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
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
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
By using cone-directed contingent derivatives, the unified necessary and sufficient optimality conditions are given for weakly and strongly minimal elements respectively in generalized preinvex set-valued optimization.
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
By using harmonic representations of distributions, set-valued derivatives of one-dimensional distributions are introduced in this paper. And several equivalent definitions of the set-valued derivative are given for c...By using harmonic representations of distributions, set-valued derivatives of one-dimensional distributions are introduced in this paper. And several equivalent definitions of the set-valued derivative are given for continuous real functions. The set-valued derivative of a local Lipschitz function coincides with the generalized gradient defined by F. H. Clarke. A distribution is Lipschitz near a point if and only if its set-valued derivative at this point is finite. When the set-valued derivative at some point of a distribution on R does not contain both +∞ and -∞ its distributional derivative is a Radon measure on some neighbourhood of this point. By using the first order'set-valued derivatives, an existence theorem of inverse functions of continuous functions is proved; and by using higher order ones, two very general sufficient conditions for a distribution to attain extremal values are obtained. A distribution is convex on an open interval if and only if its second order set-valued derivatives at all points of the interval are contained in [0, +∞]. Therefore, a satisfactory differential theory of nondifferentiable functions is developed.展开更多
This note studies the optimality conditions of vector optimization problems involving generalized convexity in locally convex spaces. Based upon the concept of Dini set-valued directional derivatives, the necessary an...This note studies the optimality conditions of vector optimization problems involving generalized convexity in locally convex spaces. Based upon the concept of Dini set-valued directional derivatives, the necessary and sufficient optimality conditions are established for Henig proper and strong minimal solutions respectively in generalized preinvex vector optimization problems.展开更多
Two tetrasubstituted carbazole derivatives TBICz and TOXDCz have been designed and synthesized,which possess the twist skeletons and exhibit excellent thermal and morphological stabilities.Utilizing these novel compou...Two tetrasubstituted carbazole derivatives TBICz and TOXDCz have been designed and synthesized,which possess the twist skeletons and exhibit excellent thermal and morphological stabilities.Utilizing these novel compounds as host material,high efficiency solution-processed green phosphorescent organic light-emitting diodes(PhOLEDs)have been achieved.The high triplet energies of TBICz and TOXDCz ensure efficient energy transfer from the host to the phosphor and triplet exciton confinement on the phosphor.Solution-processable green phospho⁃rescent devices employing Ir(ppy)3 as vip and the two tetrasubstituted carbazole derivatives as hosts exhibit high ef⁃ficiencies.The best EL performance is achieved for the TBICz-based device,with a maximum current efficiency of 27.3 cd/A,a maximum power efficiency of 15.9 lm/W,and a maximum external quantum efficiency of 7.8%,which provides more host material options for solution-processed OLEDs.展开更多
Guided by molecular networking,nine novel curvularin derivatives(1-9)and 16 known analogs(10-25)were isolated from the hydrothermal vent sediment fungus Penicillium sp.HL-50.Notably,compounds 5-7 represented a hybrid ...Guided by molecular networking,nine novel curvularin derivatives(1-9)and 16 known analogs(10-25)were isolated from the hydrothermal vent sediment fungus Penicillium sp.HL-50.Notably,compounds 5-7 represented a hybrid of curvularin and purine.The structures and absolute configurations of compounds 1-9 were elucidated via nuclear magnetic resonance(NMR)spectroscopy,X-ray diffraction,electronic circular dichroism(ECD)calculations,^(13)C NMR calculation,modified Mosher's method,and chemical derivatization.Investigation of anti-inflammatory activities revealed that compounds 7-9,11,12,14,15,and 18 exhibited significant suppressive effects against lipopolysaccharide(LPS)-induced nitric oxide(NO)production in murine macrophage RAW264.7 cells,with IC_(50)values ranging from 0.44 to 4.40μmol·L^(-1).Furthermore,these bioactive compounds were found to suppress the expression of inflammation-related proteins,including inducible NO synthase(i NOS),cyclooxygenase-2(COX-2),NLR family pyrin domain-containing protein 3(NLRP3),and nuclear factor kappa-B(NF-κB).Additional studies demonstrated that the novel compound 7 possessed potent antiinflammatory activity by inhibiting the transcription of inflammation-related genes,downregulating the expression of inflammation-related proteins,and inhibiting the release of inflammatory cytokines,indicating its potential application in the treatment of inflammatory diseases.展开更多
The poor reversibility and stability of Zn anodes greatly restrict the practical application of aqueous Zn-ion batteries(AZIBs),resulting from the uncontrollable dendrite growth and H_(2)O-induced side reactions durin...The poor reversibility and stability of Zn anodes greatly restrict the practical application of aqueous Zn-ion batteries(AZIBs),resulting from the uncontrollable dendrite growth and H_(2)O-induced side reactions during cycling.Electrolyte additive modification is considered one of the most effective and simplest methods for solving the aforementioned problems.Herein,the pyridine derivatives(PD)including 2,4-dihydroxypyridine(2,4-DHP),2,3-dihydroxypyridine(2,3-DHP),and 2-hydroxypyrdine(2-DHP),were em-ployed as novel electrolyte additives in ZnSO_(4)electrolyte.Both density functional theory calculation and experimental findings demonstrated that the incorporation of PD additives into the electrolyte effectively modulates the solvation structure of hydrated Zn ions,thereby suppressing side reactions in AZIBs.Ad-ditionally,the adsorption of PD molecules on the zinc anode surface contributed to uniform Zn deposi-tion and dendrite growth inhibition.Consequently,a 2,4-DHP-modified Zn/Zn symmetrical cell achieved an extremely long cyclic stability up to 5650 h at 1 mA cm^(-2).Furthermore,the Zn/NH_(4)V_(4)O_(10)full cell with 2,4-DHP-containing electrolyte exhibited an outstanding initial capacity of 204 mAh g^(-1),with a no-table capacity retention of 79%after 1000 cycles at 5 A g^(-1).Hence,this study expands the selection of electrolyte additives for AZIBs,and the working mechanism of PD additives provides new insights for electrolyte modification enabling highly reversible zinc anode.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
This study investigated environmental distribution and human exposure of polycyclic aromatic hydrocarbons(PAHs)and their derivatives in one Chinese petroleum refinery facility.It was found that,following with high con...This study investigated environmental distribution and human exposure of polycyclic aromatic hydrocarbons(PAHs)and their derivatives in one Chinese petroleum refinery facility.It was found that,following with high concentrations of 16 EPA PAHs(∑Parent-PAHs)in smelting subarea of studied petroleum refinery facility,total derivatives of PAHs[named as XPAHs,including nitro PAHs(NPAHs),chlorinated PAHs(Cl-PAHs),and brominated PAHs(Br-PAHs)]in gas(mean=1.57×10^(4)ng/m^(3)),total suspended particulate(TSP)(mean=4.33×10^(3) ng/m^(3))and soil(mean=4.37×10^(3) ng/g)in this subarea had 1.76-6.19 times higher levels than those from other subareas of this facility,surrounding residential areas and reference areas,indicating that petroleum refining processes would lead apparent derivation of PAHs.Especially,compared with those in residential and reference areas,gas samples in the petrochemical areas had higher∑NPAH/∑PAHs(mean=2.18),but lower∑Cl-PAH/∑PAHs(mean=1.43×10^(-1))and∑Br-PAH/∑PAHs ratios(mean=7.49×10^(-2)),indicating the richer nitrification of PAHs than chlorination during petrochemical process.The occupational exposure to PAHs and XPAHs in this petroleum refinery facility were 24-343 times higher than non-occupational exposure,and the ILCR(1.04×10^(-4))for petrochemical workers was considered to be potential high risk.Furthermore,one expanded high-resolution screening through GC Orbitrap/MS was performed for soils from petrochemical area,and another 35 PAHs were found,including alkyl-PAHs,phenyl-PAHs and other species,indicat-ing that profiles and risks of PAHs analogs in petrochemical areas deserve further expanded investigation.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
A transition-metal-free strategy for the synthesis of carboline derivatives via sequential dual C—N bond formation in a one-pot reaction is reported.Using 2,2'-dihalogenated pyridyl biaryls and primary amines as ...A transition-metal-free strategy for the synthesis of carboline derivatives via sequential dual C—N bond formation in a one-pot reaction is reported.Using 2,2'-dihalogenated pyridyl biaryls and primary amines as starting materials,this method efficiently constructs a series ofα-,β-,γ-andδ-carbolines under alkaline conditions.The reaction proceeds smoothly in the presence of lithium tert-butoxide(t-BuOLi)or cesium carbonate(Cs_(2)CO_(3))without requiring transition metal catalysts,demonstrating good functional group tolerance.This approach enables gram-scale synthesis and has been successfully applied to the preparation of the organic material 2,6-CbPy,achieving high conversion efficiency.展开更多
Chronic obstructive pulmonary disease(COPD)has garnered increased attention as a result of its persistent symptoms,which undermine patientsʼquality of life.Fudosteine has substantial advantages in the treatment of COP...Chronic obstructive pulmonary disease(COPD)has garnered increased attention as a result of its persistent symptoms,which undermine patientsʼquality of life.Fudosteine has substantial advantages in the treatment of COPD due to its high efficacy and low adverse effects.In this study,Fudosteine sulfonamide derivatives Series I and amine derivatives Series II were designed and synthesized,and their biological activities were evaluated.The results showed that compound 6f had outstanding anti-inflammatory action with an IC_(50) of 1.08 mmol/L,and a higher antioxidant capacity than the lead molecule.At the same time,molecular docking investigations have revealed that compound 6f establishes hydrogen bonds and hydrophobic contacts with the MUC5AC protein.Furthermore,derivative 1f inhibited PDE4A1 enzyme activity five times more than Fudosteine.2,2-Diphenyl-1-picrylhydrazyl(DPPH)free radical scavenging tests demonstrated that all examined substances had higher antioxidant activity than Fudosteine.This study established a solid foundation for further research into COPD drug therapy.展开更多
The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively red...The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule.This approach serves as a critical strategy for the directional synthesis of high-value molecules.However,achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds inα,β-unsaturated systems.Consequently,constructing precisely targeted catalytic systems is essential to overcome these limitations,offering both fundamental scientific significance and industrial application potential.Metal-organic frameworks(MOFs)and their derivatives have emerged as innovative platforms for designing such systems,owing to their programmable topology,tunable pore microenvironments,spatially controllable active sites,and modifiable electronic structures.This review systematically summarizes the research progress of MOF-based catalysts for selec-tive hydrogenation ofα,β-unsaturated aldehydes/ketones in the last decade,with emphasis on the design strategy,conformational relationship,and catalytic mechanism,aiming to provide new ideas for the design of targeted catalyt-ic systems for the selective hydrogenation ofα,β-unsaturated aldehydes/ketones.展开更多
This paper investigates set-valued state estimation of nonlinear systems with unknown-but-bounded(UBB)noises based on constrained polynomial zonotopes which is utilized to characterize non-convex sets.First,properties...This paper investigates set-valued state estimation of nonlinear systems with unknown-but-bounded(UBB)noises based on constrained polynomial zonotopes which is utilized to characterize non-convex sets.First,properties of constrained polynomial zonotopes are provided and the order reduction method is given to reduce the computational complexity.Then,the corresponding improved prediction-update algorithm is proposed so that it can be adapted to non-convex sets.Based on generalized intersection,the utilization of set-based estimation for attack detection is analyzed.Finally,an example is given to show the efficiency of our results.展开更多
Energy conversion and environmental pollution present significant challenges that necessitate the development of materials with optimal characteristics for effective applications in solar energy-driven photocatalysis....Energy conversion and environmental pollution present significant challenges that necessitate the development of materials with optimal characteristics for effective applications in solar energy-driven photocatalysis.Metal-organic frameworks(MOFs)serve as excellent platforms for the development of various MOF-derived materials,which have garnered extensive attention due to their unique structural features,high crystallinity,large surface areas,diverse morphologies,adjustable dimensions,tunable textural characteristics,and inherent catalytic activity.However,the sluggish charge kinetics and poor stability of MOFs and MOF-derived photocatalysts restrict their photocatalytic activity,thereby limiting their applications in the field of photocatalysis.Consequently,substantial research efforts have been directed toward maximizing the advantages of these intriguing materials while addressing their shortcomings.This review provides a comprehensive summary and analysis of various synthesis strategies of MOFs and their derivatives.Effective modification strategies to enhance the performance of these novel materials are also summarized.This review systematically explores the current advancements in the application of MOFs and their derivatives for photocatalytic water splitting,photocatalytic CO_(2)reduction,and environmental water pollution treatment.Finally,it discusses the challenges and future prospects of MOFs and MOF-derived materials in photocatalytic applications.Researchers should systematically optimize synthetic strategies and functionalize MOFs and their derivatives to enhance their application in energy conversion and environmental pollution control,thereby underscoring their extensive potential.Future research will increasingly concentrate on the intelligent design and functionalization of MOFs to attain superior catalytic performance and tackle the urgent energy and environmental challenges confronting the world.展开更多
The basidiomycetes Stereum hirsutum and Boreostereum vibrans are two fungi of the same genus.In this study,chemical investigation on the co-cultures of the two congeneric fungi led to the isolation of eleven new vibra...The basidiomycetes Stereum hirsutum and Boreostereum vibrans are two fungi of the same genus.In this study,chemical investigation on the co-cultures of the two congeneric fungi led to the isolation of eleven new vibralactone derivatives,hirsutavibrins A-K(1-11).The structures of 1-11 were elucidated by extensive NMR and HRESIMS spectroscopic analysis,and computational methods.Hirsutavibrins A(1)and B(2)showed weak cytotoxicity against the human lung cancer cell line A549.Hirsutavibrin D(4)showed moderate anti-nitric oxide activity in murine monocytic RAW 264.7 macrophages.This work not only expands the members of vibralactone derivatives with variable configurations but also opens a new avenue for fungal co-culturing study between congeneric fungi.展开更多
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Supported by the National Natural Science Foundation of China (10571035)
文摘By using cone-directed contingent derivatives, the unified necessary and sufficient optimality conditions are given for weakly and strongly minimal elements respectively in generalized preinvex set-valued optimization.
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By using harmonic representations of distributions, set-valued derivatives of one-dimensional distributions are introduced in this paper. And several equivalent definitions of the set-valued derivative are given for continuous real functions. The set-valued derivative of a local Lipschitz function coincides with the generalized gradient defined by F. H. Clarke. A distribution is Lipschitz near a point if and only if its set-valued derivative at this point is finite. When the set-valued derivative at some point of a distribution on R does not contain both +∞ and -∞ its distributional derivative is a Radon measure on some neighbourhood of this point. By using the first order'set-valued derivatives, an existence theorem of inverse functions of continuous functions is proved; and by using higher order ones, two very general sufficient conditions for a distribution to attain extremal values are obtained. A distribution is convex on an open interval if and only if its second order set-valued derivatives at all points of the interval are contained in [0, +∞]. Therefore, a satisfactory differential theory of nondifferentiable functions is developed.
文摘This note studies the optimality conditions of vector optimization problems involving generalized convexity in locally convex spaces. Based upon the concept of Dini set-valued directional derivatives, the necessary and sufficient optimality conditions are established for Henig proper and strong minimal solutions respectively in generalized preinvex vector optimization problems.
文摘Two tetrasubstituted carbazole derivatives TBICz and TOXDCz have been designed and synthesized,which possess the twist skeletons and exhibit excellent thermal and morphological stabilities.Utilizing these novel compounds as host material,high efficiency solution-processed green phosphorescent organic light-emitting diodes(PhOLEDs)have been achieved.The high triplet energies of TBICz and TOXDCz ensure efficient energy transfer from the host to the phosphor and triplet exciton confinement on the phosphor.Solution-processable green phospho⁃rescent devices employing Ir(ppy)3 as vip and the two tetrasubstituted carbazole derivatives as hosts exhibit high ef⁃ficiencies.The best EL performance is achieved for the TBICz-based device,with a maximum current efficiency of 27.3 cd/A,a maximum power efficiency of 15.9 lm/W,and a maximum external quantum efficiency of 7.8%,which provides more host material options for solution-processed OLEDs.
基金funded by the National Key Research and Development Program of China(No.2022YFC2804101)the Guangdong Provincial Key R&D Program(No.2023B1111050011)+2 种基金the Guangdong Basic and Applied Basic Research Foundation(No.2023A1515010432)the Guangzhou Basic and Applied Basic Research Foundation(No.202201010305)the High-Level Talents Special Program of Zhejiang(No.2022R52036)。
文摘Guided by molecular networking,nine novel curvularin derivatives(1-9)and 16 known analogs(10-25)were isolated from the hydrothermal vent sediment fungus Penicillium sp.HL-50.Notably,compounds 5-7 represented a hybrid of curvularin and purine.The structures and absolute configurations of compounds 1-9 were elucidated via nuclear magnetic resonance(NMR)spectroscopy,X-ray diffraction,electronic circular dichroism(ECD)calculations,^(13)C NMR calculation,modified Mosher's method,and chemical derivatization.Investigation of anti-inflammatory activities revealed that compounds 7-9,11,12,14,15,and 18 exhibited significant suppressive effects against lipopolysaccharide(LPS)-induced nitric oxide(NO)production in murine macrophage RAW264.7 cells,with IC_(50)values ranging from 0.44 to 4.40μmol·L^(-1).Furthermore,these bioactive compounds were found to suppress the expression of inflammation-related proteins,including inducible NO synthase(i NOS),cyclooxygenase-2(COX-2),NLR family pyrin domain-containing protein 3(NLRP3),and nuclear factor kappa-B(NF-κB).Additional studies demonstrated that the novel compound 7 possessed potent antiinflammatory activity by inhibiting the transcription of inflammation-related genes,downregulating the expression of inflammation-related proteins,and inhibiting the release of inflammatory cytokines,indicating its potential application in the treatment of inflammatory diseases.
基金supported by the Key Science and Technol-ogy Program of Henan Province(No.232102241020)the Ph.D.Research Startup Foundation of Henan University of Science and Technology(No.400613480015)+1 种基金the Postdoctoral Research Startup Foundation of Henan University of Science and Technology(No.400613554001)the Natural Science Foundation of Henan Province(242300420021).
文摘The poor reversibility and stability of Zn anodes greatly restrict the practical application of aqueous Zn-ion batteries(AZIBs),resulting from the uncontrollable dendrite growth and H_(2)O-induced side reactions during cycling.Electrolyte additive modification is considered one of the most effective and simplest methods for solving the aforementioned problems.Herein,the pyridine derivatives(PD)including 2,4-dihydroxypyridine(2,4-DHP),2,3-dihydroxypyridine(2,3-DHP),and 2-hydroxypyrdine(2-DHP),were em-ployed as novel electrolyte additives in ZnSO_(4)electrolyte.Both density functional theory calculation and experimental findings demonstrated that the incorporation of PD additives into the electrolyte effectively modulates the solvation structure of hydrated Zn ions,thereby suppressing side reactions in AZIBs.Ad-ditionally,the adsorption of PD molecules on the zinc anode surface contributed to uniform Zn deposi-tion and dendrite growth inhibition.Consequently,a 2,4-DHP-modified Zn/Zn symmetrical cell achieved an extremely long cyclic stability up to 5650 h at 1 mA cm^(-2).Furthermore,the Zn/NH_(4)V_(4)O_(10)full cell with 2,4-DHP-containing electrolyte exhibited an outstanding initial capacity of 204 mAh g^(-1),with a no-table capacity retention of 79%after 1000 cycles at 5 A g^(-1).Hence,this study expands the selection of electrolyte additives for AZIBs,and the working mechanism of PD additives provides new insights for electrolyte modification enabling highly reversible zinc anode.
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.
基金supported by the National Key Research and Development Program of China(No.2019YFC1804501)the National Natural Science Foundation of China(Nos.22036007 and 22122611)+1 种基金the Natural Science Foundation of Shandong Province(No.ZR2020ME228)the Introduction and Cultivation Plan for Young Innovative Talents of Colleges and Universities.
文摘This study investigated environmental distribution and human exposure of polycyclic aromatic hydrocarbons(PAHs)and their derivatives in one Chinese petroleum refinery facility.It was found that,following with high concentrations of 16 EPA PAHs(∑Parent-PAHs)in smelting subarea of studied petroleum refinery facility,total derivatives of PAHs[named as XPAHs,including nitro PAHs(NPAHs),chlorinated PAHs(Cl-PAHs),and brominated PAHs(Br-PAHs)]in gas(mean=1.57×10^(4)ng/m^(3)),total suspended particulate(TSP)(mean=4.33×10^(3) ng/m^(3))and soil(mean=4.37×10^(3) ng/g)in this subarea had 1.76-6.19 times higher levels than those from other subareas of this facility,surrounding residential areas and reference areas,indicating that petroleum refining processes would lead apparent derivation of PAHs.Especially,compared with those in residential and reference areas,gas samples in the petrochemical areas had higher∑NPAH/∑PAHs(mean=2.18),but lower∑Cl-PAH/∑PAHs(mean=1.43×10^(-1))and∑Br-PAH/∑PAHs ratios(mean=7.49×10^(-2)),indicating the richer nitrification of PAHs than chlorination during petrochemical process.The occupational exposure to PAHs and XPAHs in this petroleum refinery facility were 24-343 times higher than non-occupational exposure,and the ILCR(1.04×10^(-4))for petrochemical workers was considered to be potential high risk.Furthermore,one expanded high-resolution screening through GC Orbitrap/MS was performed for soils from petrochemical area,and another 35 PAHs were found,including alkyl-PAHs,phenyl-PAHs and other species,indicat-ing that profiles and risks of PAHs analogs in petrochemical areas deserve further expanded investigation.
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.
基金Project supported by the National Natural Science Foundation of China(No.22371303)the Zhongshan Municipal Bureau of Science and Technology(Nos.2021B2014,CXTD2022013)the Shanghai Rising-Star Program(21QA1411000)。
文摘A transition-metal-free strategy for the synthesis of carboline derivatives via sequential dual C—N bond formation in a one-pot reaction is reported.Using 2,2'-dihalogenated pyridyl biaryls and primary amines as starting materials,this method efficiently constructs a series ofα-,β-,γ-andδ-carbolines under alkaline conditions.The reaction proceeds smoothly in the presence of lithium tert-butoxide(t-BuOLi)or cesium carbonate(Cs_(2)CO_(3))without requiring transition metal catalysts,demonstrating good functional group tolerance.This approach enables gram-scale synthesis and has been successfully applied to the preparation of the organic material 2,6-CbPy,achieving high conversion efficiency.
文摘Chronic obstructive pulmonary disease(COPD)has garnered increased attention as a result of its persistent symptoms,which undermine patientsʼquality of life.Fudosteine has substantial advantages in the treatment of COPD due to its high efficacy and low adverse effects.In this study,Fudosteine sulfonamide derivatives Series I and amine derivatives Series II were designed and synthesized,and their biological activities were evaluated.The results showed that compound 6f had outstanding anti-inflammatory action with an IC_(50) of 1.08 mmol/L,and a higher antioxidant capacity than the lead molecule.At the same time,molecular docking investigations have revealed that compound 6f establishes hydrogen bonds and hydrophobic contacts with the MUC5AC protein.Furthermore,derivative 1f inhibited PDE4A1 enzyme activity five times more than Fudosteine.2,2-Diphenyl-1-picrylhydrazyl(DPPH)free radical scavenging tests demonstrated that all examined substances had higher antioxidant activity than Fudosteine.This study established a solid foundation for further research into COPD drug therapy.
文摘The selective hydrogenation ofα,β-unsaturated aldehydes/ketones enables precise control over product structures and properties by regulating hydrogen transport pathways and bond cleavage sequences to selectively reduce C=C or C=O bonds while preserving other functional groups within the molecule.This approach serves as a critical strategy for the directional synthesis of high-value molecules.However,achieving such selectivity remains challenging due to the thermodynamic equilibrium and kinetic competition between C=O and C=C bonds inα,β-unsaturated systems.Consequently,constructing precisely targeted catalytic systems is essential to overcome these limitations,offering both fundamental scientific significance and industrial application potential.Metal-organic frameworks(MOFs)and their derivatives have emerged as innovative platforms for designing such systems,owing to their programmable topology,tunable pore microenvironments,spatially controllable active sites,and modifiable electronic structures.This review systematically summarizes the research progress of MOF-based catalysts for selec-tive hydrogenation ofα,β-unsaturated aldehydes/ketones in the last decade,with emphasis on the design strategy,conformational relationship,and catalytic mechanism,aiming to provide new ideas for the design of targeted catalyt-ic systems for the selective hydrogenation ofα,β-unsaturated aldehydes/ketones.
基金supported by the National Natural Science Foundation of China(61703286,62394342,61890924,61991404)。
文摘This paper investigates set-valued state estimation of nonlinear systems with unknown-but-bounded(UBB)noises based on constrained polynomial zonotopes which is utilized to characterize non-convex sets.First,properties of constrained polynomial zonotopes are provided and the order reduction method is given to reduce the computational complexity.Then,the corresponding improved prediction-update algorithm is proposed so that it can be adapted to non-convex sets.Based on generalized intersection,the utilization of set-based estimation for attack detection is analyzed.Finally,an example is given to show the efficiency of our results.
基金The financial support for this study by the Technology Project of Qingdao(22-3-7-cspz-9-nsh)the National Key Research and Development Program(2021YFB3500102)。
文摘Energy conversion and environmental pollution present significant challenges that necessitate the development of materials with optimal characteristics for effective applications in solar energy-driven photocatalysis.Metal-organic frameworks(MOFs)serve as excellent platforms for the development of various MOF-derived materials,which have garnered extensive attention due to their unique structural features,high crystallinity,large surface areas,diverse morphologies,adjustable dimensions,tunable textural characteristics,and inherent catalytic activity.However,the sluggish charge kinetics and poor stability of MOFs and MOF-derived photocatalysts restrict their photocatalytic activity,thereby limiting their applications in the field of photocatalysis.Consequently,substantial research efforts have been directed toward maximizing the advantages of these intriguing materials while addressing their shortcomings.This review provides a comprehensive summary and analysis of various synthesis strategies of MOFs and their derivatives.Effective modification strategies to enhance the performance of these novel materials are also summarized.This review systematically explores the current advancements in the application of MOFs and their derivatives for photocatalytic water splitting,photocatalytic CO_(2)reduction,and environmental water pollution treatment.Finally,it discusses the challenges and future prospects of MOFs and MOF-derived materials in photocatalytic applications.Researchers should systematically optimize synthetic strategies and functionalize MOFs and their derivatives to enhance their application in energy conversion and environmental pollution control,thereby underscoring their extensive potential.Future research will increasingly concentrate on the intelligent design and functionalization of MOFs to attain superior catalytic performance and tackle the urgent energy and environmental challenges confronting the world.
基金supported by the National Natural Science Foundation of China(Grant number 82473810)the Fundamental Research Funds for the Central Universities,South-Central Minzu University(Grant No.CPT22033).
文摘The basidiomycetes Stereum hirsutum and Boreostereum vibrans are two fungi of the same genus.In this study,chemical investigation on the co-cultures of the two congeneric fungi led to the isolation of eleven new vibralactone derivatives,hirsutavibrins A-K(1-11).The structures of 1-11 were elucidated by extensive NMR and HRESIMS spectroscopic analysis,and computational methods.Hirsutavibrins A(1)and B(2)showed weak cytotoxicity against the human lung cancer cell line A549.Hirsutavibrin D(4)showed moderate anti-nitric oxide activity in murine monocytic RAW 264.7 macrophages.This work not only expands the members of vibralactone derivatives with variable configurations but also opens a new avenue for fungal co-culturing study between congeneric fungi.
