Biomass‐derived carbon is a promising electrode material in energy storage devices.However,how to improve its low capacity and stability,and slow diffusion kinetics during lithium storage remains a challenge.In this ...Biomass‐derived carbon is a promising electrode material in energy storage devices.However,how to improve its low capacity and stability,and slow diffusion kinetics during lithium storage remains a challenge.In this research,we propose a“self‐assembly‐template”method to prepare B,N codoped porous carbon(BN‐C)with a nanosandwich structure and abundant pyridinic N‐B species.The nanosandwich structure can increase powder density and cycle stability by constructing a stable solid electrolyte interphase film,shortening the Li^(+) diffusion pathway,and accommodating volume expansion during repeated charging/discharging.The abundant pyridinic N‐B species can simultaneously promote the adsorption/desorption of Li^(+)/PF_(6)^(−) and reduce the diffusion barrier.The BN‐C electrode showed a high lithium‐ion storage capacity of above 1140 mAh g^(−1) at 0.05 A g^(−1) and superior stability(96.5% retained after 2000 cycles).Moreover,owing to the synergistic effect of the nanosandwich structure and pyridinic N‐B species,the assembled symmetrical BN‐C//BN‐C full cell shows a high energy density of 234.7Wh kg^(−1),high power density of 39.38 kW kg−1,and excellent cycling stability,superior to most of the other cells reported in the literature.As the density functional theory simulation demonstrated,pyridinic N‐B shows enhanced adsorption activity for Li^(+) and PF_(6)^(−),which promotes an increase in the capacity of the anode and cathode,respectively.Meanwhile,the relatively lower diffusion barrier of pyridinic N‐B promotes Li^(+) migration,resulting in good rate performance.Therefore,this study provides a new approach for the synergistic modulation of a nanostructure and an active site simultaneously to fabricate the carbon electrode material in energy storage devices.展开更多
Replacing platinum for catalyzing hydrogen evolution reaction （HER） in acidic medium remains great chal- lenges. Herein, we prepared few-layered MoS2 by ball milling as an efficient catalyst for HER in acidic medium...Replacing platinum for catalyzing hydrogen evolution reaction （HER） in acidic medium remains great chal- lenges. Herein, we prepared few-layered MoS2 by ball milling as an efficient catalyst for HER in acidic medium, The activity of as-prepared MoS2 had a strong dependence on the ball milling time, Furthermore, Ketjen Black EC 300J was added into the ball-milled MoS2 followed by a second ball milling, and the resultant MoS2/carbon black hybrid material showed a much higher HER activity than MoS2 and carbon black alone. The enhanced activity of the MoS2/carbon black hybrid material was attributed to the increased abundance of catalytic edge sites of MoS） and excellent electrical coupling to the underlving carbon network.展开更多
Cordyceps sinensis(C.sinensis)is a widely used and highly valuable traditional Chinese medicine.Several dipeptides have been detected in C.sinensis,but current scientific knowledge of its chemical makeup remains limit...Cordyceps sinensis(C.sinensis)is a widely used and highly valuable traditional Chinese medicine.Several dipeptides have been detected in C.sinensis,but current scientific knowledge of its chemical makeup remains limited.In this study,an improved approach that integrates offline two-dimensional liquid chromatography(2D LC)separation,precursor ion list,library screening,and diagnostic ion filtering was established to systematically screen and characterize dipeptides in C.sinensis.Offline 2D LC integrating hydrophilic interaction LC and reverse phase separations was established to eliminate interference and identify the target dipeptides.A library containing the potential 400 dipeptides was created,and a precursor ion list with all theoretical precursor ions was adopted to trigger the MS/MS scan with high sensitivity.To identify dipeptides,the type and connection sequence of amino acids were determined according to the product ions.Ile and Leu residues were differentiated for the first time according to the characteristic ion at m/z 69.07.Ultimately,170 dipeptides were identified or tentatively characterized from C.sinensis,and most are reported for the first time in this species herein.In addition,the identified dipeptides were also applied for discrimination among the three Cordyceps species,and 11 markers were identified.The obtained results provide a deeper understanding of the chemical basis of C.sinensis.展开更多
Pheretima,also called“earthworms”,is a well-known animal-derived traditional Chinese medicine that is extensively used in over 50 Chinese patent medicines(CPMs)in Chinese Pharmacopoeia(2020 edition).However,its zool...Pheretima,also called“earthworms”,is a well-known animal-derived traditional Chinese medicine that is extensively used in over 50 Chinese patent medicines(CPMs)in Chinese Pharmacopoeia(2020 edition).However,its zoological origin is unclear,both in the herbal market and CPMs.In this study,a strategy for integrating in-house annotated protein databases constructed from close evolutionary relationship-sourced RNA sequencing data from public archival resources and various sequencing algorithms(restricted search,open search,and de novo)was developed to characterize the phenotype of natural peptides of three major commercial species of Pheretima,including Pheretima aspergillum(PA),Pheretima vulgaris(PV),and Metaphire magna(MM).We identified 10,477 natural peptides in the PA,7,451 in PV,and 5,896 in MM samples.Five specific signature peptides were screened and then validated using synthetic peptides;these demonstrated robust specificity for the authentication of PA,PV,and MM.Finally,all marker peptides were successfully applied to identify the zoological origins of Brain Heart capsules and Xiaohuoluo pills,revealing the inconsistent Pheretima species used in these CPMs.In conclusion,our integrated strategy could be used for the in-depth characterization of natural peptides of other animal-derived traditional Chinese medicines,especially non-model species with poorly annotated protein databases.展开更多
Background:While type 2 diabetes mellitus(T2DM)is considered a putative causal risk factor for coronary artery disease(CAD),the intrinsic link underlying T2DM and CAD is not fully understood.We aimed to highlight the ...Background:While type 2 diabetes mellitus(T2DM)is considered a putative causal risk factor for coronary artery disease(CAD),the intrinsic link underlying T2DM and CAD is not fully understood.We aimed to highlight the importance of integrated care targeting both diseases by investigating the phenotypic and genetic relationships between T2DM and CAD.Methods:We evaluated phenotypic associations using data from the United Kingdom Biobank(N=472,050).We investigated genetic relationships by leveraging genomic data conducted in European ancestry for T2DM,with and without adjustment for body mass index(BMI)(T2DM:N_(case)/N_(control)=74,124/824,006;T2DM adjusted for BMI[T2DM_(adj)BMI]:N_(case)/N_(control)=50,409/523,897)and for CAD(N_(case)/N_(control)=181,522/984,168).We performed additional analyses using genomic data conducted in multiancestry individuals for T2DM(N_(case)/N_(control)=180,834/1,159,055).Results:Observational analysis suggested a bidirectional relationship between T2DM and CAD(T2DM→CAD:hazard ratio[HR]=2.12,95%confidence interval[CI]:2.01–2.24;CAD→T2DM:HR=1.72,95%CI:1.63–1.81).A positive overall genetic correlation between T2DM and CAD was observed(r_(g)=0.39,P=1.43×10^(-75)),which was largely independent of BMI(T2DM_(adj)BMI–CAD:r_(g)=0.31,P=1.20×10^(–36)).This was corroborated by six local signals,among which 9p21.3 showed the strongest genetic correlation.Cross-trait meta-analysis replicated 101 previously reported loci and discovered six novel pleiotropic loci.Mendelian randomization analysis supported a bidirectional causal relationship(T2DM→CAD:odds ratio[OR]=1.13,95%CI:1.11-1.16;CAD→T2DM:OR=1.12,95%CI:1.07-1.18),which was confirmed in multiancestry individuals(T2DM→CAD:OR=1.13,95%CI:1.10-1.16;CAD→T2DM:OR=1.08,95%CI:1.04-1.13).This bidirectional relationship was significantly mediated by systolic blood pressure and intake of 3-hydroxy-3-methylglutaryl coenzyme A reductase inhibitors,with mediation proportions of 54.1%(95%CI:24.9-83.4%)and 90.4%(95%CI:29.3-151.5%),respectively.Conclusion:Our observational and genetic analyses demonstrated an intrinsic bidirectional relationship between T2DM and CAD and clarified the biological mechanisms underlying this relationship.展开更多
Thyroid-stimulating hormone(TSH)is important for the thyroid gland,development,growth,and metabolism.Defects in TSH production or the thyrotrope cells within the pituitary gland cause congenital hypothyroidism(CH),res...Thyroid-stimulating hormone(TSH)is important for the thyroid gland,development,growth,and metabolism.Defects in TSH production or the thyrotrope cells within the pituitary gland cause congenital hypothyroidism(CH),resulting in growth retardation and neurocognitive impairment.While human TSH is known to display rhythmicity,the molecular mechanisms underlying the circadian regulation of TSH and the effects of TSH-thyroid hormone(TH)signaling on the circadian clock remain elusive.Here we show that TSH,thyroxine(T4),triiodothyronine(T3),and tshba display rhythmicity in both larval and adult zebrafish and tshba is regulated directly by the circadian clock via both E′-box and D-box.Zebrafish tshba^(−/−)mutants manifest congenital hypothyroidism,with the characteristics of low levels of T_(4)and T_(3)and growth retardation.Loss or overexpression of tshba alters the rhythmicity of locomotor activities and expression of core circadian clock genes and hypothalamic-pituitary-thyroid(HPT)axis-related genes.Furthermore,TSH-TH signaling regulates clock2/npas2 via the thyroid response element(TRE)in its promoter,and transcriptome analysis reveals extensive functions of Tshba in zebrafish.Together,our results demonstrate that zebrafish tshba is a direct target of the circadian clock and in turn plays critical roles in circadian regulation along with other functions.展开更多
Splitting water into hydrogen and oxygen by dye-sensitized photoelectrochemical cell(DSPEC)is a promising approach to solar fuels production.In this study,a series of pyridine derivatives as surface additives were mod...Splitting water into hydrogen and oxygen by dye-sensitized photoelectrochemical cell(DSPEC)is a promising approach to solar fuels production.In this study,a series of pyridine derivatives as surface additives were modified on a molecular chromophore and water oxidation catalyst co-loaded TiO_(2)photoanode,TiO_(2)|RuP,1(RuP=Ru(4,4′-(PO3H2)2-2,2′-bipyridine)(2,2′-bipyridine)2,1=Ru(bda)(L)2,(bda=2,2′-bipyridine-6,6′-dicarboxylate,L=10-(pyridin-4-yloxy)decyl)phosphonic acid).The addition of pyridine additives was found to result in up to 42%increase in photocurrent.Under simulated sun-light irradiation,TiO_(2)|RuP,1,P1(P1=4-Hydroxypyridine)produced a photocurrent density of 1 mA/cm2 at a bias of 0.4 V vs.NHE in acetate buffer.Moreover,the observed photocurrents are correlated with the electron-donating ability of the substituent groups on pyridine ring.Transient absorption measurements and electrochemical impedance spectroscopy revealed that surface-bound pyridine can effectively retard the back-electron transfer from the TiO_(2)conduction band to the oxidized dye,which is a major process responsible for energy loss in DSPECs.展开更多
The development of high efficiency and stable electrocatalysts for oxygen evolution is critical for energy storage and conversion systems. Herein, a series of Co/Fe bimetal-organic frameworks (MOFs) were fabricated us...The development of high efficiency and stable electrocatalysts for oxygen evolution is critical for energy storage and conversion systems. Herein, a series of Co/Fe bimetal-organic frameworks (MOFs) were fabricated using a facile ultrasonic method at room temperature, as electrocatalysts for the oxygen evolution reaction (OER) in alkaline solution. The Co2Fe-MOF exhibited an overpotential of 280 mV at a current density of 10 mA cm^-2, a low Tafel slope of 44.7 mV dec^-1, and long-term stability over 12000 s in 1 mol L^-1 KOH. This impressive performance was attributed to the high charge transfer rate, large specific surface area, and synergistic effects of the cobalt and iron centers.展开更多
Biochar with a highly accessible specific surface area can display a higher performance when it is used as the cathode of lithium-ion capacitors.Facing the complex composition and diversity of biomass precursors,there...Biochar with a highly accessible specific surface area can display a higher performance when it is used as the cathode of lithium-ion capacitors.Facing the complex composition and diversity of biomass precursors,there is a lack of a universally applicable method to construct hierarchical porous biochar controllably.In this work,a multi-stage activation strategy combining the feature of different activation methods is proposed for this target.To confirm the porous characteristic in prepared samples,N_(2) adsorption-desorption and transmission electron microscope were used.As the optimal sample,BC-P3K4S had the highest specific surface area of 3583.3 m^(2) g^(−1).Evaluated as the electrode for a lithium-ion capacitor,BC-P3K4S displayed a capacity of 139.1 mAh g^(−1) at 0.1 A g^(−1).After coupling it with pre-lithiated hard carbon,the full device exhibited a high energy density of 129.3 W h kg^(−1) at 153 W kg^(−1).The work outlined herein offers some insights into the preparation of hierarchical porous biochar from complex biomass by multistep activation method.展开更多
A PtFe/C catalyst has been synthesized by impregnation and high-temperature reduction followed by acid-leaching. X-ray diffraction, X-ray photoelectron spectroscopy and X-ray atomic near edge spectroscopy characteriza...A PtFe/C catalyst has been synthesized by impregnation and high-temperature reduction followed by acid-leaching. X-ray diffraction, X-ray photoelectron spectroscopy and X-ray atomic near edge spectroscopy characterization reveal that PtgFe alloy formation occurs during high-temperature reduction and that unstable Fe species are dissolved into acid solution. The difference in Fe concentration from the core region to the surface and strong O-Fe bonding may drive the outward diffusion of Fe to the highly corrugated Pt-skeleton, and the resulting highly dispersed surface FeOx is stable in acidic medium, leading to the construction of a PtBFe@Pt-FeOx architecture. The as prepared PtFe/C catalyst demonstrates a higher activity and comparable durability for the oxygen reduction reaction compared with a Pt/C catalyst, which might be due to the synergetic effect of surface and subsurface Fe species in the PtFe/C catalyst.展开更多
Most lakes have undergone significant changes on the Tibetan Plateau in recent decades,affecting water resources on the Tibetan Plateau and its surrounding areas.In this paper,we investigated the variations of 25 lake...Most lakes have undergone significant changes on the Tibetan Plateau in recent decades,affecting water resources on the Tibetan Plateau and its surrounding areas.In this paper,we investigated the variations of 25 lakes in five sub-regions on the Tibetan Plateau from 1972 to 2019 based on SRTM DEM data and Landsat imagery.We used a method to derive lake-levels based on DEM and lake boundaries delineated from Landsat imagery,and then calculated the changes in lake area,level,and volume in 1972 to 2019.We also analyzed the potential impacts of temperature,precipitation,glacial and permafrost melting in lake changes during this period.The results show that the lakes tended to shrink until 2010 in southern and western plateau,after which they began to expand gradually but the overall trend is still shrinking.Limited meltwater from glaciers and permafrost and low precipitation are the main reasons for their shrinkage.The lakes in the central plateau,northwest plateau and northeast plateau tend to expand overall.The reason for the expansion of the lakes is not only precipitation but also the melting of glaciers and permafrost.Overall,the lake changes have gone through 3 phases,namely a slight decrease during 1972-2000,a rapid increase during 2000-2010,and a slowdown in the last decade(2010-2019).Multiple factors such as temperature,precipitation,the state of glaciers and permafrost have contributed to the changes in the lake.展开更多
The strategy of element substitution is an effective way to tune the electronic structures of the active sites in catalysts, thereby leading to improvements in both the catalytic activity and stability. Herein, we des...The strategy of element substitution is an effective way to tune the electronic structures of the active sites in catalysts, thereby leading to improvements in both the catalytic activity and stability. Herein, we design and synthesize pyrite-type nickel/phosphorus co-doped CoS2 nanowires on carbon cloth （NiCoPS/CC） as efficient and durable electrodes for water electrolysis. Introduction of nickel and phosphorus produced stepwise and superb enhancement of the performance of the electrodes in the hydrogen evolution reaction due to regulation of the electronic structures of the active sites of the catalyst and accelerated charge transfer over a wide pH range （0-14）. The NiCoPS/CC electrodes also delivered a nearly undecayed catalytic current density of 10 mA.cm-2 at a low overpotential of 230 mV for oxygen evolution due to in situ formation of surficial Ni-Co oxo/hydroxide in 1.0 M KOH. Thus, the NiCoPS/CC electrodes gave rise to a catalytic current density of 10 mA·cm-2 for overall water splitting at potentials as low as 1.54 V during operation over 100 h in 1.0 M KOH with a Faradic efficiency of ~100%.展开更多
Nickel(Ni)-based materials are promising electrocatalysts for the urea electrooxidation reaction, as the in situ formed NiOOH species on their surface during operation are catalytically active sites. In this work, phy...Nickel(Ni)-based materials are promising electrocatalysts for the urea electrooxidation reaction, as the in situ formed NiOOH species on their surface during operation are catalytically active sites. In this work, phytate-coordinated Ni foam(PA-NF)is shown to deliver a high catalytic performance, with a potential as low as 1.38 V at 10m A/cm2, a Tafel slope as low as 64.1 mV/dec, and superior catalytic stability. Characterizations revealed that such a high performance was ascribed to the kinetic acceleration of surface reconstruction and the enriched NiOOH active species on the PA-NF surface owing to PA-coordination induced upshift of d-band center of Ni sites.Overall, a novel and simple strategy is provided for designing the efficient as well as universal Ni-based catalyst for the electrooxidation of urea, which can also be extended to other transition-metal-based systems.展开更多
Sulfonamides(SAs)are common antimicrobial drugs,which are frequently detected in surface water systems,and are difficult to degrade,posing a potential threat to the aquatic environment.However,little is known about th...Sulfonamides(SAs)are common antimicrobial drugs,which are frequently detected in surface water systems,and are difficult to degrade,posing a potential threat to the aquatic environment.However,little is known about the potential adverse effects of SAs on nontarget organisms(e.g.,microalgae)in the aquatic ecosystem.In this study,the effect of SAs(sulfadiazine(SD),sulfamerazine(SM1),and sulfamethazine(SM2)at 1,5,20,and 50 mg/L concentrations,respectively)on the freshwater microalga Dictyosphaerium sp.was investigated,with respect to changes of biomass and chlorophyll a content and induction of extracellular polymer substances(EPS),including protein and polysaccharide contents.At the same time,the residue of SAs was determined.The results showed that Dictyosphaerium sp.was tolerant to the three SAs,and the chlorophyll a content in Dictyosphaerium sp.significantly decreased on day 7,followed by a"compensation phenomena".The increase in protein and polysaccharide contents played a defensive role in Dictyosphaerium sp.against antibiotic stress,and there was a strong positive correlation between polysaccharide contents and antibiotic concentrations.Dictyosphaerium sp.exhibited 35%–45%,30%–42%,and 26%–51%removal of SD,SM1,and SM2,respectively.This study is helpful to understand the changes of EPS in the defense process of microalgae under the action of antibiotics,and provides a new insight for the ecological removal of antibiotic pollution in natural surface water system.展开更多
Ca^(2+)plays critical roles in the development of diseases,whereas existing various Ca regulation methods have been greatly restricted in their clinical applications due to their high toxicity and inefficiency.To solv...Ca^(2+)plays critical roles in the development of diseases,whereas existing various Ca regulation methods have been greatly restricted in their clinical applications due to their high toxicity and inefficiency.To solve this issue,with the help of Ca overexpressed tumor drug resistance model,the phytic acid(PA)-modified CeO_(2) nano-inhibitors have been rationally designed as an unprecedentedly safe and efficient Ca2+inhibitor to successfully reverse tumor drug resistance through Ca^(2+)negative regulation strategy.Using doxorubicin(Dox)as a model chemotherapeutic drug,the Ca^(2+)nano-inhibitors efficiently deprived intracellular excessive free Ca2+,suppressed P-glycoprotein(P-gp)expression and significantly enhanced intracellular drug accumulation in Dox-resistant tumor cells.This Ca^(2+)negative regulation strategy improved the intratumoral Dox concentration by a factor of 12.4 and nearly eradicated tumors without obvious adverse effects.Besides,nanocerias as pH-regulated nanozyme greatly alleviated the adverse effects of chemotherapeutic drug on normal cells/organs and substantially improved survivals of mice.We anticipate that this safe and effective Ca^(2+)negative regulation strategy has potentials to conquer the pitfalls of traditional Ca inhibitors,improve therapeutic efficacy of common chemotherapeutic drugs and serves as a facile and effective treatment platform of other Ca^(2+) associated diseases.展开更多
Challenges are faced for rapid economic and social development including the global energy shortage, diversification in energy and chemical raw materials, and ecological environmental protection. The development of re...Challenges are faced for rapid economic and social development including the global energy shortage, diversification in energy and chemical raw materials, and ecological environmental protection. The development of renewable energy has become a common concern for the current society.展开更多
基金Jiangsu Key Lab of Biomass Energy and Material,Grant/Award Number:JSBEMS‐202101National Natural Science Foundation of China,Grant/Award Numbers:51902162,51902162+4 种基金National Key R&D Program of China,Grant/Award Number:2022YFB4201904Foundation of Jiangsu Key Lab of Biomass Energy and Material,Grant/Award Number:JSBEM‐S‐202101National Key R&D Program,Grant/Award Number:2022YFB4201904Jiangsu Co‐Innovation Center of Efficient Processing and Utilization of Forest Resources,the International Innovation Center for Forest Chemicals and Materialsanjing Forestry University。
文摘Biomass‐derived carbon is a promising electrode material in energy storage devices.However,how to improve its low capacity and stability,and slow diffusion kinetics during lithium storage remains a challenge.In this research,we propose a“self‐assembly‐template”method to prepare B,N codoped porous carbon(BN‐C)with a nanosandwich structure and abundant pyridinic N‐B species.The nanosandwich structure can increase powder density and cycle stability by constructing a stable solid electrolyte interphase film,shortening the Li^(+) diffusion pathway,and accommodating volume expansion during repeated charging/discharging.The abundant pyridinic N‐B species can simultaneously promote the adsorption/desorption of Li^(+)/PF_(6)^(−) and reduce the diffusion barrier.The BN‐C electrode showed a high lithium‐ion storage capacity of above 1140 mAh g^(−1) at 0.05 A g^(−1) and superior stability(96.5% retained after 2000 cycles).Moreover,owing to the synergistic effect of the nanosandwich structure and pyridinic N‐B species,the assembled symmetrical BN‐C//BN‐C full cell shows a high energy density of 234.7Wh kg^(−1),high power density of 39.38 kW kg−1,and excellent cycling stability,superior to most of the other cells reported in the literature.As the density functional theory simulation demonstrated,pyridinic N‐B shows enhanced adsorption activity for Li^(+) and PF_(6)^(−),which promotes an increase in the capacity of the anode and cathode,respectively.Meanwhile,the relatively lower diffusion barrier of pyridinic N‐B promotes Li^(+) migration,resulting in good rate performance.Therefore,this study provides a new approach for the synergistic modulation of a nanostructure and an active site simultaneously to fabricate the carbon electrode material in energy storage devices.
基金the financial support from the Ministry of Science and Technology of China (grants 2012CB215500 and 2013CB933100)the National Natural Science Foundation of China (grants 21573222 and 21103178)
文摘Replacing platinum for catalyzing hydrogen evolution reaction （HER） in acidic medium remains great chal- lenges. Herein, we prepared few-layered MoS2 by ball milling as an efficient catalyst for HER in acidic medium, The activity of as-prepared MoS2 had a strong dependence on the ball milling time, Furthermore, Ketjen Black EC 300J was added into the ball-milled MoS2 followed by a second ball milling, and the resultant MoS2/carbon black hybrid material showed a much higher HER activity than MoS2 and carbon black alone. The enhanced activity of the MoS2/carbon black hybrid material was attributed to the increased abundance of catalytic edge sites of MoS） and excellent electrical coupling to the underlving carbon network.
基金supported by the National Key R&D Program of China(Grant Nos.:2018YFC1707900,2019YFC1711000,and 2019YFC1711400)Key-Area Research and Development Program of Guangdong Province(Grant No.:2020B1111110007)+1 种基金the National Natural Science Foundation of China(Grant No.:82003938)Chief Scientist of Qi-Huang Project of National Traditional Chinese Medicine Inheritance and Innovation“One Hundred Million”Talent Project(2020).
文摘Cordyceps sinensis(C.sinensis)is a widely used and highly valuable traditional Chinese medicine.Several dipeptides have been detected in C.sinensis,but current scientific knowledge of its chemical makeup remains limited.In this study,an improved approach that integrates offline two-dimensional liquid chromatography(2D LC)separation,precursor ion list,library screening,and diagnostic ion filtering was established to systematically screen and characterize dipeptides in C.sinensis.Offline 2D LC integrating hydrophilic interaction LC and reverse phase separations was established to eliminate interference and identify the target dipeptides.A library containing the potential 400 dipeptides was created,and a precursor ion list with all theoretical precursor ions was adopted to trigger the MS/MS scan with high sensitivity.To identify dipeptides,the type and connection sequence of amino acids were determined according to the product ions.Ile and Leu residues were differentiated for the first time according to the characteristic ion at m/z 69.07.Ultimately,170 dipeptides were identified or tentatively characterized from C.sinensis,and most are reported for the first time in this species herein.In addition,the identified dipeptides were also applied for discrimination among the three Cordyceps species,and 11 markers were identified.The obtained results provide a deeper understanding of the chemical basis of C.sinensis.
基金supported by the Key Program of the National Natural Science Foundation of China(Grant No.:82130111)the National Natural Science Foundation of China(Grant No.:81803716)+1 种基金the Qi-Huang Chief Scientist Project of the National Administration of Traditional Chinese Medicine,China(2020)the SIMM-SHUTCM Traditional Chinese Medicine Innovation Joint Research Program,China(Grant No.:E2G809H).
文摘Pheretima,also called“earthworms”,is a well-known animal-derived traditional Chinese medicine that is extensively used in over 50 Chinese patent medicines(CPMs)in Chinese Pharmacopoeia(2020 edition).However,its zoological origin is unclear,both in the herbal market and CPMs.In this study,a strategy for integrating in-house annotated protein databases constructed from close evolutionary relationship-sourced RNA sequencing data from public archival resources and various sequencing algorithms(restricted search,open search,and de novo)was developed to characterize the phenotype of natural peptides of three major commercial species of Pheretima,including Pheretima aspergillum(PA),Pheretima vulgaris(PV),and Metaphire magna(MM).We identified 10,477 natural peptides in the PA,7,451 in PV,and 5,896 in MM samples.Five specific signature peptides were screened and then validated using synthetic peptides;these demonstrated robust specificity for the authentication of PA,PV,and MM.Finally,all marker peptides were successfully applied to identify the zoological origins of Brain Heart capsules and Xiaohuoluo pills,revealing the inconsistent Pheretima species used in these CPMs.In conclusion,our integrated strategy could be used for the in-depth characterization of natural peptides of other animal-derived traditional Chinese medicines,especially non-model species with poorly annotated protein databases.
基金supported by the National Key R&D Program of China(Nos.2022YFC3600600,2022YFC3600604)the National Natural Science Foundation of China(Nos.U22A20359,81874283,and 81673255)+2 种基金the Recruitment Program for Young Professionals of Chinathe Promotion Plan for Basic Medical Sciencesthe Development Plan for Cutting-Edge Disciplines,Sichuan University.
文摘Background:While type 2 diabetes mellitus(T2DM)is considered a putative causal risk factor for coronary artery disease(CAD),the intrinsic link underlying T2DM and CAD is not fully understood.We aimed to highlight the importance of integrated care targeting both diseases by investigating the phenotypic and genetic relationships between T2DM and CAD.Methods:We evaluated phenotypic associations using data from the United Kingdom Biobank(N=472,050).We investigated genetic relationships by leveraging genomic data conducted in European ancestry for T2DM,with and without adjustment for body mass index(BMI)(T2DM:N_(case)/N_(control)=74,124/824,006;T2DM adjusted for BMI[T2DM_(adj)BMI]:N_(case)/N_(control)=50,409/523,897)and for CAD(N_(case)/N_(control)=181,522/984,168).We performed additional analyses using genomic data conducted in multiancestry individuals for T2DM(N_(case)/N_(control)=180,834/1,159,055).Results:Observational analysis suggested a bidirectional relationship between T2DM and CAD(T2DM→CAD:hazard ratio[HR]=2.12,95%confidence interval[CI]:2.01–2.24;CAD→T2DM:HR=1.72,95%CI:1.63–1.81).A positive overall genetic correlation between T2DM and CAD was observed(r_(g)=0.39,P=1.43×10^(-75)),which was largely independent of BMI(T2DM_(adj)BMI–CAD:r_(g)=0.31,P=1.20×10^(–36)).This was corroborated by six local signals,among which 9p21.3 showed the strongest genetic correlation.Cross-trait meta-analysis replicated 101 previously reported loci and discovered six novel pleiotropic loci.Mendelian randomization analysis supported a bidirectional causal relationship(T2DM→CAD:odds ratio[OR]=1.13,95%CI:1.11-1.16;CAD→T2DM:OR=1.12,95%CI:1.07-1.18),which was confirmed in multiancestry individuals(T2DM→CAD:OR=1.13,95%CI:1.10-1.16;CAD→T2DM:OR=1.08,95%CI:1.04-1.13).This bidirectional relationship was significantly mediated by systolic blood pressure and intake of 3-hydroxy-3-methylglutaryl coenzyme A reductase inhibitors,with mediation proportions of 54.1%(95%CI:24.9-83.4%)and 90.4%(95%CI:29.3-151.5%),respectively.Conclusion:Our observational and genetic analyses demonstrated an intrinsic bidirectional relationship between T2DM and CAD and clarified the biological mechanisms underlying this relationship.
基金supported by grants from the National Key Research and Development Program of China(2019YFA0802400)the National Natural Science Foundation of China(NSFC)(#31300969,#31961133026,#31871187)the Natural Science Foundation of Jiangsu Province(BK20130302),a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PARD).
文摘Thyroid-stimulating hormone(TSH)is important for the thyroid gland,development,growth,and metabolism.Defects in TSH production or the thyrotrope cells within the pituitary gland cause congenital hypothyroidism(CH),resulting in growth retardation and neurocognitive impairment.While human TSH is known to display rhythmicity,the molecular mechanisms underlying the circadian regulation of TSH and the effects of TSH-thyroid hormone(TH)signaling on the circadian clock remain elusive.Here we show that TSH,thyroxine(T4),triiodothyronine(T3),and tshba display rhythmicity in both larval and adult zebrafish and tshba is regulated directly by the circadian clock via both E′-box and D-box.Zebrafish tshba^(−/−)mutants manifest congenital hypothyroidism,with the characteristics of low levels of T_(4)and T_(3)and growth retardation.Loss or overexpression of tshba alters the rhythmicity of locomotor activities and expression of core circadian clock genes and hypothalamic-pituitary-thyroid(HPT)axis-related genes.Furthermore,TSH-TH signaling regulates clock2/npas2 via the thyroid response element(TRE)in its promoter,and transcriptome analysis reveals extensive functions of Tshba in zebrafish.Together,our results demonstrate that zebrafish tshba is a direct target of the circadian clock and in turn plays critical roles in circadian regulation along with other functions.
文摘Splitting water into hydrogen and oxygen by dye-sensitized photoelectrochemical cell(DSPEC)is a promising approach to solar fuels production.In this study,a series of pyridine derivatives as surface additives were modified on a molecular chromophore and water oxidation catalyst co-loaded TiO_(2)photoanode,TiO_(2)|RuP,1(RuP=Ru(4,4′-(PO3H2)2-2,2′-bipyridine)(2,2′-bipyridine)2,1=Ru(bda)(L)2,(bda=2,2′-bipyridine-6,6′-dicarboxylate,L=10-(pyridin-4-yloxy)decyl)phosphonic acid).The addition of pyridine additives was found to result in up to 42%increase in photocurrent.Under simulated sun-light irradiation,TiO_(2)|RuP,1,P1(P1=4-Hydroxypyridine)produced a photocurrent density of 1 mA/cm2 at a bias of 0.4 V vs.NHE in acetate buffer.Moreover,the observed photocurrents are correlated with the electron-donating ability of the substituent groups on pyridine ring.Transient absorption measurements and electrochemical impedance spectroscopy revealed that surface-bound pyridine can effectively retard the back-electron transfer from the TiO_(2)conduction band to the oxidized dye,which is a major process responsible for energy loss in DSPECs.
基金supported by the National Natural Science Foundation of China(21872016)the Fundamental Research Funds for the Central Universities(DUT17ZD204)~~
文摘The development of high efficiency and stable electrocatalysts for oxygen evolution is critical for energy storage and conversion systems. Herein, a series of Co/Fe bimetal-organic frameworks (MOFs) were fabricated using a facile ultrasonic method at room temperature, as electrocatalysts for the oxygen evolution reaction (OER) in alkaline solution. The Co2Fe-MOF exhibited an overpotential of 280 mV at a current density of 10 mA cm^-2, a low Tafel slope of 44.7 mV dec^-1, and long-term stability over 12000 s in 1 mol L^-1 KOH. This impressive performance was attributed to the high charge transfer rate, large specific surface area, and synergistic effects of the cobalt and iron centers.
基金National Natural Science Foundation of China(51976234)Forestry technology projects of Zhejiang Province(2023SY04)+1 种基金Foundation of Jiangsu Key Lab of Biomass Energy and Material(JSBEM-S-202101)National Nonprofit Institute Research Grant of Chinese Academy of Forestry(CAFYBB2020ZF001).
文摘Biochar with a highly accessible specific surface area can display a higher performance when it is used as the cathode of lithium-ion capacitors.Facing the complex composition and diversity of biomass precursors,there is a lack of a universally applicable method to construct hierarchical porous biochar controllably.In this work,a multi-stage activation strategy combining the feature of different activation methods is proposed for this target.To confirm the porous characteristic in prepared samples,N_(2) adsorption-desorption and transmission electron microscope were used.As the optimal sample,BC-P3K4S had the highest specific surface area of 3583.3 m^(2) g^(−1).Evaluated as the electrode for a lithium-ion capacitor,BC-P3K4S displayed a capacity of 139.1 mAh g^(−1) at 0.1 A g^(−1).After coupling it with pre-lithiated hard carbon,the full device exhibited a high energy density of 129.3 W h kg^(−1) at 153 W kg^(−1).The work outlined herein offers some insights into the preparation of hierarchical porous biochar from complex biomass by multistep activation method.
基金This work was financially supported by the Ministry of Science and Technology of China （Grants 2012CB215500 and 2013CB933100） and the National Natural Science Foundation of China （Grants 21103178 and 21033009）.
文摘A PtFe/C catalyst has been synthesized by impregnation and high-temperature reduction followed by acid-leaching. X-ray diffraction, X-ray photoelectron spectroscopy and X-ray atomic near edge spectroscopy characterization reveal that PtgFe alloy formation occurs during high-temperature reduction and that unstable Fe species are dissolved into acid solution. The difference in Fe concentration from the core region to the surface and strong O-Fe bonding may drive the outward diffusion of Fe to the highly corrugated Pt-skeleton, and the resulting highly dispersed surface FeOx is stable in acidic medium, leading to the construction of a PtBFe@Pt-FeOx architecture. The as prepared PtFe/C catalyst demonstrates a higher activity and comparable durability for the oxygen reduction reaction compared with a Pt/C catalyst, which might be due to the synergetic effect of surface and subsurface Fe species in the PtFe/C catalyst.
基金This work is supported by the National Key Research and Development Program of China[grant number 2018YFD1100104]the National Key Research and Development Program of China[grant number 2020YFC1521900].
文摘Most lakes have undergone significant changes on the Tibetan Plateau in recent decades,affecting water resources on the Tibetan Plateau and its surrounding areas.In this paper,we investigated the variations of 25 lakes in five sub-regions on the Tibetan Plateau from 1972 to 2019 based on SRTM DEM data and Landsat imagery.We used a method to derive lake-levels based on DEM and lake boundaries delineated from Landsat imagery,and then calculated the changes in lake area,level,and volume in 1972 to 2019.We also analyzed the potential impacts of temperature,precipitation,glacial and permafrost melting in lake changes during this period.The results show that the lakes tended to shrink until 2010 in southern and western plateau,after which they began to expand gradually but the overall trend is still shrinking.Limited meltwater from glaciers and permafrost and low precipitation are the main reasons for their shrinkage.The lakes in the central plateau,northwest plateau and northeast plateau tend to expand overall.The reason for the expansion of the lakes is not only precipitation but also the melting of glaciers and permafrost.Overall,the lake changes have gone through 3 phases,namely a slight decrease during 1972-2000,a rapid increase during 2000-2010,and a slowdown in the last decade(2010-2019).Multiple factors such as temperature,precipitation,the state of glaciers and permafrost have contributed to the changes in the lake.
文摘The strategy of element substitution is an effective way to tune the electronic structures of the active sites in catalysts, thereby leading to improvements in both the catalytic activity and stability. Herein, we design and synthesize pyrite-type nickel/phosphorus co-doped CoS2 nanowires on carbon cloth （NiCoPS/CC） as efficient and durable electrodes for water electrolysis. Introduction of nickel and phosphorus produced stepwise and superb enhancement of the performance of the electrodes in the hydrogen evolution reaction due to regulation of the electronic structures of the active sites of the catalyst and accelerated charge transfer over a wide pH range （0-14）. The NiCoPS/CC electrodes also delivered a nearly undecayed catalytic current density of 10 mA.cm-2 at a low overpotential of 230 mV for oxygen evolution due to in situ formation of surficial Ni-Co oxo/hydroxide in 1.0 M KOH. Thus, the NiCoPS/CC electrodes gave rise to a catalytic current density of 10 mA·cm-2 for overall water splitting at potentials as low as 1.54 V during operation over 100 h in 1.0 M KOH with a Faradic efficiency of ~100%.
基金the financial support from the National Natural Science Foundation of Shaanxi province,China (2019JQ-486)the Young Talent Support Project of Shaanxi (20200601)the Fundamental Research Funds for the Central Universities (No. D5000210651)。
文摘Nickel(Ni)-based materials are promising electrocatalysts for the urea electrooxidation reaction, as the in situ formed NiOOH species on their surface during operation are catalytically active sites. In this work, phytate-coordinated Ni foam(PA-NF)is shown to deliver a high catalytic performance, with a potential as low as 1.38 V at 10m A/cm2, a Tafel slope as low as 64.1 mV/dec, and superior catalytic stability. Characterizations revealed that such a high performance was ascribed to the kinetic acceleration of surface reconstruction and the enriched NiOOH active species on the PA-NF surface owing to PA-coordination induced upshift of d-band center of Ni sites.Overall, a novel and simple strategy is provided for designing the efficient as well as universal Ni-based catalyst for the electrooxidation of urea, which can also be extended to other transition-metal-based systems.
基金supported by the Chinese Major Science and Technology Program for Water Pollution Control and Treat-ment(No.2017ZX07207002-03)the Science and Technology Commission of Shanghai Municipality(Nos.19050501900 and 19DZ1204504)the Scientific Research Fund for Young Teachers of Shanghai Ocean University。
文摘Sulfonamides(SAs)are common antimicrobial drugs,which are frequently detected in surface water systems,and are difficult to degrade,posing a potential threat to the aquatic environment.However,little is known about the potential adverse effects of SAs on nontarget organisms(e.g.,microalgae)in the aquatic ecosystem.In this study,the effect of SAs(sulfadiazine(SD),sulfamerazine(SM1),and sulfamethazine(SM2)at 1,5,20,and 50 mg/L concentrations,respectively)on the freshwater microalga Dictyosphaerium sp.was investigated,with respect to changes of biomass and chlorophyll a content and induction of extracellular polymer substances(EPS),including protein and polysaccharide contents.At the same time,the residue of SAs was determined.The results showed that Dictyosphaerium sp.was tolerant to the three SAs,and the chlorophyll a content in Dictyosphaerium sp.significantly decreased on day 7,followed by a"compensation phenomena".The increase in protein and polysaccharide contents played a defensive role in Dictyosphaerium sp.against antibiotic stress,and there was a strong positive correlation between polysaccharide contents and antibiotic concentrations.Dictyosphaerium sp.exhibited 35%–45%,30%–42%,and 26%–51%removal of SD,SM1,and SM2,respectively.This study is helpful to understand the changes of EPS in the defense process of microalgae under the action of antibiotics,and provides a new insight for the ecological removal of antibiotic pollution in natural surface water system.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.52002314,21872109,81802841,and 81702999)China Postdoctoral Science Foundation(Nos.2018M633504 and 2018M633749)+3 种基金The study was also supported by the National Natural Science Foundation of Shaanxi Province(No.2019JQ-486)the Natural Science Basic Research Plan in Shaanxi Province(No.2019JM-033)Technology Innovation Development Foundation of Tangdu Hospital(No.2019QYTS003)Authors also acknowledge the support from the Fundamental Research Funds for the Central Universities(Nos.D5000210829 and G2021KY05102).
文摘Ca^(2+)plays critical roles in the development of diseases,whereas existing various Ca regulation methods have been greatly restricted in their clinical applications due to their high toxicity and inefficiency.To solve this issue,with the help of Ca overexpressed tumor drug resistance model,the phytic acid(PA)-modified CeO_(2) nano-inhibitors have been rationally designed as an unprecedentedly safe and efficient Ca2+inhibitor to successfully reverse tumor drug resistance through Ca^(2+)negative regulation strategy.Using doxorubicin(Dox)as a model chemotherapeutic drug,the Ca^(2+)nano-inhibitors efficiently deprived intracellular excessive free Ca2+,suppressed P-glycoprotein(P-gp)expression and significantly enhanced intracellular drug accumulation in Dox-resistant tumor cells.This Ca^(2+)negative regulation strategy improved the intratumoral Dox concentration by a factor of 12.4 and nearly eradicated tumors without obvious adverse effects.Besides,nanocerias as pH-regulated nanozyme greatly alleviated the adverse effects of chemotherapeutic drug on normal cells/organs and substantially improved survivals of mice.We anticipate that this safe and effective Ca^(2+)negative regulation strategy has potentials to conquer the pitfalls of traditional Ca inhibitors,improve therapeutic efficacy of common chemotherapeutic drugs and serves as a facile and effective treatment platform of other Ca^(2+) associated diseases.
文摘Challenges are faced for rapid economic and social development including the global energy shortage, diversification in energy and chemical raw materials, and ecological environmental protection. The development of renewable energy has become a common concern for the current society.
