As naturally abundant and readily available starting materials,alcohols are frequently employed as synthetic building blocks in organic synthesis.The hydroxyl group,which serves as the characteristic functional group ...As naturally abundant and readily available starting materials,alcohols are frequently employed as synthetic building blocks in organic synthesis.The hydroxyl group,which serves as the characteristic functional group of alcohols,is the primary reactive site for these compounds.Consequently,dehydroxylative functionalization reaction is one of the representative transformations of alcohols and has demonstrated significant potential in constructing new chemical bonds.Over the past decade,this research field has received continuous and extensive attention.This review comprehensively summarizes the recent advances in the dehydroxylative functionalization of alcohols,discussing on the reaction methodologies and mechanisms for constructing carbon-heteroatom and carbon-carbon bonds from alcohols.展开更多
Selective functionalization of C-F bonds in trifluoromethyl groups has recently received a growing interest, as it offers atom- and step-economic pathways to access highly valuable mono- and difluoroalkyl-substituted ...Selective functionalization of C-F bonds in trifluoromethyl groups has recently received a growing interest, as it offers atom- and step-economic pathways to access highly valuable mono- and difluoroalkyl-substituted organic molecules using simple and inexpensive trifluoromethyl sources as the starting materials. In this regard, impressive progress has been made on the defluorinative functionalization reactions that proceed via radical intermediates. Nevertheless, it is still a great challenge to precisely control the defluorination process, due to the continuous decrease of the C-F bond strength after the replacement of one or two fluorine atoms with various functionalities. This review article is aimed to provide a brief overview of recently reported methods used to functionalize C-F bonds of CF_(3) groups via radical intermediates. An emphasis is placed on the discussion of mechanistic aspects and synthetic applications.展开更多
Aliphatic C-H groups are among the most abundant yet least reactive functional groups in organic molecules.Nature has evolved metalloenzymes such as those of the cytochrome P450 superfamily that efficiently activate i...Aliphatic C-H groups are among the most abundant yet least reactive functional groups in organic molecules.Nature has evolved metalloenzymes such as those of the cytochrome P450 superfamily that efficiently activate individual tertiary(3)and secondary(2)C(sp^(3))-H bonds in complex molecules with the highest level of regio-and stereoselectivity[1],thus encouraging studies aimed at engineering artificial metalloenzymes for synthetic applications[2].展开更多
Spinal cord injury represents a severe form of central nervous system trauma for which effective treatments remain limited.Microglia is the resident immune cells of the central nervous system,play a critical role in s...Spinal cord injury represents a severe form of central nervous system trauma for which effective treatments remain limited.Microglia is the resident immune cells of the central nervous system,play a critical role in spinal cord injury.Previous studies have shown that microglia can promote neuronal survival by phagocytosing dead cells and debris and by releasing neuroprotective and anti-inflammatory factors.However,excessive activation of microglia can lead to persistent inflammation and contribute to the formation of glial scars,which hinder axonal regeneration.Despite this,the precise role and mechanisms of microglia during the acute phase of spinal cord injury remain controversial and poorly understood.To elucidate the role of microglia in spinal cord injury,we employed the colony-stimulating factor 1 receptor inhibitor PLX5622 to deplete microglia.We observed that sustained depletion of microglia resulted in an expansion of the lesion area,downregulation of brain-derived neurotrophic factor,and impaired functional recovery after spinal cord injury.Next,we generated a transgenic mouse line with conditional overexpression of brain-derived neurotrophic factor specifically in microglia.We found that brain-derived neurotrophic factor overexpression in microglia increased angiogenesis and blood flow following spinal cord injury and facilitated the recovery of hindlimb motor function.Additionally,brain-derived neurotrophic factor overexpression in microglia reduced inflammation and neuronal apoptosis during the acute phase of spinal cord injury.Furthermore,through using specific transgenic mouse lines,TMEM119,and the colony-stimulating factor 1 receptor inhibitor PLX73086,we demonstrated that the neuroprotective effects were predominantly due to brain-derived neurotrophic factor overexpression in microglia rather than macrophages.In conclusion,our findings suggest the critical role of microglia in the formation of protective glial scars.Depleting microglia is detrimental to recovery of spinal cord injury,whereas targeting brain-derived neurotrophic factor overexpression in microglia represents a promising and novel therapeutic strategy to enhance motor function recovery in patients with spinal cord injury.展开更多
Zero-dimensional graphene quantum dots(GQDs)exhibit many different properties,such as strong fluorescence,nonzero bandgap and solubility in solvents,compared to two-dimensional graphene.GQDs are biocompatible and have...Zero-dimensional graphene quantum dots(GQDs)exhibit many different properties,such as strong fluorescence,nonzero bandgap and solubility in solvents,compared to two-dimensional graphene.GQDs are biocompatible and have low toxicity;hence,they are widely used in the biomedical field.The edge effect of GQDs is of particular interest because edge modification can regulate the performance of nanomaterials.In this review,various preparation methods for GQDs,which can be divided into three main categories,namely top-down,bottom-up and chemical methods,are discussed.The unique optical,electrical,thermal and magnetic properties of GQDs are reviewed.The functionalization of GQDs by doping with heteroatoms and forming composites with other materials is studied,and the characteristics of these GQDs are also discussed.The applications of these GQDs in the fields of optics,electricity,optoelectronics,biomedicine,energy,agriculture and other emerging interdisciplinary fields are reviewed to highlight the enormous potential of nanomaterials.This review reports on the recent advancement in GQD research and suggests future directions for the development of GQDs.展开更多
This study investigates the properties of high-purity starches extracted from Polygonum multiflorum(PMS)and Smilax glabra(SGS).The starches were characterized by scanning electron microscopy,Fouriertransform infrared ...This study investigates the properties of high-purity starches extracted from Polygonum multiflorum(PMS)and Smilax glabra(SGS).The starches were characterized by scanning electron microscopy,Fouriertransform infrared spectroscopy,X-ray diffraction,high-performance anion-exchange chromatography,and differential scanning calorimetry.Significant differences were observed in their morphological,physicochemical,and functional properties.PMS had a smaller particle size(13.68 μm),irregular polygonal shape,A-type,lower water absorption(62.67 %),and higher oil absorption(51.17 %).In contrast,SGS exhibited larger particles(31.75 μm),a nearly spherical shape,B-type,higher crystallinity(50.66 %),and greater amylose content(21.54 %),with superior thermal stability,shear resistance,and gelatinization enthalpy.SGS also contained higher resistant starch(83.28 %) and longer average chain length(20.58 %),but showed lower solubility,swelling power,light transmittance,and freeze-thaw stability.The physicochemical properties differences in crystal pattern and particle morphology between PMS and SGS lead to distinct behaviors during in vitro digestion and fermentation.These findings highlight the potential of medicinal plant starches in functional ingredients and industrial processes.展开更多
Gauss radial basis functions(GRBF)are frequently employed in data fitting and machine learning.Their linear independence property can theoretically guarantee the avoidance of data redundancy.In this paper,one of the m...Gauss radial basis functions(GRBF)are frequently employed in data fitting and machine learning.Their linear independence property can theoretically guarantee the avoidance of data redundancy.In this paper,one of the main contributions is proving this property using linear algebra instead of profound knowledge.This makes it easy to read and understand this fundamental fact.The proof of linear independence of a set of Gauss functions relies on the constructing method for one-dimensional space and on the deducing method for higher dimensions.Additionally,under the condition of preserving the same moments between the original function and interpolating function,both the interpolating existence and uniqueness are proven for GRBF in one-dimensional space.The final work demonstrates the application of the GRBF method to locate lunar olivine.By combining preprocessed data using GRBF with the removing envelope curve method,a program is created to find the position of lunar olivine based on spectrum data,and the numerical experiment shows that it is an effective scheme.展开更多
In this paper,we study the generalized Dedekind Rademacher sums considered by Hall,Wilson and Zagier.We establish a new formula for the products of two Bernoulli functions by using Parseval's formula,Hurwitz's...In this paper,we study the generalized Dedekind Rademacher sums considered by Hall,Wilson and Zagier.We establish a new formula for the products of two Bernoulli functions by using Parseval's formula,Hurwitz's formula and Lerch's functional equation.As applications of the result,some well-known reciprocity formulas are deduced as special cases.展开更多
BACKGROUND:Hemiplegia,a prevalent stroke-related condition,is often studied for motor dysfunction;however,spasticity remains under-researched.Abnormal muscle tone significantly hinders hemiplegic patients’walking rec...BACKGROUND:Hemiplegia,a prevalent stroke-related condition,is often studied for motor dysfunction;however,spasticity remains under-researched.Abnormal muscle tone significantly hinders hemiplegic patients’walking recovery.OBJECTIVE:To determine whether early suspension-protected training with a personal assistant machine for stroke patients enhances walking ability and prevents muscle spasms.METHODS:Thirty-two early-stage stroke patients from Shenzhen University General Hospital and the China Rehabilitation Research Center were randomly assigned to the experimental group(n=16)and the control group(n=16).Both groups underwent 4 weeks of gait training under the suspension protection system for 30 minutes daily,5 days a week.The experimental group used the personal assistant machine during training.Three-dimensional gait analysis(using the Cortex motion capture system),Brunnstrom staging,Fugl-Meyer Assessment for lower limb motor function,Fugl-Meyer balance function,and the modified Ashworth Scale were evaluated within 1 week before the intervention and after 4 weeks of intervention.RESULTS AND CONCLUSION:After the 4-week intervention,all outcome measures showed significant changes in each group.The experimental group had a small but significant increase in the modified Ashworth Scale score(P<0.05,d=|0.15|),while the control group had a large significant increase(P<0.05,d=|1.48|).The experimental group demonstrated greater improvements in walking speed(16.5 to 38.44 cm/s,P<0.05,d=|4.01|),step frequency(46.44 to 64.94 steps/min,P<0.05,d=|2.32|),stride length(15.50 to 29.81 cm,P<0.05,d=|3.44|),and peak hip and knee flexion(d=|1.82|to|2.17|).After treatment,the experimental group showed significantly greater improvements than the control group in walking speed(38.44 vs.26.63 cm/s,P<0.05,d=|2.75|),stride length,peak hip and knee flexion(d=|1.31|to|1.45|),step frequency(64.94 vs.59.38 steps/min,P<0.05,d=|0.85|),and a reduced support phase(bilateral:24.31%vs.28.38%,P<0.05,d=|0.88|;non-paretic:66.19%vs.70.13%,P<0.05,d=|0.94|).For early hemiplegia,personal assistant machine-assisted gait training under the suspension protection system helps establish a correct gait pattern,prevents muscle spasms,and improves motor function.展开更多
Photocatalysis is an important technology for using solar energy to produce hydrogen,convert CO_(2) to synthetic fuels,and decrease persistent pollutant.However,conventional photocatalysts have limitations,including p...Photocatalysis is an important technology for using solar energy to produce hydrogen,convert CO_(2) to synthetic fuels,and decrease persistent pollutant.However,conventional photocatalysts have limitations,including poor spectral absorption,inefficient charge separation,and structural instability under operational stress,which demand innovative durable materials with tailored electronic properties.Nanodiamond(ND)has recently been recognized as a suitable material because of its exceptional chemical stability,superior charge carrier mobility,and possible surface functionalization.While its intrinsic wide bandgap limits its response to visible-light,different methods have been demonstrated to activate its catalytic potential.Here,several emerging strategies for improving the catalytic performance of ND-based photocatalytic systems are summarized,including surface functionalization,plasmonic hybridization,heteroatom doping,and heterostructure design.And the structure-activity relationship and design principle are proposed to improve the light harvesting,charge transport,and redox kinetics for constructing high efficiency ND-based photocatalysts used in the renewable energy and environmental industries.展开更多
Behavior recognition of Hu sheep contributes to their intensive and intelligent farming.Due to the generally high density of Hu sheep farming,severe occlusion occurs among different behaviors and even among sheep perf...Behavior recognition of Hu sheep contributes to their intensive and intelligent farming.Due to the generally high density of Hu sheep farming,severe occlusion occurs among different behaviors and even among sheep performing the same behavior,leading to missing and false detection issues in existing behavior recognition methods.A high-low frequency aggregated attention and negative sample comprehensive score loss and comprehensive score soft non-maximum suppression-YOLO(HLNC-YOLO)was proposed for identifying the behavior of Hu sheep,addressing the issues of missed and erroneous detections caused by occlusion between Hu sheep in intensive farming.Firstly,images of four typical behaviors-standing,lying,eating,and drinking-were collected from the sheep farm to construct the Hu sheep behavior dataset(HSBD).Next,to solve the occlusion issues,during the training phase,the C2F-HLAtt module was integrated,which combined high-low frequency aggregation attention,into the YOLO v8 Backbone to perceive occluded objects and introduce an auxiliary reversible branch to retain more effective features.Using comprehensive score regression loss(CSLoss)to reduce the scores of suboptimal boxes and enhance the comprehensive scores of occluded object boxes.Finally,the soft comprehensive score non-maximal suppression(Soft-CS-NMS)algorithm filtered prediction boxes during the inferencing.Testing on the HSBD,HLNC-YOLO achieved a mean average precision(mAP@50)of 87.8%,with a memory footprint of 17.4 MB.This represented an improvement of 7.1,2.2,4.6,and 11 percentage points over YOLO v8,YOLO v9,YOLO v10,and Faster R-CNN,respectively.Research indicated that the HLNC-YOLO accurately identified the behavior of Hu sheep in intensive farming and possessed generalization capabilities,providing technical support for smart farming.展开更多
Hydrogen peroxide(H_(2)O_(2))oxidation and reduction reactions(HPOR/HPRR)are pivotal in various innovative electrochemical energy conversion devices.A comprehensive understanding of these mechanisms is critical for ca...Hydrogen peroxide(H_(2)O_(2))oxidation and reduction reactions(HPOR/HPRR)are pivotal in various innovative electrochemical energy conversion devices.A comprehensive understanding of these mechanisms is critical for catalyst design and performance improvement in these applications.In this work,we systematically investigate the HPOR/HPRR mechanisms on low-index Pt surfaces,specifically Pt(111),Pt(100)and Pt(110),through density functional theory(DFT)calculations combined with the computational hydrogen electrode(CHE)model.For HPOR,all the low-index Pt surfaces exhibit a unified potential-determining step(PDS)involving the electrochemical oxidation of hydroperoxyl intermediates(HOO*).The binding free energy of HOO*(Δ_(GHOO*))emerges as an activity descriptor,with Pt(110)exhibiting the highest HPOR activity.The HPRR mechanism follows a chem-electrochemical(C-EC)pathway.The rate-determining step(RDS)of HPRR is either the cleavage of the HO-OH bond(chemical)or the reduction of HO(electrochemical),depending on their respective activation energies.These activation energies are functions of the HO*binding free energy,Δ_(GHO*),establishingΔ_(GHO*)as the descriptor for HPRR activity prediction.Pt(111)and Pt(100)are identified as the most active HPRR catalysts among the studied metal surfaces,although they still experience a significant overpotential.The scaling relationship betweenΔ_(GHOO*)andΔ_(GHO*)reveals a thermodynamic coupling of HPOR and HPRR,explaining their occurrence on Pt surfaces.These findings provide important insights and activity descriptors for both HPOR and HPRR,providing valuable guidance for the design of electrocatalysts in H_(2)O_(2)-related energy applications and fuel cells.展开更多
The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecul...The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecules and{[Co2(BINDI)(DMA)_(2)]·DMA}_(n)(Co-MOF,H4BINDI=N,N'-bis(5-isophthalic acid)naphthalenediimide,DMA=N,N-dimethylacetamide)was synthesized via a one-pot method,leveragingπ-πinteractions between pyrene and Co-MOF to modulate electrical conductivity.Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes,achieving an overpotential of 246 mV at a current density of 10 mA·cm^(-2) along with excellent stability.Density functional theory(DFT)calculations reveal that the formation of O*in the second step is the rate-determining step(RDS)during the OER process on Co-MOF,with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH*intermediate for Co sites.CCDC:2419276.展开更多
Biomass-derived carbon materials are favored for their abundance and sustainability,and ease of preparation and modification.By surface activation and modification they can have a good electrical conductivity,excellen...Biomass-derived carbon materials are favored for their abundance and sustainability,and ease of preparation and modification.By surface activation and modification they can have a good electrical conductivity,excellent catalytic activity,a remarkable adsorption capacity,and different interfacial physicochemical functionalities.Surface-modified biochars have found wide applications in energy storage,environmental remediation,and catalysis.However,achieving precise and controllable modification of their active sites remains a challenge.Recent advances and future prospects for controlling their surface morphology,defect engineering,and surface coating strategies,with particular attention to their means of fabrication,are reviewed.展开更多
A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescenc...A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.展开更多
Spinal cord injury(SCI)is a debilitating ailment that leads to the loss of motor and sensory functions,often leaving the patient paralyzed below the injury site(Chen et al.,2013).Globally around 250,000-300,000 people...Spinal cord injury(SCI)is a debilitating ailment that leads to the loss of motor and sensory functions,often leaving the patient paralyzed below the injury site(Chen et al.,2013).Globally around 250,000-300,000 people are diagnosed with SCI annually(Singh et al.,2014),and while this number appears quite low,the effect that an SCI has on the patient’s quality of life is drastic,due to the current difficulties to comprehensively treat this illness.The cost of patient care can also be quite costly,amounting to an estimated$1.69 billion in healthcare costs in the USA alone(Mahabaleshwarkar and Khanna,2014).展开更多
The advantages of genome selection(GS) in animal and plant breeding are self-evident.Traditional parametric models have disadvantage in better fit the increasingly large sequencing data and capture complex effects acc...The advantages of genome selection(GS) in animal and plant breeding are self-evident.Traditional parametric models have disadvantage in better fit the increasingly large sequencing data and capture complex effects accurately.Machine learning models have demonstrated remarkable potential in addressing these challenges.In this study,we introduced the concept of mixed kernel functions to explore the performance of support vector machine regression(SVR) in GS.Six single kernel functions(SVR_L,SVR_C,SVR_G,SVR_P,SVR_S,SVR_L) and four mixed kernel functions(SVR_GS,SVR_GP,SVR_LS,SVR_LP) were used to predict genome breeding values.The prediction accuracy,mean squared error(MSE) and mean absolute error(MAE) were used as evaluation indicators to compare with two traditional parametric models(GBLUP,BayesB) and two popular machine learning models(RF,KcRR).The results indicate that in most cases,the performance of the mixed kernel function model significantly outperforms that of GBLUP,BayesB and single kernel function.For instance,for T1 in the pig dataset,the predictive accuracy of SVR_GS is improved by 10% compared to GBLUP,and by approximately 4.4 and 18.6% compared to SVR_G and SVR_S respectively.For E1 in the wheat dataset,SVR_GS achieves 13.3% higher prediction accuracy than GBLUP.Among single kernel functions,the Laplacian and Gaussian kernel functions yield similar results,with the Gaussian kernel function performing better.The mixed kernel function notably reduces the MSE and MAE when compared to all single kernel functions.Furthermore,regarding runtime,SVR_GS and SVR_GP mixed kernel functions run approximately three times faster than GBLUP in the pig dataset,with only a slight increase in runtime compared to the single kernel function model.In summary,the mixed kernel function model of SVR demonstrates speed and accuracy competitiveness,and the model such as SVR_GS has important application potential for GS.展开更多
Functional gastrointestinal disorders(FGIDs),including irritable bowel syndrome(IBS),functional dyspepsia(FD),and gastroesophageal reflux disease(GERD),present persistent diagnostic and therapeutic challenges due to s...Functional gastrointestinal disorders(FGIDs),including irritable bowel syndrome(IBS),functional dyspepsia(FD),and gastroesophageal reflux disease(GERD),present persistent diagnostic and therapeutic challenges due to symptom heterogeneity and the absence of reliable biomarkers.Artificial intelligence(AI)enables the integration of multimodal data to enhance FGID management through precision diagnostics and preventive healthcare.This minireview summarizes recent advancements in AI applications for FGIDs,highlighting progress in diagnostic accuracy,subtype classification,personalized interventions,and preventive strategies inspired by the traditional Chinese medicine concept of“treating the undiseased”.Machine learning and deep learning algorithms have demonstrated value in improving IBS diagnosis,refining FD neuro-gastrointestinal subtyping,and screening for GERD-related complications.Moreover,AI supports dietary,psychological,and integrative medicine-based interventions to improve patient adherence and quality of life.Nonetheless,key challenges remain,including data heterogeneity,limited model interpretability,and the need for robust clinical validation.Future directions emphasize interdisciplinary collaboration,the development of multimodal and explainable AI models,and the creation of patientcentered platforms to facilitate a shift from reactive treatment to proactive prevention.This review provides a systematic framework to guide the clinical application and theoretical innovation of AI in FGIDs.展开更多
The incorporation of small fluorinated functional groups,including CF_(3),CF_(2)H,and CFH_(2),into small molecules represents a crucial strategy for modulating their physical,chemical,and biological characteristics[1,...The incorporation of small fluorinated functional groups,including CF_(3),CF_(2)H,and CFH_(2),into small molecules represents a crucial strategy for modulating their physical,chemical,and biological characteristics[1,2].Consequently,organofluorine compounds are frequently encountered in pharmaceuticals and agrochemicals.Significant advances have been made in the introduction of fluoroalkyl groups into small molecules since the beginning of the 21st century.展开更多
基金Project supported by the Technology Program of Zhoukou(No.2023GG02054)the Natural Science Foundation of Shandong Province(No.ZR2024MB082)the Open Foundation Supported by Jiangsu Province Engineering Research Center of Precision Diagnostics and Therapeutics Development(No.SDGC2401)。
文摘As naturally abundant and readily available starting materials,alcohols are frequently employed as synthetic building blocks in organic synthesis.The hydroxyl group,which serves as the characteristic functional group of alcohols,is the primary reactive site for these compounds.Consequently,dehydroxylative functionalization reaction is one of the representative transformations of alcohols and has demonstrated significant potential in constructing new chemical bonds.Over the past decade,this research field has received continuous and extensive attention.This review comprehensively summarizes the recent advances in the dehydroxylative functionalization of alcohols,discussing on the reaction methodologies and mechanisms for constructing carbon-heteroatom and carbon-carbon bonds from alcohols.
基金National Natural Science Foundation of China (No.21971226)the Fundamental Research Funds for the Central Universities (No. WK2060000017) for financial support。
文摘Selective functionalization of C-F bonds in trifluoromethyl groups has recently received a growing interest, as it offers atom- and step-economic pathways to access highly valuable mono- and difluoroalkyl-substituted organic molecules using simple and inexpensive trifluoromethyl sources as the starting materials. In this regard, impressive progress has been made on the defluorinative functionalization reactions that proceed via radical intermediates. Nevertheless, it is still a great challenge to precisely control the defluorination process, due to the continuous decrease of the C-F bond strength after the replacement of one or two fluorine atoms with various functionalities. This review article is aimed to provide a brief overview of recently reported methods used to functionalize C-F bonds of CF_(3) groups via radical intermediates. An emphasis is placed on the discussion of mechanistic aspects and synthetic applications.
基金supported by the Russian Science Foundation Project (20-13-00032)。
文摘Aliphatic C-H groups are among the most abundant yet least reactive functional groups in organic molecules.Nature has evolved metalloenzymes such as those of the cytochrome P450 superfamily that efficiently activate individual tertiary(3)and secondary(2)C(sp^(3))-H bonds in complex molecules with the highest level of regio-and stereoselectivity[1],thus encouraging studies aimed at engineering artificial metalloenzymes for synthetic applications[2].
基金supported by the National Natural Science Foundation of China,Nos.82072165 and 82272256(both to XM)the Key Project of Xiangyang Central Hospital,No.2023YZ03(to RM)。
文摘Spinal cord injury represents a severe form of central nervous system trauma for which effective treatments remain limited.Microglia is the resident immune cells of the central nervous system,play a critical role in spinal cord injury.Previous studies have shown that microglia can promote neuronal survival by phagocytosing dead cells and debris and by releasing neuroprotective and anti-inflammatory factors.However,excessive activation of microglia can lead to persistent inflammation and contribute to the formation of glial scars,which hinder axonal regeneration.Despite this,the precise role and mechanisms of microglia during the acute phase of spinal cord injury remain controversial and poorly understood.To elucidate the role of microglia in spinal cord injury,we employed the colony-stimulating factor 1 receptor inhibitor PLX5622 to deplete microglia.We observed that sustained depletion of microglia resulted in an expansion of the lesion area,downregulation of brain-derived neurotrophic factor,and impaired functional recovery after spinal cord injury.Next,we generated a transgenic mouse line with conditional overexpression of brain-derived neurotrophic factor specifically in microglia.We found that brain-derived neurotrophic factor overexpression in microglia increased angiogenesis and blood flow following spinal cord injury and facilitated the recovery of hindlimb motor function.Additionally,brain-derived neurotrophic factor overexpression in microglia reduced inflammation and neuronal apoptosis during the acute phase of spinal cord injury.Furthermore,through using specific transgenic mouse lines,TMEM119,and the colony-stimulating factor 1 receptor inhibitor PLX73086,we demonstrated that the neuroprotective effects were predominantly due to brain-derived neurotrophic factor overexpression in microglia rather than macrophages.In conclusion,our findings suggest the critical role of microglia in the formation of protective glial scars.Depleting microglia is detrimental to recovery of spinal cord injury,whereas targeting brain-derived neurotrophic factor overexpression in microglia represents a promising and novel therapeutic strategy to enhance motor function recovery in patients with spinal cord injury.
基金the National Natural Science Foundation of China(Grant Nos.61106098,51201150 and 11374250)Key Project of Applied Basic Research of Yunnan Province,China(Grant No.2012FA003)PolyU Grant(1-ZVGH)and Research Grants Council of Hong Kong(Project Nos.PolyU 153030/15P and PolyU 153271/16P).
文摘Zero-dimensional graphene quantum dots(GQDs)exhibit many different properties,such as strong fluorescence,nonzero bandgap and solubility in solvents,compared to two-dimensional graphene.GQDs are biocompatible and have low toxicity;hence,they are widely used in the biomedical field.The edge effect of GQDs is of particular interest because edge modification can regulate the performance of nanomaterials.In this review,various preparation methods for GQDs,which can be divided into three main categories,namely top-down,bottom-up and chemical methods,are discussed.The unique optical,electrical,thermal and magnetic properties of GQDs are reviewed.The functionalization of GQDs by doping with heteroatoms and forming composites with other materials is studied,and the characteristics of these GQDs are also discussed.The applications of these GQDs in the fields of optics,electricity,optoelectronics,biomedicine,energy,agriculture and other emerging interdisciplinary fields are reviewed to highlight the enormous potential of nanomaterials.This review reports on the recent advancement in GQD research and suggests future directions for the development of GQDs.
基金supported by the National Natural Science Foundation of China (No.82174074)。
文摘This study investigates the properties of high-purity starches extracted from Polygonum multiflorum(PMS)and Smilax glabra(SGS).The starches were characterized by scanning electron microscopy,Fouriertransform infrared spectroscopy,X-ray diffraction,high-performance anion-exchange chromatography,and differential scanning calorimetry.Significant differences were observed in their morphological,physicochemical,and functional properties.PMS had a smaller particle size(13.68 μm),irregular polygonal shape,A-type,lower water absorption(62.67 %),and higher oil absorption(51.17 %).In contrast,SGS exhibited larger particles(31.75 μm),a nearly spherical shape,B-type,higher crystallinity(50.66 %),and greater amylose content(21.54 %),with superior thermal stability,shear resistance,and gelatinization enthalpy.SGS also contained higher resistant starch(83.28 %) and longer average chain length(20.58 %),but showed lower solubility,swelling power,light transmittance,and freeze-thaw stability.The physicochemical properties differences in crystal pattern and particle morphology between PMS and SGS lead to distinct behaviors during in vitro digestion and fermentation.These findings highlight the potential of medicinal plant starches in functional ingredients and industrial processes.
基金Supported by the National Basic Research Program of China(2012CB025904)Zhengzhou Shengda University of Economics,Business and Management(SD-YB2025085)。
文摘Gauss radial basis functions(GRBF)are frequently employed in data fitting and machine learning.Their linear independence property can theoretically guarantee the avoidance of data redundancy.In this paper,one of the main contributions is proving this property using linear algebra instead of profound knowledge.This makes it easy to read and understand this fundamental fact.The proof of linear independence of a set of Gauss functions relies on the constructing method for one-dimensional space and on the deducing method for higher dimensions.Additionally,under the condition of preserving the same moments between the original function and interpolating function,both the interpolating existence and uniqueness are proven for GRBF in one-dimensional space.The final work demonstrates the application of the GRBF method to locate lunar olivine.By combining preprocessed data using GRBF with the removing envelope curve method,a program is created to find the position of lunar olivine based on spectrum data,and the numerical experiment shows that it is an effective scheme.
基金Supported by the Natural Science Foundation of Sichuan Province(No.2023NSFSC0065)。
文摘In this paper,we study the generalized Dedekind Rademacher sums considered by Hall,Wilson and Zagier.We establish a new formula for the products of two Bernoulli functions by using Parseval's formula,Hurwitz's formula and Lerch's functional equation.As applications of the result,some well-known reciprocity formulas are deduced as special cases.
文摘BACKGROUND:Hemiplegia,a prevalent stroke-related condition,is often studied for motor dysfunction;however,spasticity remains under-researched.Abnormal muscle tone significantly hinders hemiplegic patients’walking recovery.OBJECTIVE:To determine whether early suspension-protected training with a personal assistant machine for stroke patients enhances walking ability and prevents muscle spasms.METHODS:Thirty-two early-stage stroke patients from Shenzhen University General Hospital and the China Rehabilitation Research Center were randomly assigned to the experimental group(n=16)and the control group(n=16).Both groups underwent 4 weeks of gait training under the suspension protection system for 30 minutes daily,5 days a week.The experimental group used the personal assistant machine during training.Three-dimensional gait analysis(using the Cortex motion capture system),Brunnstrom staging,Fugl-Meyer Assessment for lower limb motor function,Fugl-Meyer balance function,and the modified Ashworth Scale were evaluated within 1 week before the intervention and after 4 weeks of intervention.RESULTS AND CONCLUSION:After the 4-week intervention,all outcome measures showed significant changes in each group.The experimental group had a small but significant increase in the modified Ashworth Scale score(P<0.05,d=|0.15|),while the control group had a large significant increase(P<0.05,d=|1.48|).The experimental group demonstrated greater improvements in walking speed(16.5 to 38.44 cm/s,P<0.05,d=|4.01|),step frequency(46.44 to 64.94 steps/min,P<0.05,d=|2.32|),stride length(15.50 to 29.81 cm,P<0.05,d=|3.44|),and peak hip and knee flexion(d=|1.82|to|2.17|).After treatment,the experimental group showed significantly greater improvements than the control group in walking speed(38.44 vs.26.63 cm/s,P<0.05,d=|2.75|),stride length,peak hip and knee flexion(d=|1.31|to|1.45|),step frequency(64.94 vs.59.38 steps/min,P<0.05,d=|0.85|),and a reduced support phase(bilateral:24.31%vs.28.38%,P<0.05,d=|0.88|;non-paretic:66.19%vs.70.13%,P<0.05,d=|0.94|).For early hemiplegia,personal assistant machine-assisted gait training under the suspension protection system helps establish a correct gait pattern,prevents muscle spasms,and improves motor function.
文摘Photocatalysis is an important technology for using solar energy to produce hydrogen,convert CO_(2) to synthetic fuels,and decrease persistent pollutant.However,conventional photocatalysts have limitations,including poor spectral absorption,inefficient charge separation,and structural instability under operational stress,which demand innovative durable materials with tailored electronic properties.Nanodiamond(ND)has recently been recognized as a suitable material because of its exceptional chemical stability,superior charge carrier mobility,and possible surface functionalization.While its intrinsic wide bandgap limits its response to visible-light,different methods have been demonstrated to activate its catalytic potential.Here,several emerging strategies for improving the catalytic performance of ND-based photocatalytic systems are summarized,including surface functionalization,plasmonic hybridization,heteroatom doping,and heterostructure design.And the structure-activity relationship and design principle are proposed to improve the light harvesting,charge transport,and redox kinetics for constructing high efficiency ND-based photocatalysts used in the renewable energy and environmental industries.
文摘Behavior recognition of Hu sheep contributes to their intensive and intelligent farming.Due to the generally high density of Hu sheep farming,severe occlusion occurs among different behaviors and even among sheep performing the same behavior,leading to missing and false detection issues in existing behavior recognition methods.A high-low frequency aggregated attention and negative sample comprehensive score loss and comprehensive score soft non-maximum suppression-YOLO(HLNC-YOLO)was proposed for identifying the behavior of Hu sheep,addressing the issues of missed and erroneous detections caused by occlusion between Hu sheep in intensive farming.Firstly,images of four typical behaviors-standing,lying,eating,and drinking-were collected from the sheep farm to construct the Hu sheep behavior dataset(HSBD).Next,to solve the occlusion issues,during the training phase,the C2F-HLAtt module was integrated,which combined high-low frequency aggregation attention,into the YOLO v8 Backbone to perceive occluded objects and introduce an auxiliary reversible branch to retain more effective features.Using comprehensive score regression loss(CSLoss)to reduce the scores of suboptimal boxes and enhance the comprehensive scores of occluded object boxes.Finally,the soft comprehensive score non-maximal suppression(Soft-CS-NMS)algorithm filtered prediction boxes during the inferencing.Testing on the HSBD,HLNC-YOLO achieved a mean average precision(mAP@50)of 87.8%,with a memory footprint of 17.4 MB.This represented an improvement of 7.1,2.2,4.6,and 11 percentage points over YOLO v8,YOLO v9,YOLO v10,and Faster R-CNN,respectively.Research indicated that the HLNC-YOLO accurately identified the behavior of Hu sheep in intensive farming and possessed generalization capabilities,providing technical support for smart farming.
基金Supported by the Shanxi Province Grant(202203021212007,2023SHB003).
文摘Hydrogen peroxide(H_(2)O_(2))oxidation and reduction reactions(HPOR/HPRR)are pivotal in various innovative electrochemical energy conversion devices.A comprehensive understanding of these mechanisms is critical for catalyst design and performance improvement in these applications.In this work,we systematically investigate the HPOR/HPRR mechanisms on low-index Pt surfaces,specifically Pt(111),Pt(100)and Pt(110),through density functional theory(DFT)calculations combined with the computational hydrogen electrode(CHE)model.For HPOR,all the low-index Pt surfaces exhibit a unified potential-determining step(PDS)involving the electrochemical oxidation of hydroperoxyl intermediates(HOO*).The binding free energy of HOO*(Δ_(GHOO*))emerges as an activity descriptor,with Pt(110)exhibiting the highest HPOR activity.The HPRR mechanism follows a chem-electrochemical(C-EC)pathway.The rate-determining step(RDS)of HPRR is either the cleavage of the HO-OH bond(chemical)or the reduction of HO(electrochemical),depending on their respective activation energies.These activation energies are functions of the HO*binding free energy,Δ_(GHO*),establishingΔ_(GHO*)as the descriptor for HPRR activity prediction.Pt(111)and Pt(100)are identified as the most active HPRR catalysts among the studied metal surfaces,although they still experience a significant overpotential.The scaling relationship betweenΔ_(GHOO*)andΔ_(GHO*)reveals a thermodynamic coupling of HPOR and HPRR,explaining their occurrence on Pt surfaces.These findings provide important insights and activity descriptors for both HPOR and HPRR,providing valuable guidance for the design of electrocatalysts in H_(2)O_(2)-related energy applications and fuel cells.
文摘The poor electrical conductivity of metal-organic frameworks(MOFs)limits their electrocatalytic performance in the oxygen evolution reaction(OER).In this study,a Py@Co-MOF composite material based on pyrene(Py)molecules and{[Co2(BINDI)(DMA)_(2)]·DMA}_(n)(Co-MOF,H4BINDI=N,N'-bis(5-isophthalic acid)naphthalenediimide,DMA=N,N-dimethylacetamide)was synthesized via a one-pot method,leveragingπ-πinteractions between pyrene and Co-MOF to modulate electrical conductivity.Results demonstrate that the Py@Co-MOF catalyst exhibited significantly enhanced OER performance compared to pure Co-MOF or pyrene-based electrodes,achieving an overpotential of 246 mV at a current density of 10 mA·cm^(-2) along with excellent stability.Density functional theory(DFT)calculations reveal that the formation of O*in the second step is the rate-determining step(RDS)during the OER process on Co-MOF,with an energy barrier of 0.85 eV due to the weak adsorption affinity of the OH*intermediate for Co sites.CCDC:2419276.
文摘Biomass-derived carbon materials are favored for their abundance and sustainability,and ease of preparation and modification.By surface activation and modification they can have a good electrical conductivity,excellent catalytic activity,a remarkable adsorption capacity,and different interfacial physicochemical functionalities.Surface-modified biochars have found wide applications in energy storage,environmental remediation,and catalysis.However,achieving precise and controllable modification of their active sites remains a challenge.Recent advances and future prospects for controlling their surface morphology,defect engineering,and surface coating strategies,with particular attention to their means of fabrication,are reviewed.
文摘A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.
基金supported by the Irish Research Council under the Government of Ireland Postdoctoral Fellowship Project ID-GOIPD/2023/1431(to AS).
文摘Spinal cord injury(SCI)is a debilitating ailment that leads to the loss of motor and sensory functions,often leaving the patient paralyzed below the injury site(Chen et al.,2013).Globally around 250,000-300,000 people are diagnosed with SCI annually(Singh et al.,2014),and while this number appears quite low,the effect that an SCI has on the patient’s quality of life is drastic,due to the current difficulties to comprehensively treat this illness.The cost of patient care can also be quite costly,amounting to an estimated$1.69 billion in healthcare costs in the USA alone(Mahabaleshwarkar and Khanna,2014).
基金supported by the China Agriculture Research System of MOF and MARAthe National Natural Science Foundation of China (31872337 and 31501919)the Agricultural Science and Technology Innovation Project,China (ASTIP-IAS02)。
文摘The advantages of genome selection(GS) in animal and plant breeding are self-evident.Traditional parametric models have disadvantage in better fit the increasingly large sequencing data and capture complex effects accurately.Machine learning models have demonstrated remarkable potential in addressing these challenges.In this study,we introduced the concept of mixed kernel functions to explore the performance of support vector machine regression(SVR) in GS.Six single kernel functions(SVR_L,SVR_C,SVR_G,SVR_P,SVR_S,SVR_L) and four mixed kernel functions(SVR_GS,SVR_GP,SVR_LS,SVR_LP) were used to predict genome breeding values.The prediction accuracy,mean squared error(MSE) and mean absolute error(MAE) were used as evaluation indicators to compare with two traditional parametric models(GBLUP,BayesB) and two popular machine learning models(RF,KcRR).The results indicate that in most cases,the performance of the mixed kernel function model significantly outperforms that of GBLUP,BayesB and single kernel function.For instance,for T1 in the pig dataset,the predictive accuracy of SVR_GS is improved by 10% compared to GBLUP,and by approximately 4.4 and 18.6% compared to SVR_G and SVR_S respectively.For E1 in the wheat dataset,SVR_GS achieves 13.3% higher prediction accuracy than GBLUP.Among single kernel functions,the Laplacian and Gaussian kernel functions yield similar results,with the Gaussian kernel function performing better.The mixed kernel function notably reduces the MSE and MAE when compared to all single kernel functions.Furthermore,regarding runtime,SVR_GS and SVR_GP mixed kernel functions run approximately three times faster than GBLUP in the pig dataset,with only a slight increase in runtime compared to the single kernel function model.In summary,the mixed kernel function model of SVR demonstrates speed and accuracy competitiveness,and the model such as SVR_GS has important application potential for GS.
基金Supported by The Natural Science Foundation of China,No.82374292the Plans for Major Provincial Science and Technology Projects of Anhui Province,No.202303a07020003the Innovation Team and Talents Cultivation Program of the National Administration of Traditional Chinese Medicine,No.ZYYCXTD-C-202401.
文摘Functional gastrointestinal disorders(FGIDs),including irritable bowel syndrome(IBS),functional dyspepsia(FD),and gastroesophageal reflux disease(GERD),present persistent diagnostic and therapeutic challenges due to symptom heterogeneity and the absence of reliable biomarkers.Artificial intelligence(AI)enables the integration of multimodal data to enhance FGID management through precision diagnostics and preventive healthcare.This minireview summarizes recent advancements in AI applications for FGIDs,highlighting progress in diagnostic accuracy,subtype classification,personalized interventions,and preventive strategies inspired by the traditional Chinese medicine concept of“treating the undiseased”.Machine learning and deep learning algorithms have demonstrated value in improving IBS diagnosis,refining FD neuro-gastrointestinal subtyping,and screening for GERD-related complications.Moreover,AI supports dietary,psychological,and integrative medicine-based interventions to improve patient adherence and quality of life.Nonetheless,key challenges remain,including data heterogeneity,limited model interpretability,and the need for robust clinical validation.Future directions emphasize interdisciplinary collaboration,the development of multimodal and explainable AI models,and the creation of patientcentered platforms to facilitate a shift from reactive treatment to proactive prevention.This review provides a systematic framework to guide the clinical application and theoretical innovation of AI in FGIDs.
基金supported by the National Natural Science Foundation of China(22378205)the Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Center for Advanced Materials and Technology in Nanjing University of Science and Technology。
文摘The incorporation of small fluorinated functional groups,including CF_(3),CF_(2)H,and CFH_(2),into small molecules represents a crucial strategy for modulating their physical,chemical,and biological characteristics[1,2].Consequently,organofluorine compounds are frequently encountered in pharmaceuticals and agrochemicals.Significant advances have been made in the introduction of fluoroalkyl groups into small molecules since the beginning of the 21st century.
