.46 % to 102.40 %,and relative standard deviations(RSDs)< 5.0 %.For bioimaging applications,NIR-RS has low cytotoxicity and good mitochondrial-targeting ability,making it suitable for imaging exogenous and endogenous SO_(2) in mitochondria.Additionally,NIR-RS was successfully applied to image SO_(2) content of P.rhizoma samples within cells,revealing that high SO_(2) residue elevated mitochondria adenosine triphosphate(ATP) content,these findings reveal that P.rhizoma with excessive SO_(2) can affect the organism's growth mechanisms through alterations in ATP pathways.In vivo,SO_(2) was found to predominantly accumulate in the liver following gavage with P.rhizoma solution,with accumulation levels increasing in proportion to SO_(2) residue concentration.High SO_(2) concentrations in P.rhizoma can cause pulmonary fibrosis and gastric mucosal damage.This work provides a valuable tool for regulating SO_(2) content in P.rhizoma and may help researcher better understand the metabolism of SO_(2) derivatives and explore their physiological roles in biological systems.展开更多
Rational design of non-noble electrocatalysts with high performance for oxygen evolution reaction(OER)still remains a challenge.In this study,a ZIF-derived electrocatalyst(Co@Fe-P)with a core-shell structure is design...Rational design of non-noble electrocatalysts with high performance for oxygen evolution reaction(OER)still remains a challenge.In this study,a ZIF-derived electrocatalyst(Co@Fe-P)with a core-shell structure is designed by using Co-compounds as the core and PO_(4)^(3-)decorated Fe-compounds as the shell.The inner Co-core and outer Fe-shell are connected through Co-O-Fe and Fe-O-P linkage.The Co@Fe-P electrocatalyst exhibits an enhanced performance for OER with a low overpotential(280 mV),low Tafel slope(41.9 mV dec^(-1))at 10 mA cm^(-2),and a 60-h durability.The electron transfer from the CoOOH-core to the FeOOH-shell is greatly facilitated,which improves the OER activity of Co@Fe-P kinetically.Theoretical calculations indicate that the interaction of Co-O-Fe and Fe-O-P in Co@Fe-P reduces the overlap between the O 2p and Fe 3d orbitals,which greatly facilitates the transformation from*OH to*O during the OER process via the adsorbate evolution mechanism(AEM)pathway.This finding provides insight for the design of efficient electrocatalysts for OER.展开更多
Neuroinflammation is a key process in the pathogenesis of various neurodegenerative diseases,such as multiple sclerosis(MS),Alzheimer's disease,and traumatic brain injury.Even for disorders historically unrelated ...Neuroinflammation is a key process in the pathogenesis of various neurodegenerative diseases,such as multiple sclerosis(MS),Alzheimer's disease,and traumatic brain injury.Even for disorders historically unrelated to neuroinflammation,such as Alzheimer's disease,it is now shown to precede pathological protein aggregations.展开更多
Endochondral ossification is a physiological process involving a sequential formation of cartilage and bone tissues.Classically,cartilage and bone formation have been considered independent processes at cellular level...Endochondral ossification is a physiological process involving a sequential formation of cartilage and bone tissues.Classically,cartilage and bone formation have been considered independent processes at cellular level.However,the recently described multiple cell differentiation dynamics suggest that some bone cells are indeed the progeny of cartilage cells,or chondrocyte-derived osteoblasts.We hypothesized that the cartilage-to-bone phenotype transition is triggered by specific molecular events.First,the process was assessed in mouse bone tissue,and then,it was mimicked using in vivo cell implantation and in vitro serial differentiation protocols.Data indicates that cartilage cells transition to bone cell phenotype during postnatal physiological bone formation.This process can be reproduced using cartilage precursor cells coupled to specific implantation procedures or differentiation protocols.Gene expression profiling reveals that NOTCH,BMP and MAPK signaling pathways are relevant at the phenotype-switch,while the transcription factors Mesp1,Alx1,Grhl3 and Hmx3 are the feasible driver genes for chondrocyte-derived osteoblasts formation.Altogether,this report shows that endochondral ossification can be modeled using primary cell cultures and data indicate that this process is regulated by specific molecular events,previously described at skeleton morphogenesis during embryo development,and from now on also linkable to postnatal bone development and regeneration processes.展开更多
This paper introduces a novel fractional-order model based on the Caputo-Fabrizio(CF)derivative for analyzing computer virus propagation in networked environments.The model partitions the computer population into four...This paper introduces a novel fractional-order model based on the Caputo-Fabrizio(CF)derivative for analyzing computer virus propagation in networked environments.The model partitions the computer population into four compartments:susceptible,latently infected,breaking-out,and antivirus-capable systems.By employing the CF derivative—which uses a nonsingular exponential kernel—the framework effectively captures memory-dependent and nonlocal characteristics intrinsic to cyber systems,aspects inadequately represented by traditional integer-order models.Under Lipschitz continuity and boundedness assumptions,the existence and uniqueness of solutions are rigorously established via fixed-point theory.We develop a tailored two-step Adams-Bashforth numerical scheme for the CF framework and prove its second-order accuracy.Extensive numerical simulations across various fractional orders reveal that memory effects significantly influence virus transmission and control dynamics;smaller fractional orders produce more pronounced memory effects,delaying both infection spread and antivirus activation.Further theoretical analysis,including Hyers-Ulam stability and sensitivity assessments,reinforces the model’s robustness and identifies key parameters governing virus dynamics.The study also extends the framework to incorporate stochastic effects through a stochastic CF formulation.These results underscore fractional-order modeling as a powerful analytical tool for developing robust and effective cybersecurity strategies.展开更多
Neurodegenerative disorders represent an increasingly pertinent public health crisis.As a greater proportion of the population ages,neurodegenerative disorders and other diseases of aging place undue burdens on patien...Neurodegenerative disorders represent an increasingly pertinent public health crisis.As a greater proportion of the population ages,neurodegenerative disorders and other diseases of aging place undue burdens on patients,caregivers,and healthcare workers.Alzheimer’s disease(AD)and Parkinson’s disease represent the two most common neurodegenerative disorders in the population,affecting over 65 million people,worldwide.展开更多
Previous research has demonstrated the feasibility of repairing nerve defects through acellular allogeneic nerve grafting with bone marrow mesenchymal stem cells.However,adult tissue–derived mesenchymal stem cells en...Previous research has demonstrated the feasibility of repairing nerve defects through acellular allogeneic nerve grafting with bone marrow mesenchymal stem cells.However,adult tissue–derived mesenchymal stem cells encounter various obstacles,including limited tissue sources,invasive acquisition methods,cellular heterogeneity,purification challenges,cellular senescence,and diminished pluripotency and proliferation over successive passages.In this study,we used induced pluripotent stem cell-derived mesenchymal stem cells,known for their self-renewal capacity,multilineage differentiation potential,and immunomodulatory characteristics.We used induced pluripotent stem cell-derived mesenchymal stem cells in conjunction with acellular nerve allografts to address a 10 mm-long defect in a rat model of sciatic nerve injury.Our findings reveal that induced pluripotent stem cell-derived mesenchymal stem cells exhibit survival for up to 17 days in a rat model of peripheral nerve injury with acellular nerve allograft transplantation.Furthermore,the combination of acellular nerve allograft and induced pluripotent stem cell-derived mesenchymal stem cells significantly accelerates the regeneration of injured axons and improves behavioral function recovery in rats.Additionally,our in vivo and in vitro experiments indicate that induced pluripotent stem cell-derived mesenchymal stem cells play a pivotal role in promoting neovascularization.Collectively,our results suggest the potential of acellular nerve allografts with induced pluripotent stem cell-derived mesenchymal stem cells to augment nerve regeneration in rats,offering promising therapeutic strategies for clinical translation.展开更多
Background There is still limited data on predictive value of coronary computed tomography angiography(CCTA)–derived fractional flow reserve(CT-FFR) for long term outcomes. We examined the long-term prognostic value ...Background There is still limited data on predictive value of coronary computed tomography angiography(CCTA)–derived fractional flow reserve(CT-FFR) for long term outcomes. We examined the long-term prognostic value of CT-FFR combined with CCTA–defined atherosclerotic extent in diabetic patients with coronary artery disease(CAD).Methods A retrospective pooled analysis of individual patient data was performed. Deep-learning-based vessel-specific CTFFR was calculated. All patients enrolled were followed-up for at least 5 years. Predictive abilities for major adverse cardiac events(MACE) were compared among three models(model 1), constructed using clinical variables;model 2, model 1+CCTA–derived atherosclerotic extent(Leiden risk score);and model 3, model 2+CT-FFR.Results A total of 480 diabetic patients [median age, 61(55–66) years;52.9% men] were included. During a median follow-up time of 2197(2126–2355) days, 55 patients(11.5%) experienced MACE. In multivariate-adjusted Cox models, Leiden risk score(HR: 1.06;95% CI: 1.01–1.11;P = 0.013) and CT-FFR ≤ 0.80(HR: 6.54;95% CI: 3.18–13.45;P < 0.001) were the independent predictors. The discriminant ability was higher in model 2 than in model 1(C-index, 0.75 vs. 0.63;P < 0.001) and was further promoted by adding CT-FFR to model 3(C-index, 0.81 vs. 0.75;P = 0.002). Net reclassification improvement(NRI) was 0.19(P = 0.009) for model 2 beyond model 1. Of note, adding CT-FFR to model 3 also exhibited significantly improved reclassification compared with model 2(NRI = 0.14;P = 0.011).Conclusion In diabetic patients with CAD, CT-FFR provides robust and incremental prognostic information for predicting longterm outcomes. The combined model exhibits improved prediction abilities, which is beneficial for risk stratification.展开更多
Organocatalyzed atom transfer radical polymerization(O-ATRP)is a pivotal technique for the synthesis of polymers with well-defined structures that are devoid of metallic residues.A major challenge in this area is the ...Organocatalyzed atom transfer radical polymerization(O-ATRP)is a pivotal technique for the synthesis of polymers with well-defined structures that are devoid of metallic residues.A major challenge in this area is the reduction of catalyst loading while maintaining precise control over polymer architecture and properties.Herein,we systematically evaluate the efficacy of six pyrazino[2,3-f][1,10]phenanthroline(pyzPhen)-based photoredox catalysts in photoinduced O-ATRP.Experimental results indicate that the introduction of various substituents markedly influences the photophysical properties and redox behavior of the catalysts,thereby resulting in differing catalytic efficiencies in the O-ATRP of methyl methacrylate(MMA).Following additional optimization,two highly efficient O-ATRP photocatalysts capable of exhibiting thermally activated delayed fluorescence(TADF)were successfully identified.Under visible light irradiation,TADF catalysts effectively mediated the controlled polymerization of MMA at a low loading level of 50 ppm,particularly when used in conjunction with the initiator DBMM.The catalytic systems demonstrate excellent temporal control,broad monomer applicability,and favorable compatibility with various initiators and solvent systems.This work offers new insights into the development of efficient,low-catalyst-loading,metal-free ATRP systems.展开更多
Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1....Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.展开更多
We report five coordination polymers(CPs)based on fluorescent ligands[1,6-di(1H-imidazol-1-yl)pyrene(dip),9,10-di(1H-imidazol-1-yl)anthracene(dia)]and anionic ligands[cyclohexane-1,4-dicarboxylic acid(H_(2)cda),campho...We report five coordination polymers(CPs)based on fluorescent ligands[1,6-di(1H-imidazol-1-yl)pyrene(dip),9,10-di(1H-imidazol-1-yl)anthracene(dia)]and anionic ligands[cyclohexane-1,4-dicarboxylic acid(H_(2)cda),camphoric acid(H_(2)cpa)].In[Cd(dip)(cda)]·4H_(2)O}_(n)(1),the Cd^(2+)ions,acting as tetrahedral nodes,are linked by dipand cda^(2-)ligands with four Cd^(2+)ions into five-fold interpenetrating network array of topology of dia.In{[Cd(dip)(cpa)]·4H_(2)O}_(n)(2),the Cd^(2+)ions,acting as a 4-connector,are linked by cpa^(2-)and dip ligands into a 3D framework ofcds topology.In{[Ni(dia)_(2)Cl_(2)]·DMF}_(n)(3),the Ni^(2+)ion is linked by four dia ligands into a layer structure,and 1Dchannels of a cross-section of 1.35 nm×0.96 nm are formed.In{[Cd(dia)_(2)(H_(2)O)_(2)](NO_(3))_(2)·2DMSO}n(4),the dia ligandsconnected Cd^(2+)ions into a 2D layer,and 1D channels are formed between adjacent layers with a cross-section of0.87 nm×0.43 nm.In[Zn(dip)Cl_(2)]_(n)(5),the Zn^(2+)ion is linked by dip ligands into an infinite 1D chain.The infrared,thermal gravimetric,and fluorescent emission data were collected and analyzed for these coordination polymers.CCDC:2356055,1;2440075,2;2356057,3;2356057,4;2356059,5.展开更多
An efficient strategy for construction of tricyclic thiazino[3,4-a]isoquinolines has been achieved via 4-dimethylamino-pyridine(DMAP)promoted[5+1]annulation of simple and readily available isoquinoline 1,4-zwitterion ...An efficient strategy for construction of tricyclic thiazino[3,4-a]isoquinolines has been achieved via 4-dimethylamino-pyridine(DMAP)promoted[5+1]annulation of simple and readily available isoquinoline 1,4-zwitterion withα-bromoketone.This protocol showed good substrate compatibility as an array of structurally and electronically diverse thiazino[3,4-a]isoquinolines prepared efficiently in moderate to good yields.It is particularly emphasized that although this reaction exhibits moderate stereoselectivity,the two diastereomers can be separated by column chromatography,providing an important molecular diversity foundation for the screening and structural optimization of subsequent drug lead compounds,as well as a simple and efficient method for constructing complex nitrogen-containing and sulfur-containing heterocyclic compounds.It has potential application value in the fields of medicinal chemistry and organic synthesis.展开更多
基金supported by project Emerging Infectious Diseases One Health Basic and Translational Research Actions addressing Unmet Needs on Emerging Infectious Diseases,INF-ACT,Spoke 1 and Spoke 5,Project number PE00000007,CUP B53C20040570005(to PP and DN).
文摘Introduction:One of the main events that regulate a cell’s well-being is cell-to-cell communication.This intercellular mechanism of information transfer is often mediated by vesicular trafficking.Mitochondrial-derived vesicles(MDVs)are an emerging subpopulation of extracellular vesicle(EV)first discovered in 2008 that allow mitochondria to communicate with their surroundings.
基金supported by the National Natural Science Foundation of China(Nos.21977058 and 82473840)the Key R&D Program of Jiangsu Province(No.BE2021677)+2 种基金China Postdoctoral Science Foundation(No.2018T110533)the Key Natural Science Foundation of Jiangsu Higher Education Institutions(No.20KJA350002)Jiangsu Province Innovation Project of Postgraduate Training(No.KYCX22_3380).
文摘Ischemic stroke(IS)presents a major threat to human life and health due to its high disability and mortality rates.3-n-Butylphthalide(NBP),derived from celery seeds of the Apiaceae family native to the Mediterranean region,was first introduced in China for acute IS treatment in 2004.NBP demonstrates multiple therapeutic actions,including reconstruction of microcirculation in the cerebral ischemia area,inhibition of platelet aggregation,reduction of cerebral infarction volume,maintenance of blood-brain barrier(BBB)integrity,and enhancement of cerebral blood perfusion.However,its overall efficacy remains moderate,limited by poor water solubility and low bioavailability,which constrains its clinical application.To address these limitations,researchers have actively pursued the development of NBP derivatives and analogs,achieving notable progress.These efforts,including substituent introduction,ring opening derivatization,esterification,and atom substitution,have generated diverse NBP derivatives.Several of these derivatives have advanced to clinical studies.Specifically,potassium 2-(1-hydroxypentyl)-benzoate(PHPB),brozopentyl sodium(BZP),and XY-03-EA(ZONK1103)have reached phase II clinical trials,while(S)-2-(1-acetoxypentyl)benzoic acid L-arginine salt(AAPB)has received clinical trial approval for 2024.This review examines the structural modification and optimization of NBP over the past two decades from a medicinal chemistry perspective,aiming to facilitate the development of superior derivatives and advance cerebral ischemia treatment.
基金Supported by Basic Research Foundation of Yunnan Education Department(Nos.2020J0748,2021J0635)Talent Project Foundation of Yunnan Provincial Science and Technology Department(No.202105AC160089)NSF of Yunnan Province(No.202101BA070001198).
文摘In this paper,we investigate the problem of describing the form of Jordan triple derivations on trivial extension algebras.We show that every Jordan triple derivation on a 2-torsion free *-type trivial extension algebra is a sum of a derivation and an antiderivation.As its applications,Jordan triple derivations on triangular algebras are characterized.
基金Sponsored the National Natural Science Foundation of China(42502088)the National Major Science and Technology Project of China(2025ZD1007504-1)+2 种基金the Special Research Fund of Natural Science(Special Post)of Guizhou University(X202402)the Guizhou Provincial Science and Technology Projects(QKHJC[2024]youth 153)the Xinjiang Uygur Autonomous Region Natural Science Foundation(2024D01A147)。
文摘Lithium(Li)is an‘emerging'environmental pollutant,especially in soil,which is a great concern because it can endanger human health through the food chain.Compared with traditional chemical analyses,hyperspectral techniques have achieved many exciting results in soil metal monitoring due to their advantages of being fast and non-destructive.However,insufficient attention has been paid to lithium in soil,and the feasibility of its estimation using hyperspectral techniques needs to be investigated.We studied 97 soil samples from claytype lithium mines in the Ertanggou area of the East Tianshan Mountains of Xinjiang to explore the effects of spectral resolution,fractional order derivatives(FOD),and characteristic band selection on the estimation accuracy of clay Li content,to obtain a fast and effective method for estimating clay Li content.Finally,we developed a new method for rapid and nondestructive estimation of soil lithium content.We have obtained some important results from the study.Spectral resolution exerts a significant impact on model performance,and its reduction usually leads to a decline in model performance.For the full band,the models constructed with low-order derivatives were superior to those with high-order derivatives,and the best model was obtained at the 0.4-order derivative(coefficient of determination(R^(2))and relative predictive deviation(RPD)of 0.777 and 2.118,respectively).In the characteristic bands,the lower order is sensitive to the visible-near-infrared range,and the higher order is sensitive to the short-wave infrared range,and the model constructed with the higher-order derivatives outperforms the lower-order derivatives.In this study,the combination of FOD and Random Forest(RF)can significantly improve the model performance,with R^(2),Relative Root Mean Squared Error(RRMSE),and RPD being 0.849,1.526,and 2.574,respectively.Therefore,this research provides a theoretical basis and technical reference for imaging hyperspectral exploration of anomalous areas of clay-type Li resources.
基金Science and Technology Agency of Jilin Provincial Project(Grant/Award Number:20230203075SF)Youth Project of Jilin Provincial Health Commission(Grant/Award Number:2024A123)。
文摘Background:Myeloid-derived suppressor cells(MDSCs)are important tumor microenvironment components in small cell lung cancer(SCLC).We successfully identified MDSCs expressing the surface marker CD33 in SCLC;nonetheless,whether CD33^(+)MDSCs promote SCLC angiogenesis remains unclear.This study aims to explore the angiogenic effect and clinical significance of CD33^(+)MDSCs derived from SCLC.Method:Nineteen patients diagnosed with extensive-stage SCLC at Jilin Cancer Hospital were selected as the research subjects.CD33^(+)MDSCs were isolated from the peripheral blood of patients with SCLC using magnetic bead separation and CD33 expression was detected by flow cytometry.The angiogenic potential of CD33^(+)MDSCs derived from the peripheral blood of patients with SCLC and healthy individuals was assessed using human umbilical vein endothelial cell(HUVEC)angiogenesis assays,and the clinical significance of CD33^(+)MDSCs in promoting angiogenesis in patients with SCLC was analyzed using clinical data.Results:Compared to healthy individuals,the CD33^(+)MDSCs(CD14^(+)CD33^(+))isolated from the peripheral blood of SCLC patients exhibited a greater ability to promote HUVEC tubular growth(average vessel length:57.60 mm[47.78 mm]vs.39.07 mm[15.84 mm],p=0.000;vessel area:371,890 mm^(3)[699,927 mm^(3)]vs.334,652 mm^(3)[219,520 mm^(3)],p<0.000;total number of junctions:141[301]vs.120[94],p<0.005),and their angiogenic ability was associated with older age,female sex,high performance status scores,no systematic treatment,and treatment unresponsiveness(p<0.050).Furthermore,the enhanced angiogenic ability of CD33^(+)MDSCs may represent a risk factor for treatment unresponsiveness(average vessel length:Odds ratio=3.904,95%CI=1.812-8.409,p=0.001;vessel area:Odds ratio=2.501,95%CI=1.187-5.267,p=0.016;total number of junctions:Odds ratio=3.630,95%CI=1.686-7.815,p=0.001)and is associated with a poor SCLC prognosis(average vessel length:Hazard ratio=2.210,95%CI=1.299-3.758,p=0.003;vessel area:Hazard ratio=2.170,95%CI=1.274-3.693,p=0.004;total number of junctions:Hazard ratio=2.267,95%CI=1.333-3.853,p=0.003).Conclusion:CD33^(+)MDSCs derived from the peripheral blood of patients with SCLC promote angiogenesis,which is a risk factor for treatment unresponsiveness and is associated with poor prognosis.
文摘Mitophagy is a well-characterized and redundant recycling system for damaged mitochondria and a marker of organelle quality(Picca et al.,2023).Yet,the assessment of mitophagy in vivo remains a challenge.The characterization of the endosomallysosomal pathways supporting the endocytic tra fficking has provided invaluable information also into mitophagy signaling.
基金supported by the National Natural ScienceFoundation of China(Grant No.52203332)。
文摘The thermal decomposition characteristic of ammonium perchlorate(AP)represents a critical factor in determining the performance of solid propellants,which has aroused significant interest on the structure and performance improvement of kinds of catalysts.In this study,bimetallic metal-organic frameworks(MOFs),such as CuCo-BTC(BTC=1,3,5-Benzenetricarboxylic acid,H_(3)BTC),CuNi-BTC,and CoNi-BTC,were synthesized by solvothermal(ST)and spray-drying(SD)methods,and then calcined at 400℃for 2 h to form metal oxides.The catalysts as well as their catalytic effects for AP decomposition were characterized by FTIR,XRD,SEM,XPS,TG,DSC,TG-IR,EIS,CV,and LSV.It was found that the rapid coordination of metal ions with ligands during spray drying may lead to catalytic structural defects,promoting the exposure of reactive active sites and increasing the catalytic active region.The results showed that the addition of 2 wt%binary transition metal oxides(BTMOs)as catalysts significantly reduced the high-temperature decomposition(HTD)temperature of AP and enhanced its heat release.Of particular significance is the observation that SD-CoNiO_(x),prepared by spray-drying,reduced the decomposition temperature of AP from 413.26℃(pure AP)to 306℃and enhanced the heat release from 256.79 J/g(pure AP)to 1496.82 J/g,while concomitantly reducing the activation energy by 42%.By analysing the gaseous products during the decomposition of AP+SD-CoNiO_(x)and AP+ST-CoNiO_(x),it was found that SD-CoNiO_(x)could significantly increase the content of high-valent nitrogen oxides during the AP decomposition reaction,which indicates that the BTMOs prepared by spray-drying in the reaction system are more conducive to accelerating the electron transfer in the thermal decomposition process of AP,and can provide a high concentration of reactive oxygen species that oxidize AP to high-valent nitrogen oxide-containing compounds.The present study shows that the structure selectivity of the spray-drying technique influences surfactant molecular arrangement on catalyst surfaces,resulting in their ability to promote higher electron transfer during the catalytic process.Therefore,BTMOs prepared by spray drying method have higher potential for application.
基金Funded by the Natural Science Foundation of Guangdong(Nos.2014A030313241,2014B090901068,and 2016A010103003)。
文摘Two viologen derivatives containing fluorine substituent(F)with an asymmetric structures,1,1'-bis(4-(trifluoromethyl)phenyl)-[4,4'-bipyridine]dihexafluorophosphate(DFPV)and 1-benzyl-1'-(4-(trifluoromethyl)phenyl)-[4,4'-bipyridine]di-hexafluorophosphate(Bn-FPV),were synthesized.These viologen derivatives as active materials were used to assemble both flexible and rigid electrochromic devices(ECDs).ECDs based on DFPV exhibited reversible color change from colorless to deep green and ECDs based on Bn-FPV exhibited reversible color change from colorless to blue-green within applied voltage.It was found that the devices based on DFPV showed cycle stability,which could still maintain more than 90% after 1000 cycles.In addition,the modulation rate of the device to the solar irradiance is also calculated to characterize its application potential in smart windows.Among them,the rigid device(R-DFPV)based on the DFPV has a large solar irradiance modulation rate of 54.66%,which has the potential to be used as smart windows.
基金supported by the Natural Science Foundation of Hubei Province (Nos.2023AFB376 and 2024AFD287)National Key Research and Development Program (No.2023YFC3503804)the National Natural Science Foundation of China (No.22077044)。
文摘Sulfur dioxide(SO_(2)) and its derivatives have been recognized as harmful environmental pollutants.However,they are often produced during the processing of traditional Chinese medicines,potentially compromising the quality of these medicinal materials and contributing to various health issues.Due to a lack of effective monitoring and imaging tools,the physiological effects of excessive SO_(2) residues in traditional Chinese medicine remain unclear.Therefore,developing a rapid and effective tool for detecting SO_(2) is crucial for understanding its metabolic pathways and effects in vivo.In this study,we developed a near infrared(NIR) and ratiometric fluorescent probe,NIR-RS,which exhibits high sensitivity,selectivity,and rapid response for SO_(2) detection.Notably,NIR-RS accurately quantifies SO_(2) contents in Pinelliae rhizoma(P.rhizoma) samples,with recovery rates from 98.46 % to 102.40 %,and relative standard deviations(RSDs)< 5.0 %.For bioimaging applications,NIR-RS has low cytotoxicity and good mitochondrial-targeting ability,making it suitable for imaging exogenous and endogenous SO_(2) in mitochondria.Additionally,NIR-RS was successfully applied to image SO_(2) content of P.rhizoma samples within cells,revealing that high SO_(2) residue elevated mitochondria adenosine triphosphate(ATP) content,these findings reveal that P.rhizoma with excessive SO_(2) can affect the organism's growth mechanisms through alterations in ATP pathways.In vivo,SO_(2) was found to predominantly accumulate in the liver following gavage with P.rhizoma solution,with accumulation levels increasing in proportion to SO_(2) residue concentration.High SO_(2) concentrations in P.rhizoma can cause pulmonary fibrosis and gastric mucosal damage.This work provides a valuable tool for regulating SO_(2) content in P.rhizoma and may help researcher better understand the metabolism of SO_(2) derivatives and explore their physiological roles in biological systems.
基金financially supported by the National Natural Science Foundation of China(Nos.22372143 and 22208281)the Hebei Natural Science Foundation(Nos.B2023203001 and B2025203050)the Science Research Project of Hebei Education Department(BJK2024122)。
文摘Rational design of non-noble electrocatalysts with high performance for oxygen evolution reaction(OER)still remains a challenge.In this study,a ZIF-derived electrocatalyst(Co@Fe-P)with a core-shell structure is designed by using Co-compounds as the core and PO_(4)^(3-)decorated Fe-compounds as the shell.The inner Co-core and outer Fe-shell are connected through Co-O-Fe and Fe-O-P linkage.The Co@Fe-P electrocatalyst exhibits an enhanced performance for OER with a low overpotential(280 mV),low Tafel slope(41.9 mV dec^(-1))at 10 mA cm^(-2),and a 60-h durability.The electron transfer from the CoOOH-core to the FeOOH-shell is greatly facilitated,which improves the OER activity of Co@Fe-P kinetically.Theoretical calculations indicate that the interaction of Co-O-Fe and Fe-O-P in Co@Fe-P reduces the overlap between the O 2p and Fe 3d orbitals,which greatly facilitates the transformation from*OH to*O during the OER process via the adsorbate evolution mechanism(AEM)pathway.This finding provides insight for the design of efficient electrocatalysts for OER.
基金supported by FWO(Fonds voor Wetenschappelijk Onderzoek),grant number G07562NFWO(to BB)。
文摘Neuroinflammation is a key process in the pathogenesis of various neurodegenerative diseases,such as multiple sclerosis(MS),Alzheimer's disease,and traumatic brain injury.Even for disorders historically unrelated to neuroinflammation,such as Alzheimer's disease,it is now shown to precede pathological protein aggregations.
基金funded by Grants PID2021-127191OB-I00,RTI2018-101708-A-I00,PRE2018-084542 and PRE2022-102680 funded by MCIN/AEI/10.13039/501100011033 and by“ERDF A way of making Europe”Grant RYC2018-025502-I is funded by MCIN/AEI/10.13039/501100011033 and by“ESF Investing in your future”+1 种基金Grant MDM-20170720 Maria de Maeztu Units of Excellence Program funded by the Spanish State Research Agencysupported by Instituto de Salud CarlosⅢ,Infrastructure of Precision Medicine associated with Science and Technology(IMPaCT)of the Strategic Action in Health(iDATA-MP)。
文摘Endochondral ossification is a physiological process involving a sequential formation of cartilage and bone tissues.Classically,cartilage and bone formation have been considered independent processes at cellular level.However,the recently described multiple cell differentiation dynamics suggest that some bone cells are indeed the progeny of cartilage cells,or chondrocyte-derived osteoblasts.We hypothesized that the cartilage-to-bone phenotype transition is triggered by specific molecular events.First,the process was assessed in mouse bone tissue,and then,it was mimicked using in vivo cell implantation and in vitro serial differentiation protocols.Data indicates that cartilage cells transition to bone cell phenotype during postnatal physiological bone formation.This process can be reproduced using cartilage precursor cells coupled to specific implantation procedures or differentiation protocols.Gene expression profiling reveals that NOTCH,BMP and MAPK signaling pathways are relevant at the phenotype-switch,while the transcription factors Mesp1,Alx1,Grhl3 and Hmx3 are the feasible driver genes for chondrocyte-derived osteoblasts formation.Altogether,this report shows that endochondral ossification can be modeled using primary cell cultures and data indicate that this process is regulated by specific molecular events,previously described at skeleton morphogenesis during embryo development,and from now on also linkable to postnatal bone development and regeneration processes.
基金supported and funded by the Deanship of Scientific Research at Imam Mohammad Ibn Saud Islamic University(IMSIU)(grant number IMSIU-DDRSP2601).
文摘This paper introduces a novel fractional-order model based on the Caputo-Fabrizio(CF)derivative for analyzing computer virus propagation in networked environments.The model partitions the computer population into four compartments:susceptible,latently infected,breaking-out,and antivirus-capable systems.By employing the CF derivative—which uses a nonsingular exponential kernel—the framework effectively captures memory-dependent and nonlocal characteristics intrinsic to cyber systems,aspects inadequately represented by traditional integer-order models.Under Lipschitz continuity and boundedness assumptions,the existence and uniqueness of solutions are rigorously established via fixed-point theory.We develop a tailored two-step Adams-Bashforth numerical scheme for the CF framework and prove its second-order accuracy.Extensive numerical simulations across various fractional orders reveal that memory effects significantly influence virus transmission and control dynamics;smaller fractional orders produce more pronounced memory effects,delaying both infection spread and antivirus activation.Further theoretical analysis,including Hyers-Ulam stability and sensitivity assessments,reinforces the model’s robustness and identifies key parameters governing virus dynamics.The study also extends the framework to incorporate stochastic effects through a stochastic CF formulation.These results underscore fractional-order modeling as a powerful analytical tool for developing robust and effective cybersecurity strategies.
基金supported by the Canadian Institutes of Health Research(DFD-181599)the National Institutes of Health(T32AG058527)to RJB and R0190106435 to VM.
文摘Neurodegenerative disorders represent an increasingly pertinent public health crisis.As a greater proportion of the population ages,neurodegenerative disorders and other diseases of aging place undue burdens on patients,caregivers,and healthcare workers.Alzheimer’s disease(AD)and Parkinson’s disease represent the two most common neurodegenerative disorders in the population,affecting over 65 million people,worldwide.
基金supported by the National Natural Science Foundation of China,No.32171356(to YW)Self-Support Research Projects of Shihezi University,No.ZZZC2021105(to WJ)+1 种基金Capital Medical University Natural Science Cultivation Fund,No.PYZ23044(to FQM)Beijing Municipal Natural Science Foundation,No.7244410(to JHD)。
文摘Previous research has demonstrated the feasibility of repairing nerve defects through acellular allogeneic nerve grafting with bone marrow mesenchymal stem cells.However,adult tissue–derived mesenchymal stem cells encounter various obstacles,including limited tissue sources,invasive acquisition methods,cellular heterogeneity,purification challenges,cellular senescence,and diminished pluripotency and proliferation over successive passages.In this study,we used induced pluripotent stem cell-derived mesenchymal stem cells,known for their self-renewal capacity,multilineage differentiation potential,and immunomodulatory characteristics.We used induced pluripotent stem cell-derived mesenchymal stem cells in conjunction with acellular nerve allografts to address a 10 mm-long defect in a rat model of sciatic nerve injury.Our findings reveal that induced pluripotent stem cell-derived mesenchymal stem cells exhibit survival for up to 17 days in a rat model of peripheral nerve injury with acellular nerve allograft transplantation.Furthermore,the combination of acellular nerve allograft and induced pluripotent stem cell-derived mesenchymal stem cells significantly accelerates the regeneration of injured axons and improves behavioral function recovery in rats.Additionally,our in vivo and in vitro experiments indicate that induced pluripotent stem cell-derived mesenchymal stem cells play a pivotal role in promoting neovascularization.Collectively,our results suggest the potential of acellular nerve allografts with induced pluripotent stem cell-derived mesenchymal stem cells to augment nerve regeneration in rats,offering promising therapeutic strategies for clinical translation.
文摘Background There is still limited data on predictive value of coronary computed tomography angiography(CCTA)–derived fractional flow reserve(CT-FFR) for long term outcomes. We examined the long-term prognostic value of CT-FFR combined with CCTA–defined atherosclerotic extent in diabetic patients with coronary artery disease(CAD).Methods A retrospective pooled analysis of individual patient data was performed. Deep-learning-based vessel-specific CTFFR was calculated. All patients enrolled were followed-up for at least 5 years. Predictive abilities for major adverse cardiac events(MACE) were compared among three models(model 1), constructed using clinical variables;model 2, model 1+CCTA–derived atherosclerotic extent(Leiden risk score);and model 3, model 2+CT-FFR.Results A total of 480 diabetic patients [median age, 61(55–66) years;52.9% men] were included. During a median follow-up time of 2197(2126–2355) days, 55 patients(11.5%) experienced MACE. In multivariate-adjusted Cox models, Leiden risk score(HR: 1.06;95% CI: 1.01–1.11;P = 0.013) and CT-FFR ≤ 0.80(HR: 6.54;95% CI: 3.18–13.45;P < 0.001) were the independent predictors. The discriminant ability was higher in model 2 than in model 1(C-index, 0.75 vs. 0.63;P < 0.001) and was further promoted by adding CT-FFR to model 3(C-index, 0.81 vs. 0.75;P = 0.002). Net reclassification improvement(NRI) was 0.19(P = 0.009) for model 2 beyond model 1. Of note, adding CT-FFR to model 3 also exhibited significantly improved reclassification compared with model 2(NRI = 0.14;P = 0.011).Conclusion In diabetic patients with CAD, CT-FFR provides robust and incremental prognostic information for predicting longterm outcomes. The combined model exhibits improved prediction abilities, which is beneficial for risk stratification.
基金financially supported by the National Natural Science Foundation of China (No. 22271044).
文摘Organocatalyzed atom transfer radical polymerization(O-ATRP)is a pivotal technique for the synthesis of polymers with well-defined structures that are devoid of metallic residues.A major challenge in this area is the reduction of catalyst loading while maintaining precise control over polymer architecture and properties.Herein,we systematically evaluate the efficacy of six pyrazino[2,3-f][1,10]phenanthroline(pyzPhen)-based photoredox catalysts in photoinduced O-ATRP.Experimental results indicate that the introduction of various substituents markedly influences the photophysical properties and redox behavior of the catalysts,thereby resulting in differing catalytic efficiencies in the O-ATRP of methyl methacrylate(MMA).Following additional optimization,two highly efficient O-ATRP photocatalysts capable of exhibiting thermally activated delayed fluorescence(TADF)were successfully identified.Under visible light irradiation,TADF catalysts effectively mediated the controlled polymerization of MMA at a low loading level of 50 ppm,particularly when used in conjunction with the initiator DBMM.The catalytic systems demonstrate excellent temporal control,broad monomer applicability,and favorable compatibility with various initiators and solvent systems.This work offers new insights into the development of efficient,low-catalyst-loading,metal-free ATRP systems.
文摘Six coordination polymers based on 9,10-di(pyridine-4-yl)-anthracene(DPA)and 1,6-di(1H-imidazol-1-yl)pyrene(DIP)were obtained by solvothermal reactions.{[Zn(DPA)Cl_(2)]·DMF·2H_(2)O}n(1)and{[Zn_(1.5)(DPA)_(1.5)Cl_(3)]·5H_(2)O}n(2)are framework isomers,which both contain zigzag chains formed by DPA,Zn^(2+),and Cl-.The zigzag chains in 1 are further assembled by C—H…Cl interactions into layers,and these layers exhibit two different orientations,displaying a rare 2D to 3D interpenetration mode.The zigzag chains in 2 are parallelly arranged.{[Zn_(3)(DPA)_(3)Br_(6)]·2DMF·_(1.5)H_(2)O}n(3)is isostructural to 2.3 was obtained using ZnBr_(2)instead of ZnCl_(2).[M(DPA)(formate)_(2)(H_(2)O)_(2)]n[M=Co(4),Cu(5)]are isostructural,contain chain structures formed by DPA,Cu^(2+)/Co^(2+),and for-mate ions,which were formed in situ in the solvothermal reaction.{[Zn(DIP)_(2)Cl]ClO_(4)}n(6)contains a layer structure formed by DIP and Zn^(2+).Free DPA and DIP ligands exhibited high fluorescence at room temperature,and coordina-tion polymers 3 and 6 displayed enhanced fluorescent emissions.
文摘We report five coordination polymers(CPs)based on fluorescent ligands[1,6-di(1H-imidazol-1-yl)pyrene(dip),9,10-di(1H-imidazol-1-yl)anthracene(dia)]and anionic ligands[cyclohexane-1,4-dicarboxylic acid(H_(2)cda),camphoric acid(H_(2)cpa)].In[Cd(dip)(cda)]·4H_(2)O}_(n)(1),the Cd^(2+)ions,acting as tetrahedral nodes,are linked by dipand cda^(2-)ligands with four Cd^(2+)ions into five-fold interpenetrating network array of topology of dia.In{[Cd(dip)(cpa)]·4H_(2)O}_(n)(2),the Cd^(2+)ions,acting as a 4-connector,are linked by cpa^(2-)and dip ligands into a 3D framework ofcds topology.In{[Ni(dia)_(2)Cl_(2)]·DMF}_(n)(3),the Ni^(2+)ion is linked by four dia ligands into a layer structure,and 1Dchannels of a cross-section of 1.35 nm×0.96 nm are formed.In{[Cd(dia)_(2)(H_(2)O)_(2)](NO_(3))_(2)·2DMSO}n(4),the dia ligandsconnected Cd^(2+)ions into a 2D layer,and 1D channels are formed between adjacent layers with a cross-section of0.87 nm×0.43 nm.In[Zn(dip)Cl_(2)]_(n)(5),the Zn^(2+)ion is linked by dip ligands into an infinite 1D chain.The infrared,thermal gravimetric,and fluorescent emission data were collected and analyzed for these coordination polymers.CCDC:2356055,1;2440075,2;2356057,3;2356057,4;2356059,5.
文摘An efficient strategy for construction of tricyclic thiazino[3,4-a]isoquinolines has been achieved via 4-dimethylamino-pyridine(DMAP)promoted[5+1]annulation of simple and readily available isoquinoline 1,4-zwitterion withα-bromoketone.This protocol showed good substrate compatibility as an array of structurally and electronically diverse thiazino[3,4-a]isoquinolines prepared efficiently in moderate to good yields.It is particularly emphasized that although this reaction exhibits moderate stereoselectivity,the two diastereomers can be separated by column chromatography,providing an important molecular diversity foundation for the screening and structural optimization of subsequent drug lead compounds,as well as a simple and efficient method for constructing complex nitrogen-containing and sulfur-containing heterocyclic compounds.It has potential application value in the fields of medicinal chemistry and organic synthesis.
