Situs inversus totalis(SIT)is a rare congenital anomaly in which the major organs are reversed from their normal positions.In patients with SIT,the right-lobe graft must be placed in the left upper quadrant(LUQ).Howev...Situs inversus totalis(SIT)is a rare congenital anomaly in which the major organs are reversed from their normal positions.In patients with SIT,the right-lobe graft must be placed in the left upper quadrant(LUQ).However,hepatic outflow obstruction is a critical issue,often requiring radiologic intervention because of compression or kinking following graft regeneration of the vessels[1–3].Therefore,preoperative planning is essential to address the challenges of graft placement and vein reconstruction.Despite these complexities,we previously reported techniques using a reversed modified right-lobe(mRL)graft from a donor in a conventional recipient with SIT[2].Here,we successfully applied a similar concept.展开更多
Optimizing the microchannel design of the next generation of chips requires an understanding of the in situ property evolution of the chip-based materials under fast cooling.This work overcomes the conventional relian...Optimizing the microchannel design of the next generation of chips requires an understanding of the in situ property evolution of the chip-based materials under fast cooling.This work overcomes the conventional reliance on reheating data of melt-quenched glasses by demonstrating direct observations of glass transition on cooling curves utilizing the most advanced fast differential scanning calorimetry.By leveraging an MEMS chip sensor that allows for rapid heat extraction from microgram-sized samples to a purged gas coolant,the device is able to reach ultra-fast cooling rates of up to 40,000 K·s^(−1).Four thermal regions are identified by examining the cooling behaviors of two metallic glasses.This is because the actual rate of the specimen can differ from the programmed rate,especially at high set rate when the actual rate decreases before the glass transition is completed.We define the operational window for reliable cooling curve analysis,build models with empirical and theoretical analyses to determine the maximum feasible cooling rate,and demonstrate how optimizing sample mass and environment temperature broaden this window.The method avoids deceptive structural relaxation effects verified by fictivetemperature analysis and permits the capture of full glass transition during cooling.展开更多
By means the in situ halogenation of the vinyl C-H bond in o-hydroxyphenyl enaminones,the step efficient synthesis of 3-diphenylphosphinyl chromones has been realized through the challenging construction of C-P(Ⅲ) bo...By means the in situ halogenation of the vinyl C-H bond in o-hydroxyphenyl enaminones,the step efficient synthesis of 3-diphenylphosphinyl chromones has been realized through the challenging construction of C-P(Ⅲ) bond by using diphenyl phosphine as reaction partner.In addition,the tunable synthesis of 2-phosphoryl chromanones has been achieved via hydrophosphorylation by simply modifying reaction conditions without using metal reagent.展开更多
Escalating global energy demands and climate urgency necessitate advanced electrochemical energy conversion and storage technologies(EECSTs)like electrocatalysis and rechargeable batteries.Improving their performance ...Escalating global energy demands and climate urgency necessitate advanced electrochemical energy conversion and storage technologies(EECSTs)like electrocatalysis and rechargeable batteries.Improving their performance relies on elucidating reaction mechanisms and structure-performance relationships via in situ studies.This review summarizes recent in situ studies of EECSTs through a variety of advanced characterization techniques aiming at mapping reaction pathways for the rational design of overall high-performance reaction systems.We outline the principles,capabilities,advantages,and limitations of various in situ techniques.Their applications in in situ studies of fuel cells,water/CO_(2)electrolysis,and lithium batteries are highlighted with representative examples.These studies enable dynamic tracking of chemical and structural evolution of overall reaction systems,including materials,intermediates,products,and surroundings during operation,providing insights critical to rational system design.Future advancements will involve integrating multimodal in situ/operando approaches with artificial intelligence to enable real-time monitoring at practical scales.Such integration promises precise mechanistic insights and robust structure-performance correlations,ultimately accelerating the development of high-performance EECSTs aligned with sustainability and market requirements.展开更多
The formation of copper deposits is closely related to hydrothermal processes.Understanding the migration of copper in hydrothermal fluids aids in reconstructing mineralization processes and deciphering deposit genesi...The formation of copper deposits is closely related to hydrothermal processes.Understanding the migration of copper in hydrothermal fluids aids in reconstructing mineralization processes and deciphering deposit genesis.Copper primarily exists as Cu^(+)and Cu^(2+)in hydrothermal solutions,with redox conditions governing their interconversion.In chloride-rich geological fluids,Cu-Cl complexes are considered critical for copper transport.However,the specific types and valence transitions of Cu-Cl complexes under varying hydrothermal conditions remain poorly understood.This study employed in situ Raman spectroscopy to systematically analyze Cu+HCl and CuCl_(2)+K_(2)S_(2)O_(3)/H_(2) systems under saturated vapor pressure at 25-300℃,elucidating the effects of temperature,Cl^(-)concentration,and redox conditions on copper speciation.In the Cu^(+)HCl system,copper dissolved as monovalent Cu-Cl complexes.At high temperatures(>200℃),[CuCl_(2)]^(-)is the dominated species,whereas[CuCl_(3)]^(2-)becomes prevalent at lower temperatures and higher HCl concentrations.For the Cu^(2+)-Cl system,the dominant species transitioned from[Cu(H_(2)O)n]^(2+)(<50℃)to[CuCl_(4)]^(2-)(100℃)and further to[CuCl]^(+)and[CuCl_(2)]^(0) at 300℃.The introduction of reducing agents(K_(2)S_(2)O_(3)/H_(2))facilitated Cu^(2+)→Cu^(+)reduction,thereby stabilizing Cu^(+)-Cl complexes and inducing partial copper precipitation.The behavior of copper in chloriderich hydrothermal fluids observed in this study indicates that high-temperature oxidizing fluids facilitate Cu mobilization,while cooling and redox changes promote deposition and ore minerals formation.展开更多
In situ tumor vaccines,which leverage the antigenic profile of individual tumors,have demonstrated significant potential in tumor immunotherapy.However,their efficacy is often limited by the immunosuppressive tumor mi...In situ tumor vaccines,which leverage the antigenic profile of individual tumors,have demonstrated significant potential in tumor immunotherapy.However,their efficacy is often limited by the immunosuppressive tumor microenvironment(TME)and insufficient tumor targeting.To address these challenges,we engineered in situ nanovaccines through the self-assembly of the photosensitizer indocyanine green,immune adjuvant aluminum(Al^(3+)),and hydrophilic drug zoledronic acid(ZOL).Intravenous injection of these nanovaccines led to efficient tumor accumulation,enhancing drug bioavailability and enabling the release of tumor-associated antigens via photothermal therapy.Additionally,the built-in ZOL induces polarization of tumor-associated macrophages,reversing the immunosuppressive TME.The potent antitumor immune response triggered by these nanovaccines effectively suppresses tumor growth.This study,which integrates a straightforward assembly method,substantial drug loading capacity,and promising therapeutic outcomes,introduces a novel and effective paradigm for carrier-free in situ nanovaccines in cancer treatment.展开更多
Successful ex situ conservation of plant populations requires a high degree of genetic representativeness.However,spatially biased sampling in ex situ conservation efforts may fail to capture all wild genetic clusters...Successful ex situ conservation of plant populations requires a high degree of genetic representativeness.However,spatially biased sampling in ex situ conservation efforts may fail to capture all wild genetic clusters for species with range-wide genetic structure.To investigate the extent of spatially biased sampling in living collections and the coverage of wild genetic clusters in plant populations under ex situ conservation worldwide,we combined a global synthesis of ex situ conservation efforts with a case study of an endangered riparian plant species,Myricaria laxiflora.Our analysis of ex situ conservation worldwide revealed that the majority(82.6%)of ex situ populations fail to cover all wild genetic clusters,largely due to spatially biased sampling with low geographic coverage.Our case study of M.laxiflora showed that genetic diversity differed between the ex situ and upstream populations,while it was comparable between ex situ populations and other wild populations.However,current ex situ populations did not cover all wild genetic clusters,as the upstream genetic cluster was previously uncollected.Our study suggests that the failure to cover all wild genetic clusters in ex situ populations is a widespread issue,and ex situ populations with high genetic diversity can also fail to cover all wild genetic clusters.In future ex situ conservation programs,both the importance of high genetic diversity and the high coverage of wild genetic clusters should be prioritized.展开更多
Although manganese Prussian blue analogues(Mn-PBAs)offer advantages as cost-effective,high-energy-density cathode materials for sodium-ion batteries,their practical application is severely constrained by substantial c...Although manganese Prussian blue analogues(Mn-PBAs)offer advantages as cost-effective,high-energy-density cathode materials for sodium-ion batteries,their practical application is severely constrained by substantial capacity degradation during long-term cycling.This performance deterioration is closely associated with the structural instability of the material during the cycling process,which is mainly attributed to the gradual dissolution of the active material into the electrolyte and severe lattice distortion during Na+intercalation/deintercalation.Fortunately,the aforementioned challenges can be effectively addressed by fabricating an in situ engineered nickel cage(ISE-NC)on Mn-PBAs(denoted as Mn-PBAs-NC).Experimental characterization combined with theoretical calculations reveals that this spontaneously formed nickel cage not only suppresses the diffusion of Mn-PBAs into the electrolyte but also acts as a structural stabilizer,significantly alleviating lattice distortion during cycling.This dual stabilization mechanism ensures remarkable cycling stability,with Mn-PBAs-NC delivering a retained capacity of 96.4 mA h g^(−1)(80%capacity retention)over 2,300 cycles at 2 C,elevating the cycle life of Mn-PBAs to unprecedented levels.展开更多
The space environment, particularly highly reactive atomic oxygen(AO), often causes performance degradation and accelerated wear of solid-lubricating materials used in aerospace applications. In this study, an in situ...The space environment, particularly highly reactive atomic oxygen(AO), often causes performance degradation and accelerated wear of solid-lubricating materials used in aerospace applications. In this study, an in situ oxygen-passivated WS_(2) lubricating film(W–S–Ti–O composite film) was deposited to withstand AO irradiation. The structural and tribological evolution of the film was examined after a six-month space exposure experiment conducted outside the Chinese Space Station. The results show that in situ oxygen passivation of sulfur vacancies in the WS_(2) film promoted the formation of a dominant WS_(x)O_(y) phase within the W–S–Ti–O composite film. This phase effectively suppressed excessive WO_(3) formation during prolonged AO exposure while maintaining a low friction coefficient. After space exposure, the film exhibited a low friction coefficient and a wear life exceeding 4.5 × 10^(5) cycles. This performance is attributed to two main factors:(1) the presence of friction-induced spherical WO_(3) nanoparticles(approximately 11 nm) embedded in the transfer film, which promoted a transition from pure sliding to a mixed rolling–sliding regime;and(2) the retention of oriented WS_(2)(002) crystalline layers in the tribofilm, which mitigated the plowing effect of nanoparticles and prevented a significant increase in the wear rate.展开更多
Economical,stable,and corrosion-resistant catalytic electrodes are still urgently needed for the oxygen evolution reaction(OER)in water and seawater.Herein,a mild electroless plating strategy is used to achieve large-...Economical,stable,and corrosion-resistant catalytic electrodes are still urgently needed for the oxygen evolution reaction(OER)in water and seawater.Herein,a mild electroless plating strategy is used to achieve large-scale preparation of the“integrated”phosphorus-based precatalyst(FeP-NiP)on nickel foam(NF),which is in situ reconstructed into a highly active and corrosion-resistant(Fe)NiOOH phase for OER.The interaction between phosphate anions(PO_(x)^(y-))and iron ions(Fe^(3+))tunes the electronic structure of the catalytic phase to further enhance OER kinetics.The integrated FeP-NiP@NF electrode exhibits low overpotentials for OER in alkaline water/seawater,requiring only 275/289,320/336,and 349/358 mV to reach 0.1,0.5,and 1.0 A cm^(−2),respectively.The in situ reconstructed PO_(x)^(y-)anion electrostatically repels Cl−in seawater electrolytes,allowing stable operation for over 7 days at 1.0 A cm^(−2) in extreme electrolytes(1.0 M KOH+seawater and 6.0 M KOH+seawater),demonstrating industrial-level stability.This study overcomes the complex synthesis limitations of P-based materials through innovative material design,opening new avenues for electrochemical energy conversion.展开更多
High-pressure research has emerged as a pivotal approach for advancing our understanding and development of optoelectronic materials,which are vital for a wide range of applications,including photovoltaics,light-emitt...High-pressure research has emerged as a pivotal approach for advancing our understanding and development of optoelectronic materials,which are vital for a wide range of applications,including photovoltaics,light-emitting devices,and photodetectors.This review highlights various in situ characterization methods employed in high-pressure research to investigate the optical,electronic,and structural properties of optoelectronic materials.We explore the advances that have been made in techniques such as X-ray diffraction,absorption spectroscopy,nonlinear optics,photoluminescence spectroscopy,Raman spectroscopy,and photoresponse measurement,emphasizing how these methods have enhanced the elucidation of structural transitions,bandgap modulation,performance optimization,and carrier dynamics engineering.These insights underscore the pivotal role of high-pressure techniques in optimizing and tailoring optoelectronic materials for future applications.展开更多
Introduction Early cancer detection represents a critical evolution in healthcare,addressing a significant pain point in cancer treatment:the tendency for diagnoses to occur at advanced stages.Traditionally,many cance...Introduction Early cancer detection represents a critical evolution in healthcare,addressing a significant pain point in cancer treatment:the tendency for diagnoses to occur at advanced stages.Traditionally,many cancers are not identified until they have progressed to late stages,where treatment options become limited,less effective,and more costly.This late detection results in poorer prognoses,higher mortality rates,and increased healthcare costs.Without early detection tools like Fluorescence In Situ Hybridization(FISH),these challenges persist,leaving patients with fewer opportunities for successful outcomes.展开更多
Despite the ongoing increase in the efficiency of perovskite solar cells(PSCs),residual lead iodide(PbI2and moisture sensitivity issues continue to constrain their further commercialization.Herein,we propose a thermal...Despite the ongoing increase in the efficiency of perovskite solar cells(PSCs),residual lead iodide(PbI2and moisture sensitivity issues continue to constrain their further commercialization.Herein,we propose a thermally mediated in situ repair and encapsulation strategy to construct high-performance PSCs by incorporating piperazine thioctic acid salt(TAPPZ)as a dopant into the perovskite precursor Thermally dissociated piperazine(PPZ)from TAPPZ integrates microcrystals to form larger grain(>2000 nm),while the carboxylic acid in thioctic acid(TA)and the amine salt in TAPPZ synergistically passivate and transform PbI_(2),significantly reducing its residual amount.Additionally,TAPPZ undergoe thermal self-crosslinking during perovskite annealing,enabling melt-polymerization to form in situ encapsulation for enhanced water resistance.The TAPPZ-incorporated device achieves a remarkable efficiency of 25.65% and exhibits excellent operational stability,retaining over 90% of its initial efficiency after 2000 h under ambient conditions(20-30℃,20%-30% relative humidity).This study provide new insights into the construction of high-performance perovskite solar cells by designing and synthe sizing multifunctional single molecules for in situ repair and encapsulation of perovskites.展开更多
The pressure-preserving controller is the key component of deep in situ pressure-preserving coring(IPP-Coring).With increasing drilling depth,the environmental temperature and pressure increase accordingly.However,due...The pressure-preserving controller is the key component of deep in situ pressure-preserving coring(IPP-Coring).With increasing drilling depth,the environmental temperature and pressure increase accordingly.However,due to the strength and sealing problems of pressure-preserving controllers,the coring pressure is generally lower than 70 MPa.Establishing a high-temperature and ultrahigh-pressure test system is highly important for improving the strength and sealing performance of pressure-preserving controllers.This paper introduces a high-temperature and ultrahigh-pressure test system for deep IPP-Coring controller performance analysis.The device includes six parts:an auxiliary air source system,a pressurization system,a temperature control system,a hydraulic system,a data acquisition and electrical control system,and an ultrahigh-pressure vessel.The test system can reconstruct a 150℃ and 200 MPa in situ environment and simulate and test the movement state of the corer and the stability of the pressure-preserving action trigger of the pressure-preserving controller in the deep IPP-Coring process.To verify the performance of this test system,saddle-shaped pressure-preserving controllers made of four different materials were subjected to pressure tests under normal-temperature and high-temperature conditions.The results showed that the ultimate pressure-bearing capability of the pressure-preserving controller greatly varied between normal-temperature and high-temperature conditions.The pressure-preserving ability and sealing performance of the pressure-preserving controller decreased significantly at high temperature,and the pressure-preserving controller exhibited significantly different sealing failure characteristics due to material differences.This study is important for progressing the extraction and evaluation of deep reservoir resources.展开更多
High-nickel ternary cathodes hold a great application prospect in solid-state lithium metal batteries to achieve high-energy density,but they still suffer from structural instability and detrimental side reactions wit...High-nickel ternary cathodes hold a great application prospect in solid-state lithium metal batteries to achieve high-energy density,but they still suffer from structural instability and detrimental side reactions with the solid-state electrolytes.To circumvent these issues,a continuous uniform layer polyacrylonitrile(PAN)was introduced on the surface of LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2) via in situ polymerization of acrylonitrile(AN).Furthermore,the partial-cyclized treatment of PAN(cPAN)coating layer presents high ionic and electron conductivity,which can accelerate interfacial Li+and electron diffusion simultaneously.And the thermodynamically stabilized cPAN coating layer cannot only effectively inhibit detrimental side reactions between cathode and solid-state electrolytes but also provide a homogeneous stress to simultaneously address the problems of bulk structural degradation,which contributes to the exceptional mechanical and electrochemical stabilities of the modified electrode.Besides,the coordination bond interaction between the cPAN and NCM811 can suppress the migration of Ni to elevate the stability of the crystal structure.Benefited from these,the In-cPAN-260@NCM811 shows excellent cycling performance with a retention of 86.8%after 300 cycles and superior rate capability.And endow the solid-state battery with thermal safety stability even at hightemperature extreme environment.This facile and scalable surface engineering represents significant progress in developing high-performance solid-state lithium metal batteries.展开更多
In this work,silicon-carbon hybrid materials were adopted as an example to illustrate the novel strategy to in situ construct heterostructure with adjustable microstructure.Based on the temperature-dependent thermodyn...In this work,silicon-carbon hybrid materials were adopted as an example to illustrate the novel strategy to in situ construct heterostructure with adjustable microstructure.Based on the temperature-dependent thermodynamics and kinetics of reaction between Si and C,the processes for Si nanocrystals growth and C decoration were coupled at different zones of plasma flame according to its temperature and velocity fields by theoretical modeling,aiming to intentionally suppress the formation of undesirable carbide,and enable adjusting the microstructure of each counterpart separately in transient process.As a result,well-controlled Si/C nanocomposites,including nanospheres and nanowires with core-shell structures,were achieved,and this continuous and in-flight route is also potential for large-scale production.Further investigation on the electrochemical properties highlights the advantage of as proposed strategy to efficiently construct heterostructures with superior performance for various applications.展开更多
The clinical application of tumor vaccines is hindered by challenges such as timeconsuming and costly production processes.In this context,in situ cancer vaccines represent a promising strategy by leveraging endogenou...The clinical application of tumor vaccines is hindered by challenges such as timeconsuming and costly production processes.In this context,in situ cancer vaccines represent a promising strategy by leveraging endogenous tumor antigens to elicit robust antitumor T cell responses.Herein,a photoactivatable tumor-targeting in situ nanovaccine,Lipo-D8-6,was constructed using cRGD-functionalized liposomes that co-encapsulated the photosensitizer chlorin e6 and a cleavable immunoadjuvant conjugate D8,allowing light-triggered synchronous activation of three therapeutic modules.Upon near-infrared light irradiation,Lipo-D8-6 generates reactive oxygen species that exert direct cytotoxicity on tumor cells and induce immunogenic cell death,while concurrently cleaving the responsive linker within D8 to achieve the controlled release of R848.In vivo biodistribution analysis confirmed the superior intratumoral accumulation of Lipo-D8-6,facilitating precise treatment.In a large-volume tumor model,the nanovaccine exhibited pronounced antitumor efficacy,accompanied by enhanced tumor infiltration of CD8t T cells.Overall,this work provides a simplified and effective approach for developing in situ nanovaccines that enable synergistic photodynamic immunotherapy with precise spatiotemporal control over immune activation.展开更多
Electrocatalytic nitrate reduction reaction (NO_(3)-RR) to ammonia under ambient conditions is expected to be a green process for ammonia synthesis and alleviate water pollution issues.We report a CuO nanoparticles in...Electrocatalytic nitrate reduction reaction (NO_(3)-RR) to ammonia under ambient conditions is expected to be a green process for ammonia synthesis and alleviate water pollution issues.We report a CuO nanoparticles incorporated on nitrogen-doped porous carbon (CuO@NC) catalyst for NO_(3)-RR.Part of Cu(Ⅱ) is reduced to Cu(Ⅰ) during the NO_(3)-RR process to construct Cu(Ⅰ)-Cu(Ⅱ) pairs,confirmed by in situ X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy.Density functional theory (DFT) calculations indicated that the formation of Cu(Ⅰ) could provide a reaction path with smaller energy barrier for NO_(3)-RR,while Cu(Ⅱ) effectively suppressed the competition of hydrogen evolution reaction (HER).As a result,CuO@NC catalyst achieved a Faradaic efficiency of 84.2% at -0.49 V versus reversible hydrogen electrode (RHE),and a NH_(3)yield rate of 17.2 mg h^(-1)mg^(-1)cat.at -0.79 V vs.RHE,higher than the HaberBosch process (<3.4 g h^(-1)g^(-1)cat.).This work may open a new avenue for effective NO_(3)-RR by modulating oxidation states.展开更多
The global demand for effective skin injury treatments has prompted the exploration of tissue engineering solutions.While three-dimensional(3D)bioprinting has shown promise,challenges persist with respect to achieving...The global demand for effective skin injury treatments has prompted the exploration of tissue engineering solutions.While three-dimensional(3D)bioprinting has shown promise,challenges persist with respect to achieving timely and compatible solutions to treat diverse skin injuries.In situ bioprinting has emerged as a key new technology,since it reduces risks during the implantation of printed scaffolds and demonstrates superior therapeutic effects.However,maintaining printing fidelity during in situ bioprinting remains a critical challenge,particularly with respect to model layering and path planning.This study proposes a novel optimization-based conformal path planning strategy for in situ bioprinting-based repair of complex skin injuries.This strategy employs constrained optimization to identify optimal waypoints on a point cloud-approximated curved surface,thereby ensuring a high degree of similarity between predesigned planar and surface-mapped 3D paths.Furthermore,this method is applicable for skin wound treatments,since it generates 3D-equidistant zigzag curves along surface tangents and enables multi-layer conformal path planning to facilitate the treatment of volumetric injuries.Furthermore,the proposed algorithm was found to be a feasible and effective treatment in a murine back injury model as well as in other complex models,thereby showcasing its potential to guide in situ bioprinting,enhance bioprinting fidelity,and facilitate improvement of clinical outcomes.展开更多
1.Introduction Various geological phenomena on the surface and in the interior of the Earth,as well as their associated physical and chemical pro-cesses,are closely correlated with the action of in situ rock stress[1-...1.Introduction Various geological phenomena on the surface and in the interior of the Earth,as well as their associated physical and chemical pro-cesses,are closely correlated with the action of in situ rock stress[1-5].Understanding the rock stress state at great depths is not only an indispensable foundation for solving scientific problems associated with geology,geophysics,and geodynamics-such as plate-driving mechanisms,the earth’s energy equilibrium,earth-quake mechanisms,and tectonic activities-but also a necessary prerequisite for the evaluation,exploitation,and disposal of deep energy and resources,such as coal and metal minerals.Due to the complexity and uncertainty of the origin of in situ rock stress,it is a difficult quantity to evaluate,in comparison with other rock properties.Currently,reliable information on the stress state in a region can only be determined through field stress measurement.Therefore,a variety of stress measurement techniques have been developed and applied worldwide to provide information on crus-tal contemporary stress at specific depth ranges[6].展开更多
文摘Situs inversus totalis(SIT)is a rare congenital anomaly in which the major organs are reversed from their normal positions.In patients with SIT,the right-lobe graft must be placed in the left upper quadrant(LUQ).However,hepatic outflow obstruction is a critical issue,often requiring radiologic intervention because of compression or kinking following graft regeneration of the vessels[1–3].Therefore,preoperative planning is essential to address the challenges of graft placement and vein reconstruction.Despite these complexities,we previously reported techniques using a reversed modified right-lobe(mRL)graft from a donor in a conventional recipient with SIT[2].Here,we successfully applied a similar concept.
基金supported by the National Natural Science Foundation of China (Grant Nos.92580120 and 52471188)。
文摘Optimizing the microchannel design of the next generation of chips requires an understanding of the in situ property evolution of the chip-based materials under fast cooling.This work overcomes the conventional reliance on reheating data of melt-quenched glasses by demonstrating direct observations of glass transition on cooling curves utilizing the most advanced fast differential scanning calorimetry.By leveraging an MEMS chip sensor that allows for rapid heat extraction from microgram-sized samples to a purged gas coolant,the device is able to reach ultra-fast cooling rates of up to 40,000 K·s^(−1).Four thermal regions are identified by examining the cooling behaviors of two metallic glasses.This is because the actual rate of the specimen can differ from the programmed rate,especially at high set rate when the actual rate decreases before the glass transition is completed.We define the operational window for reliable cooling curve analysis,build models with empirical and theoretical analyses to determine the maximum feasible cooling rate,and demonstrate how optimizing sample mass and environment temperature broaden this window.The method avoids deceptive structural relaxation effects verified by fictivetemperature analysis and permits the capture of full glass transition during cooling.
基金financially supported by the National Natural Science Foundation of China (No.22261026)。
文摘By means the in situ halogenation of the vinyl C-H bond in o-hydroxyphenyl enaminones,the step efficient synthesis of 3-diphenylphosphinyl chromones has been realized through the challenging construction of C-P(Ⅲ) bond by using diphenyl phosphine as reaction partner.In addition,the tunable synthesis of 2-phosphoryl chromanones has been achieved via hydrophosphorylation by simply modifying reaction conditions without using metal reagent.
基金supported by the National Key Research and Development Program of China(2023YFA1508004)the National Natural Science Foundation of China(T2293692,22502164,92472203,22222903,52271229,22472074,22272069,22361132532,and 22021001)+6 种基金the Industry-University-Research Joint Innovation Project of Fujian Province(2023H6029)the Beijing National Laboratory for Molecular Sciences(BNLMS202305)the Scientific and Technological Project of Yunnan Precious Metals Laboratory(YPML-20240502063)the Liaoning Binhai Laboratory(Grant No.2024-05)the State Key Laboratory of Fine Chemicals,Dalian University of Technology(KF 2401)the Postdoctoral Fellowship Program of CPSF under Grant Number GZC20240897the China Postdoctoral Science Foundation(No.2025M770016).
文摘Escalating global energy demands and climate urgency necessitate advanced electrochemical energy conversion and storage technologies(EECSTs)like electrocatalysis and rechargeable batteries.Improving their performance relies on elucidating reaction mechanisms and structure-performance relationships via in situ studies.This review summarizes recent in situ studies of EECSTs through a variety of advanced characterization techniques aiming at mapping reaction pathways for the rational design of overall high-performance reaction systems.We outline the principles,capabilities,advantages,and limitations of various in situ techniques.Their applications in in situ studies of fuel cells,water/CO_(2)electrolysis,and lithium batteries are highlighted with representative examples.These studies enable dynamic tracking of chemical and structural evolution of overall reaction systems,including materials,intermediates,products,and surroundings during operation,providing insights critical to rational system design.Future advancements will involve integrating multimodal in situ/operando approaches with artificial intelligence to enable real-time monitoring at practical scales.Such integration promises precise mechanistic insights and robust structure-performance correlations,ultimately accelerating the development of high-performance EECSTs aligned with sustainability and market requirements.
基金jointly funded by the Strategic Priority Research Program of the Chinese Academy of Sciences(grant No.XDA0430301)the National Natural Science Foundation of China(grant Nos.42130109,41973059)。
文摘The formation of copper deposits is closely related to hydrothermal processes.Understanding the migration of copper in hydrothermal fluids aids in reconstructing mineralization processes and deciphering deposit genesis.Copper primarily exists as Cu^(+)and Cu^(2+)in hydrothermal solutions,with redox conditions governing their interconversion.In chloride-rich geological fluids,Cu-Cl complexes are considered critical for copper transport.However,the specific types and valence transitions of Cu-Cl complexes under varying hydrothermal conditions remain poorly understood.This study employed in situ Raman spectroscopy to systematically analyze Cu+HCl and CuCl_(2)+K_(2)S_(2)O_(3)/H_(2) systems under saturated vapor pressure at 25-300℃,elucidating the effects of temperature,Cl^(-)concentration,and redox conditions on copper speciation.In the Cu^(+)HCl system,copper dissolved as monovalent Cu-Cl complexes.At high temperatures(>200℃),[CuCl_(2)]^(-)is the dominated species,whereas[CuCl_(3)]^(2-)becomes prevalent at lower temperatures and higher HCl concentrations.For the Cu^(2+)-Cl system,the dominant species transitioned from[Cu(H_(2)O)n]^(2+)(<50℃)to[CuCl_(4)]^(2-)(100℃)and further to[CuCl]^(+)and[CuCl_(2)]^(0) at 300℃.The introduction of reducing agents(K_(2)S_(2)O_(3)/H_(2))facilitated Cu^(2+)→Cu^(+)reduction,thereby stabilizing Cu^(+)-Cl complexes and inducing partial copper precipitation.The behavior of copper in chloriderich hydrothermal fluids observed in this study indicates that high-temperature oxidizing fluids facilitate Cu mobilization,while cooling and redox changes promote deposition and ore minerals formation.
基金supported by Natural Science Foundation of Shandong Province(Nos.ZR2023MB081,ZR2024QB346)Shandong Traditional Chinese Medicine Technology Project(No.Q-2023127).
文摘In situ tumor vaccines,which leverage the antigenic profile of individual tumors,have demonstrated significant potential in tumor immunotherapy.However,their efficacy is often limited by the immunosuppressive tumor microenvironment(TME)and insufficient tumor targeting.To address these challenges,we engineered in situ nanovaccines through the self-assembly of the photosensitizer indocyanine green,immune adjuvant aluminum(Al^(3+)),and hydrophilic drug zoledronic acid(ZOL).Intravenous injection of these nanovaccines led to efficient tumor accumulation,enhancing drug bioavailability and enabling the release of tumor-associated antigens via photothermal therapy.Additionally,the built-in ZOL induces polarization of tumor-associated macrophages,reversing the immunosuppressive TME.The potent antitumor immune response triggered by these nanovaccines effectively suppresses tumor growth.This study,which integrates a straightforward assembly method,substantial drug loading capacity,and promising therapeutic outcomes,introduces a novel and effective paradigm for carrier-free in situ nanovaccines in cancer treatment.
基金supported by National Key Research and Development Program of China(2024YFF1307400)Hubei Provincial Natural Science Foundation and Three Gorges Innovation Development Joint Fund(Grant No.2023AFD195)China Three Gorges Corporation(NBZZ202300130).
文摘Successful ex situ conservation of plant populations requires a high degree of genetic representativeness.However,spatially biased sampling in ex situ conservation efforts may fail to capture all wild genetic clusters for species with range-wide genetic structure.To investigate the extent of spatially biased sampling in living collections and the coverage of wild genetic clusters in plant populations under ex situ conservation worldwide,we combined a global synthesis of ex situ conservation efforts with a case study of an endangered riparian plant species,Myricaria laxiflora.Our analysis of ex situ conservation worldwide revealed that the majority(82.6%)of ex situ populations fail to cover all wild genetic clusters,largely due to spatially biased sampling with low geographic coverage.Our case study of M.laxiflora showed that genetic diversity differed between the ex situ and upstream populations,while it was comparable between ex situ populations and other wild populations.However,current ex situ populations did not cover all wild genetic clusters,as the upstream genetic cluster was previously uncollected.Our study suggests that the failure to cover all wild genetic clusters in ex situ populations is a widespread issue,and ex situ populations with high genetic diversity can also fail to cover all wild genetic clusters.In future ex situ conservation programs,both the importance of high genetic diversity and the high coverage of wild genetic clusters should be prioritized.
基金financially supported by the Ten-thousand Talents Programthe K. C. Wong Pioneer Talent Program+3 种基金China Three Gorges Corporation (WWKY-2021–0027)Inner Mongolia Science and Technology Plan (2021ZD0033)the National Natural Science Foundation of China (52202121)funded by China Petroleum&Chemical Corporation (123091)
文摘Although manganese Prussian blue analogues(Mn-PBAs)offer advantages as cost-effective,high-energy-density cathode materials for sodium-ion batteries,their practical application is severely constrained by substantial capacity degradation during long-term cycling.This performance deterioration is closely associated with the structural instability of the material during the cycling process,which is mainly attributed to the gradual dissolution of the active material into the electrolyte and severe lattice distortion during Na+intercalation/deintercalation.Fortunately,the aforementioned challenges can be effectively addressed by fabricating an in situ engineered nickel cage(ISE-NC)on Mn-PBAs(denoted as Mn-PBAs-NC).Experimental characterization combined with theoretical calculations reveals that this spontaneously formed nickel cage not only suppresses the diffusion of Mn-PBAs into the electrolyte but also acts as a structural stabilizer,significantly alleviating lattice distortion during cycling.This dual stabilization mechanism ensures remarkable cycling stability,with Mn-PBAs-NC delivering a retained capacity of 96.4 mA h g^(−1)(80%capacity retention)over 2,300 cycles at 2 C,elevating the cycle life of Mn-PBAs to unprecedented levels.
基金financially supported by the Space Utilization System of China Manned Space Engineering (Grant No.KJZ-YY-WCL05)。
文摘The space environment, particularly highly reactive atomic oxygen(AO), often causes performance degradation and accelerated wear of solid-lubricating materials used in aerospace applications. In this study, an in situ oxygen-passivated WS_(2) lubricating film(W–S–Ti–O composite film) was deposited to withstand AO irradiation. The structural and tribological evolution of the film was examined after a six-month space exposure experiment conducted outside the Chinese Space Station. The results show that in situ oxygen passivation of sulfur vacancies in the WS_(2) film promoted the formation of a dominant WS_(x)O_(y) phase within the W–S–Ti–O composite film. This phase effectively suppressed excessive WO_(3) formation during prolonged AO exposure while maintaining a low friction coefficient. After space exposure, the film exhibited a low friction coefficient and a wear life exceeding 4.5 × 10^(5) cycles. This performance is attributed to two main factors:(1) the presence of friction-induced spherical WO_(3) nanoparticles(approximately 11 nm) embedded in the transfer film, which promoted a transition from pure sliding to a mixed rolling–sliding regime;and(2) the retention of oriented WS_(2)(002) crystalline layers in the tribofilm, which mitigated the plowing effect of nanoparticles and prevented a significant increase in the wear rate.
基金funding support from Natural Science Foundation of Shanghai(Grant No.23ZR1443900)the National Natural Science Foundation of China(Grant Nos.22178309,22476131 and 22176127)。
文摘Economical,stable,and corrosion-resistant catalytic electrodes are still urgently needed for the oxygen evolution reaction(OER)in water and seawater.Herein,a mild electroless plating strategy is used to achieve large-scale preparation of the“integrated”phosphorus-based precatalyst(FeP-NiP)on nickel foam(NF),which is in situ reconstructed into a highly active and corrosion-resistant(Fe)NiOOH phase for OER.The interaction between phosphate anions(PO_(x)^(y-))and iron ions(Fe^(3+))tunes the electronic structure of the catalytic phase to further enhance OER kinetics.The integrated FeP-NiP@NF electrode exhibits low overpotentials for OER in alkaline water/seawater,requiring only 275/289,320/336,and 349/358 mV to reach 0.1,0.5,and 1.0 A cm^(−2),respectively.The in situ reconstructed PO_(x)^(y-)anion electrostatically repels Cl−in seawater electrolytes,allowing stable operation for over 7 days at 1.0 A cm^(−2) in extreme electrolytes(1.0 M KOH+seawater and 6.0 M KOH+seawater),demonstrating industrial-level stability.This study overcomes the complex synthesis limitations of P-based materials through innovative material design,opening new avenues for electrochemical energy conversion.
基金supported by the National Nature Science Foundation of China(NSFC)(Grant Nos.22275004,62274040,and 62304046)the Shanghai Science and Technology Committee(Grant No.22JC1410300)+2 种基金the Shanghai Key Laboratory of Novel Extreme Condition Materials(Grant No.22dz2260800)the National Key Research and Development Program of China(Grant No.2022YFE0137400)the Shanghai Science and Technology Innovationaction Plan(Grant No.24DZ3001200).
文摘High-pressure research has emerged as a pivotal approach for advancing our understanding and development of optoelectronic materials,which are vital for a wide range of applications,including photovoltaics,light-emitting devices,and photodetectors.This review highlights various in situ characterization methods employed in high-pressure research to investigate the optical,electronic,and structural properties of optoelectronic materials.We explore the advances that have been made in techniques such as X-ray diffraction,absorption spectroscopy,nonlinear optics,photoluminescence spectroscopy,Raman spectroscopy,and photoresponse measurement,emphasizing how these methods have enhanced the elucidation of structural transitions,bandgap modulation,performance optimization,and carrier dynamics engineering.These insights underscore the pivotal role of high-pressure techniques in optimizing and tailoring optoelectronic materials for future applications.
基金supported by Guangzhou Development Zone Science and Technology(2021GH10,2020GH10,2023GH02)the University of Macao(MYRG2022-00271-FST)The Science and Technology Development Fund(FDCT)of Macao(0032/2022/A).
文摘Introduction Early cancer detection represents a critical evolution in healthcare,addressing a significant pain point in cancer treatment:the tendency for diagnoses to occur at advanced stages.Traditionally,many cancers are not identified until they have progressed to late stages,where treatment options become limited,less effective,and more costly.This late detection results in poorer prognoses,higher mortality rates,and increased healthcare costs.Without early detection tools like Fluorescence In Situ Hybridization(FISH),these challenges persist,leaving patients with fewer opportunities for successful outcomes.
基金supported by the National Natural Science Foundation of China(22238002 and 22208047)the China Postdoctoral Science Foundation(2024T170086 and 2022M720639)+1 种基金the Research and Innovation Team Project of Dalian University of Technology(DUT2022TB10)the Fundamental Research Funds for the Central Universities(DUT22LAB610)。
文摘Despite the ongoing increase in the efficiency of perovskite solar cells(PSCs),residual lead iodide(PbI2and moisture sensitivity issues continue to constrain their further commercialization.Herein,we propose a thermally mediated in situ repair and encapsulation strategy to construct high-performance PSCs by incorporating piperazine thioctic acid salt(TAPPZ)as a dopant into the perovskite precursor Thermally dissociated piperazine(PPZ)from TAPPZ integrates microcrystals to form larger grain(>2000 nm),while the carboxylic acid in thioctic acid(TA)and the amine salt in TAPPZ synergistically passivate and transform PbI_(2),significantly reducing its residual amount.Additionally,TAPPZ undergoe thermal self-crosslinking during perovskite annealing,enabling melt-polymerization to form in situ encapsulation for enhanced water resistance.The TAPPZ-incorporated device achieves a remarkable efficiency of 25.65% and exhibits excellent operational stability,retaining over 90% of its initial efficiency after 2000 h under ambient conditions(20-30℃,20%-30% relative humidity).This study provide new insights into the construction of high-performance perovskite solar cells by designing and synthe sizing multifunctional single molecules for in situ repair and encapsulation of perovskites.
基金funding support from National Natural Science Foundation of China(Grant Nos.52225403,51827901,and 52304146).
文摘The pressure-preserving controller is the key component of deep in situ pressure-preserving coring(IPP-Coring).With increasing drilling depth,the environmental temperature and pressure increase accordingly.However,due to the strength and sealing problems of pressure-preserving controllers,the coring pressure is generally lower than 70 MPa.Establishing a high-temperature and ultrahigh-pressure test system is highly important for improving the strength and sealing performance of pressure-preserving controllers.This paper introduces a high-temperature and ultrahigh-pressure test system for deep IPP-Coring controller performance analysis.The device includes six parts:an auxiliary air source system,a pressurization system,a temperature control system,a hydraulic system,a data acquisition and electrical control system,and an ultrahigh-pressure vessel.The test system can reconstruct a 150℃ and 200 MPa in situ environment and simulate and test the movement state of the corer and the stability of the pressure-preserving action trigger of the pressure-preserving controller in the deep IPP-Coring process.To verify the performance of this test system,saddle-shaped pressure-preserving controllers made of four different materials were subjected to pressure tests under normal-temperature and high-temperature conditions.The results showed that the ultimate pressure-bearing capability of the pressure-preserving controller greatly varied between normal-temperature and high-temperature conditions.The pressure-preserving ability and sealing performance of the pressure-preserving controller decreased significantly at high temperature,and the pressure-preserving controller exhibited significantly different sealing failure characteristics due to material differences.This study is important for progressing the extraction and evaluation of deep reservoir resources.
基金financially supported by the National Natural Science Foundation of China(Nos.22102212 and 22479067).
文摘High-nickel ternary cathodes hold a great application prospect in solid-state lithium metal batteries to achieve high-energy density,but they still suffer from structural instability and detrimental side reactions with the solid-state electrolytes.To circumvent these issues,a continuous uniform layer polyacrylonitrile(PAN)was introduced on the surface of LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2) via in situ polymerization of acrylonitrile(AN).Furthermore,the partial-cyclized treatment of PAN(cPAN)coating layer presents high ionic and electron conductivity,which can accelerate interfacial Li+and electron diffusion simultaneously.And the thermodynamically stabilized cPAN coating layer cannot only effectively inhibit detrimental side reactions between cathode and solid-state electrolytes but also provide a homogeneous stress to simultaneously address the problems of bulk structural degradation,which contributes to the exceptional mechanical and electrochemical stabilities of the modified electrode.Besides,the coordination bond interaction between the cPAN and NCM811 can suppress the migration of Ni to elevate the stability of the crystal structure.Benefited from these,the In-cPAN-260@NCM811 shows excellent cycling performance with a retention of 86.8%after 300 cycles and superior rate capability.And endow the solid-state battery with thermal safety stability even at hightemperature extreme environment.This facile and scalable surface engineering represents significant progress in developing high-performance solid-state lithium metal batteries.
基金financially supported by the National Natural Science Foundation of China(No.52174342)Beijing Natural Sci-ence Foundation(No.2232044)Beijing Municipal Education Commission Research Plan General Project(No.KM202410005009).
文摘In this work,silicon-carbon hybrid materials were adopted as an example to illustrate the novel strategy to in situ construct heterostructure with adjustable microstructure.Based on the temperature-dependent thermodynamics and kinetics of reaction between Si and C,the processes for Si nanocrystals growth and C decoration were coupled at different zones of plasma flame according to its temperature and velocity fields by theoretical modeling,aiming to intentionally suppress the formation of undesirable carbide,and enable adjusting the microstructure of each counterpart separately in transient process.As a result,well-controlled Si/C nanocomposites,including nanospheres and nanowires with core-shell structures,were achieved,and this continuous and in-flight route is also potential for large-scale production.Further investigation on the electrochemical properties highlights the advantage of as proposed strategy to efficiently construct heterostructures with superior performance for various applications.
基金supported by National Natural Science Foundation of China(22090011)Liaoning Binhai Laboratory(LBLB-2023-03)Fundamental Research Funds for the Central Universities(DUT22LAB608).
文摘The clinical application of tumor vaccines is hindered by challenges such as timeconsuming and costly production processes.In this context,in situ cancer vaccines represent a promising strategy by leveraging endogenous tumor antigens to elicit robust antitumor T cell responses.Herein,a photoactivatable tumor-targeting in situ nanovaccine,Lipo-D8-6,was constructed using cRGD-functionalized liposomes that co-encapsulated the photosensitizer chlorin e6 and a cleavable immunoadjuvant conjugate D8,allowing light-triggered synchronous activation of three therapeutic modules.Upon near-infrared light irradiation,Lipo-D8-6 generates reactive oxygen species that exert direct cytotoxicity on tumor cells and induce immunogenic cell death,while concurrently cleaving the responsive linker within D8 to achieve the controlled release of R848.In vivo biodistribution analysis confirmed the superior intratumoral accumulation of Lipo-D8-6,facilitating precise treatment.In a large-volume tumor model,the nanovaccine exhibited pronounced antitumor efficacy,accompanied by enhanced tumor infiltration of CD8t T cells.Overall,this work provides a simplified and effective approach for developing in situ nanovaccines that enable synergistic photodynamic immunotherapy with precise spatiotemporal control over immune activation.
基金National Natural Science Foundation of China (52371228, 52402045)fund of Key Laboratory of Advanced Materials of Ministry of Education(Advmat-2414)。
文摘Electrocatalytic nitrate reduction reaction (NO_(3)-RR) to ammonia under ambient conditions is expected to be a green process for ammonia synthesis and alleviate water pollution issues.We report a CuO nanoparticles incorporated on nitrogen-doped porous carbon (CuO@NC) catalyst for NO_(3)-RR.Part of Cu(Ⅱ) is reduced to Cu(Ⅰ) during the NO_(3)-RR process to construct Cu(Ⅰ)-Cu(Ⅱ) pairs,confirmed by in situ X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy.Density functional theory (DFT) calculations indicated that the formation of Cu(Ⅰ) could provide a reaction path with smaller energy barrier for NO_(3)-RR,while Cu(Ⅱ) effectively suppressed the competition of hydrogen evolution reaction (HER).As a result,CuO@NC catalyst achieved a Faradaic efficiency of 84.2% at -0.49 V versus reversible hydrogen electrode (RHE),and a NH_(3)yield rate of 17.2 mg h^(-1)mg^(-1)cat.at -0.79 V vs.RHE,higher than the HaberBosch process (<3.4 g h^(-1)g^(-1)cat.).This work may open a new avenue for effective NO_(3)-RR by modulating oxidation states.
基金supported in part by the National Natural Science Foundation of China(Nos.52205532 and 624B2077)the National Key Research and Development Program of China(No.2023YFB4302003).
文摘The global demand for effective skin injury treatments has prompted the exploration of tissue engineering solutions.While three-dimensional(3D)bioprinting has shown promise,challenges persist with respect to achieving timely and compatible solutions to treat diverse skin injuries.In situ bioprinting has emerged as a key new technology,since it reduces risks during the implantation of printed scaffolds and demonstrates superior therapeutic effects.However,maintaining printing fidelity during in situ bioprinting remains a critical challenge,particularly with respect to model layering and path planning.This study proposes a novel optimization-based conformal path planning strategy for in situ bioprinting-based repair of complex skin injuries.This strategy employs constrained optimization to identify optimal waypoints on a point cloud-approximated curved surface,thereby ensuring a high degree of similarity between predesigned planar and surface-mapped 3D paths.Furthermore,this method is applicable for skin wound treatments,since it generates 3D-equidistant zigzag curves along surface tangents and enables multi-layer conformal path planning to facilitate the treatment of volumetric injuries.Furthermore,the proposed algorithm was found to be a feasible and effective treatment in a murine back injury model as well as in other complex models,thereby showcasing its potential to guide in situ bioprinting,enhance bioprinting fidelity,and facilitate improvement of clinical outcomes.
基金financially supported by the National Key Research and Development Program of China(2022YFC3004601)the National Natural Science Foundation of China(52204084)the Science,Technology and Innovation Project of Xiongan New Area(2023XAGG0061).
文摘1.Introduction Various geological phenomena on the surface and in the interior of the Earth,as well as their associated physical and chemical pro-cesses,are closely correlated with the action of in situ rock stress[1-5].Understanding the rock stress state at great depths is not only an indispensable foundation for solving scientific problems associated with geology,geophysics,and geodynamics-such as plate-driving mechanisms,the earth’s energy equilibrium,earth-quake mechanisms,and tectonic activities-but also a necessary prerequisite for the evaluation,exploitation,and disposal of deep energy and resources,such as coal and metal minerals.Due to the complexity and uncertainty of the origin of in situ rock stress,it is a difficult quantity to evaluate,in comparison with other rock properties.Currently,reliable information on the stress state in a region can only be determined through field stress measurement.Therefore,a variety of stress measurement techniques have been developed and applied worldwide to provide information on crus-tal contemporary stress at specific depth ranges[6].
