Most previous land-surface model calibration studies have defined globalranges for their parameters to search for optimal parameter sets. Little work has been conducted tostudy the impacts of realistic versus global r...Most previous land-surface model calibration studies have defined globalranges for their parameters to search for optimal parameter sets. Little work has been conducted tostudy the impacts of realistic versus global ranges as well as model complexities on the calibrationand uncertainty estimates. The primary purpose of this paper is to investigate these impacts byemploying Bayesian Stochastic Inversion (BSI) to the Chameleon Surface Model (CHASM). The CHASM wasdesigned to explore the general aspects of land-surface energy balance representation within acommon modeling framework that can be run from a simple energy balance formulation to a complexmosaic type structure. The BSI is an uncertainty estimation technique based on Bayes theorem,importance sampling, and very fast simulated annealing. The model forcing data and surface flux datawere collected at seven sites representing a wide range of climate and vegetation conditions. Foreach site, four experiments were performed with simple and complex CHASM formulations as well asrealistic and global parameter ranges. Twenty eight experiments were conducted and 50 000 parametersets were used for each run. The results show that the use of global and realistic ranges givessimilar simulations for both modes for most sites, but the global ranges tend to produce someunreasonable optimal parameter values. Comparison of simple and complex modes shows that the simplemode has more parameters with unreasonable optimal values. Use of parameter ranges and modelcomplexities have significant impacts on frequency distribution of parameters, marginal posteriorprobability density functions, and estimates of uncertainty of simulated sensible and latent heatfluxes. Comparison between model complexity and parameter ranges shows that the former has moresignificant impacts on parameter and uncertainty estimations.展开更多
Severe water erosion is notorious for its harmful effects on land-water resources as well as local societies. The scale effects of water erosion, however, greatly exacerbate the difficulties of accurate erosion evalua...Severe water erosion is notorious for its harmful effects on land-water resources as well as local societies. The scale effects of water erosion, however, greatly exacerbate the difficulties of accurate erosion evaluation and hazard control in the real world. Analyzing the related scale issues is thus urgent for a better understanding of erosion variations as well as reducing such erosion. In this review article, water erosion dynamics across three spatial scales including plot, watershed, and regional scales were selected and discussed. For the study purposes and objectives, the advantages and disadvantages of these scales all demonstrate clear spatial-scale dependence. Plot scale studies are primarily focused on abundant data collection and mechanism discrimination of erosion generation, while watershed scale studies provide valuable information for watershed management and hazard control as well as the development of quantitatively distributed models. Regional studies concentrate more on large-scale erosion assessment, and serve policymakers and stakeholders in achieving the basis for regulatory policy for comprehensive land uses. The results of this study show that the driving forces and mechanisms of water erosion variations among the scales are quite different. As a result, several major aspects contributing to variations in water erosion across the scales are stressed: differences in the methodologies across various scales, different sink-source roles on water erosion processes, and diverse climatic zones and morphological regions. This variability becomes more complex in the context of accelerated global change. The changing climatic factors and earth surface features are considered the fourth key reason responsible for the increased variability of water erosion across spatial scales.展开更多
Three copper(Ⅱ),nickel and cadmium(Ⅱ)complexes,namely[Cu_(2)(μ-H2dbda)2(phen)2]·2H_(2)O(1),[Ni(μ-H2dbda)(μ-bpb)(H_(2)O)2]n(2),and[Cd(μ-H2dbda)(μ-bpa)]n(3),have been constructed hydrothermally using H4dbda(...Three copper(Ⅱ),nickel and cadmium(Ⅱ)complexes,namely[Cu_(2)(μ-H2dbda)2(phen)2]·2H_(2)O(1),[Ni(μ-H2dbda)(μ-bpb)(H_(2)O)2]n(2),and[Cd(μ-H2dbda)(μ-bpa)]n(3),have been constructed hydrothermally using H4dbda(4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid),phen(1,10-phenanthroline),bpb(1,4-bis(pyrid-4-yl)benzene),bpa(bis(4-pyridyl)amine),and copper,nickel and cadmium chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and singlecrystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the monoclinic P21/n,tetragonal I42d,and orthorhombic P21212 space groups.The complexes exhibit molecular dimers(1)or 2D metal-organic networks(2 and 3).The catalytic performances in the Knoevenagel reaction of these complexes were investigated.Complex 1 exhibits an effective catalytic activity and excellent reusability as a heterogeneous catalyst in the Knoevenagel reaction at room temperature.CCDC:2463800,1;2463801,2;2463802,3.展开更多
Three zinc(Ⅱ),nickel(Ⅱ),and cadmium(Ⅱ)complexes,namely[Zn(μ-Htpta)(py)_(2)]n(1),[Ni(H_(2)biim)2(H_(2)O)2][Ni(tpta)(H_(2)biim)2(H_(2)O)]2·3H_(2)O(2),and[Cd_(3)(μ4-tpta)2(μ-dpe)_(3)]_(n)(3),have been construc...Three zinc(Ⅱ),nickel(Ⅱ),and cadmium(Ⅱ)complexes,namely[Zn(μ-Htpta)(py)_(2)]n(1),[Ni(H_(2)biim)2(H_(2)O)2][Ni(tpta)(H_(2)biim)2(H_(2)O)]2·3H_(2)O(2),and[Cd_(3)(μ4-tpta)2(μ-dpe)_(3)]_(n)(3),have been constructed hydrothermally at 160℃ using H_(3)tpta([1,1':3',1″-terphenyl]-4,4',5'-tricarboxylic acid),py(pyridine),H_(2)biim(2,2'-biimidazole),dpe(1,2-di(4-pyridyl)ethylene),and zinc,nickel and cadmium chlorides,resulting in the formation of stable crystalline solids which were subsequently analyzed using infrared spectroscopy,element analysis,thermogravimetric analysis,as well as structural analyses conducted via single-crystal X-ray diffraction.The findings from these single-crystal Xray diffraction studies indicate that complexes 1-3 form crystals within the monoclinic system P2_(1)/c space group(1)or triclinic system P1 space group(2 and 3),and possess 1D,0D,and 3D structures,respectively.Complex 1 demonstrated substantial catalytic efficiency and excellent reusability as a heterogeneous catalyst in the reaction of Knoevenagel condensation under ambient temperature conditions.In addition,complex 1 also showcased notable anti-wear performance when used in polyalphaolefin synthetic lubricants.CCDC:2449810,1;2449811,2;2449812,3.展开更多
Six new lanthanide complexes:[Ln(3,4-DEOBA)3(4,4'-DM-2,2'-bipy)]2·2C_(2)H_(5)OH,[Ln=Dy(1),Eu(2),Tb(3),Sm(4),Ho(5),Gd(6);3,4-DEOBA-=3,4-diethoxybenzoate,4,4'-DM-2,2'-bipy=4,4'-dimethyl-2,2'...Six new lanthanide complexes:[Ln(3,4-DEOBA)3(4,4'-DM-2,2'-bipy)]2·2C_(2)H_(5)OH,[Ln=Dy(1),Eu(2),Tb(3),Sm(4),Ho(5),Gd(6);3,4-DEOBA-=3,4-diethoxybenzoate,4,4'-DM-2,2'-bipy=4,4'-dimethyl-2,2'-bipyridine]were successfully synthesized by the volatilization of the solution at room temperature.The crystal structures of six complexes were determined by single-crystal X-ray diffraction technology.The results showed that the complexes all have a binuclear structure,and the structures contain free ethanol molecules.Moreover,the coordination number of the central metal of each structural unit is eight.Adjacent structural units interact with each other through hydrogen bonds and further expand to form 1D chain-like and 2D planar structures.After conducting a systematic study on the luminescence properties of complexes 1-4,their emission and excitation spectra were obtained.Experimental results indicated that the fluorescence lifetimes of complexes 2 and 3 were 0.807 and 0.845 ms,respectively.The emission spectral data of complexes 1-4 were imported into the CIE chromaticity coordinate system,and their corre sponding luminescent regions cover the yellow light,red light,green light,and orange-red light bands,respectively.Within the temperature range of 299.15-1300 K,the thermal decomposition processes of the six complexes were comprehensively analyzed by using TG-DSC/FTIR/MS technology.The hypothesis of the gradual loss of ligand groups during the decomposition process was verified by detecting the escaped gas,3D infrared spectroscopy,and ion fragment information detected by mass spectrometry.The specific decomposition path is as follows:firstly,free ethanol molecules and neutral ligands are removed,and finally,acidic ligands are released;the final product is the corresponding metal oxide.CCDC:2430420,1;2430422,2;2430419,3;2430424,4;2430421,5;2430423,6.展开更多
This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the correspo...This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the corresponding ester[Fe_(2)(CO)_(6)(μ‑tedt)](2),where tedt=SCH_(2)CH(CH_(2)OOC(5‑C_(3)HNSCH_(3)))S.Further reactions of complex 2 with tri(ptolyl)phosphine(tp)or tris(4‑fluorophenyl)phosphine(fp)gave the phosphine‑substituted derivatives[Fe_(2)(CO)_(5)(tp)(μ‑tedt)](3)and[Fe_(2)(CO)_(5)(fp)(μ‑tedt)](4).The structures of the newly prepared complexes were elucidated by elemental analysis,NMR,IR,and X‑ray photoelectron spectroscopy.Moreover,single‑crystal X‑ray diffraction analysis confirmed their molecular structures,showing that they contain a di‑iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls.The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry,revealing that three complexes can catalyze the reduction of protons to H_(2) under the electrochemical conditions.For comparison,complex 4 possessed the best efficiency with a turnover frequency of 23.5 s^(-1)at 10 mmol·L^(-1)HOAc concentration.In addition,the fungicidal activity of these complexes was also investigated in this study.CCDC:2477511,2;2477512,3;2477513,4.展开更多
The complexes 1-4 of cyclobutanocucurbit[5]uril(CyB5Q[5])with Na^(+)/K^(+)have been synthesized and characterized by single-crystal X-ray diffraction.The results show that although the inorganic salts are used when th...The complexes 1-4 of cyclobutanocucurbit[5]uril(CyB5Q[5])with Na^(+)/K^(+)have been synthesized and characterized by single-crystal X-ray diffraction.The results show that although the inorganic salts are used when the cations are the same and the anions are different,in complex 1,Na^(+)closes one port of CyB5Q[5]through Na—O seven coordination bonds to form a molecular bowl;in complex 3,Na^(+)completely closes the two ports of CyB5Q[5]to form a molecular capsule with six Na—O coordination bonds;in complexes 2 and 4,the two ports of CyB5Q[5]are completely closed to form K—O coordinated molecular capsules,but the K^(+)of complex 2 is six-coordinated and that of complex 4 is eight-/nine-coordinated.and complex 4 are connected by three oxygen bridges to form a 1D molecular chain.CCDC:2457122,1;2457121,2;2457400,3;2457120,4.展开更多
A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescenc...A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.展开更多
1.Objective Nigeria lies between the West African Craton and the Congo Craton,south of the Tuareg Shield(Ogunmola JK et al.,2015).The Nasarawa pegmatite field mainly comprises of the Precambrian Basement Complex(inclu...1.Objective Nigeria lies between the West African Craton and the Congo Craton,south of the Tuareg Shield(Ogunmola JK et al.,2015).The Nasarawa pegmatite field mainly comprises of the Precambrian Basement Complex(including Archean-Proterozoic migmatite,gneiss,schists and Pan-African “Older Granites”),Mesozoic alkaline ring complexes(“Younger Granites”) and sedimentary basins(Yang QD et al.,2023;Fig.1a).“Older Granites” are part of the Pan-African mobile belt;“Younger Granites” has significant peralkaline characteristics.“Younger Granites” has a wide distribution in the north-central region of Nigeria,including areas such as Kano,Jos-Bauchi,Mada,and Nasarawa,and the emplacement age gradually decreases from north to south from 213 Ma(Dutse complex) to 141 Ma(Afu complex)(Amuda AK et al.,2021).展开更多
Dear Editor,We present a case of acute zonal occult outer retinopathy(AZOOR)complex in a myopic patient with angioid streaks(ASs).A 19-year-old female has been experiencing visual field defects in her left eye for mor...Dear Editor,We present a case of acute zonal occult outer retinopathy(AZOOR)complex in a myopic patient with angioid streaks(ASs).A 19-year-old female has been experiencing visual field defects in her left eye for more than 3y.She was diagnosed with ASs and choroiditis at a local hospital.She has a seven-year history of bilateral high myopia.A fundus examination confirmed the presence of ASs and myopic fundus changes in both eyes.Multimodal imaging revealed an AZOOR complex in the left eye.展开更多
Multi-organ-on-a-chip(MOOC)technology represents a pivotal direction in the organ-on-a-chip field,seeking to emulate the complex interactions of multiple human organs in vitro through microfluidic systems.This technol...Multi-organ-on-a-chip(MOOC)technology represents a pivotal direction in the organ-on-a-chip field,seeking to emulate the complex interactions of multiple human organs in vitro through microfluidic systems.This technology overcomes the limitations of traditional single-organ models,providing a novel platform for investigating complex disease mechanisms and evaluating drug efficacy and toxicity.Although it demonstrates broad application prospects,its development still faces critical bottlenecks,including inadequate physiological coupling between organs,short functional maintenance durations,and limited real-time monitoring capabilities.Contemporary research is advancing along three key directions,including functional coupling,sensor integration,and full-process automation systems,to propel the technology toward enhanced levels of physiological relevance and predictive accuracy.展开更多
There have been active work to extend the Prolog style Horn Clause logic programming to non-Horn clauses.In this paper,we will analyze the complexities of several such extensions.The purpose is to understand the compu...There have been active work to extend the Prolog style Horn Clause logic programming to non-Horn clauses.In this paper,we will analyze the complexities of several such extensions.The purpose is to understand the computational complexity of these inference systems.The analyses do not prove that any one system is better than the others all the time.But they do suggest that one system may be better than the others for some particular problems.We also discuss the effect of caching.展开更多
Herein,we report a novel,visible-light-induced approach for the selective construction of both gem-difluoroalkenes and trifluoromethyl alkanes from α-trifluoromethyl olefins using alcohol-derived N-alkoxyphthalimides...Herein,we report a novel,visible-light-induced approach for the selective construction of both gem-difluoroalkenes and trifluoromethyl alkanes from α-trifluoromethyl olefins using alcohol-derived N-alkoxyphthalimides as alkyl radical precursors.This strategy leverages Eosin Y as a photocatalyst in a defluorinative alkylation reaction and a catalyst-free electron donor-acceptor(EDA)complex-mediated hydroalkylation process.By modulating the reaction conditions,the desired products were selectively obtained with excellent chemo-selectivity and in high yields.The protocol accommodates a wide variety of substrates,including primary,secondary,and tertiary alcohols,as well as diverse α-trifluoromethyl styrenes,and is applicable to late-stage functionalization of natural products and bioactive molecules.展开更多
Cisplatin(CDDP)-based chemotherapy is an effective strategy for the treatment of advanced nasopharyngeal carcinoma(NPC).However,serious toxic side effects of CDDP limit patient tolerance and treatment compliance,which...Cisplatin(CDDP)-based chemotherapy is an effective strategy for the treatment of advanced nasopharyngeal carcinoma(NPC).However,serious toxic side effects of CDDP limit patient tolerance and treatment compliance,which urgently needs to be addressed in clinical application.Liposomes have been considered ideal vehicles for reducing CDDP toxicity due to their high biocompatibility,low toxicity and passive targeting ability.Nevertheless,CDDP's poor water/lipid solubility usually results in a low liposome druglipid ratio,limiting tumor delivery ability.Herein,a CDDP-polyphenol complex liposome was designed to increase the drug loading capacity of CDDP to realize the reduction of toxicity and effective antitumor effect simultaneously.The complex was prepared via complexation reaction of different stoichiometric ratios of CDDP and polyphenolic substances(gallic acid,epigallocatechin gallate and tannic acid),followed by encapsulation of complex in liposomes to improve tumor targeting.Notably,the molecular interaction forces between CDDP and polyphenolic substances were intensively investigated through a binding force disruption assay.In vitro studies demonstrated that the optimal formulation of CDDP-epigallocatechin gallate complex liposome(CDDP-EGCG Lips) showed the highest CDDP encapsulation efficiency,favorable stability,pH-sensitive release,enhanced cellular uptake and apoptosis effect.In vivo studies revealed that CDDP-EGCG Lips retarded the elimination of CDDP to prolong their circulation time,inhibited the growth of tumors,and significantly reduced the toxic side effects compared to CDDP monotherapy.This delivery strategy holds great promise for improving the clinical use of platinum-based drugs.展开更多
Anthocyanin biosynthesis in plants is spatiotemporally controlled by a suite of transcription factors,with MYB proteins playing a key regulatory role.However,the evolution of the distinct roles of MYB paralogs remains...Anthocyanin biosynthesis in plants is spatiotemporally controlled by a suite of transcription factors,with MYB proteins playing a key regulatory role.However,the evolution of the distinct roles of MYB paralogs remains poorly understood.Our previous studies have established GmMYBA2 and GmMYBA3 as the regulators of seed coat and floral anthocyanin production in soybean(Glycine max),respectively.In this study,we reveal the functional divergence of their paralog GmMYBA1 in orchestrating light-responsive anthocyanin biosynthesis in juvenile tissues and stems.In brief,hypocotyl/stem-and young leaf-predominant expression of GmMYBA1 correlates with photoprotective anthocyanin accumulation.Ectopic overexpression of GmMYBA1 induces systemic pigmentation across leaves,stems,and reproductive organs,whereas RNAi-mediated silencing of GmMYBA1 significantly reduces anthocyanin accumulation in the hypocotyl.Light-dark shift assays confirmed that GmMYBA1 is required for hypocotyl pigmentation,while dual-luciferase assays revealed the specific regulation of the GmMYBA paralogs by GmSTF1/2(soybean TGACG-motif binding factor 1/2).GmSTF1/2 both activate GmMYBA1,with only GmSTF2 weakly inducing GmMYBA2 and neither affecting GmMYBA3.Further investigation indicated that the differential transactivation of GmMYBA promoters largely resulted from their cis-element difference,suggesting regulatory divergence as a driver of MYB paralog diversification.Our findings position GmMYBA1 as the central MYB activator integrating light signaling with anthocyanin biosynthesis,with paralog specialization reflecting evolutionary subfunctionalization post-gene duplication.展开更多
Ultra-high-strength aluminumalloy profile is an ideal choice for aerospace structuralmaterials due to its excellent specific strength and corrosion resistance.However,issues such as uneven metal flow,stress concentrat...Ultra-high-strength aluminumalloy profile is an ideal choice for aerospace structuralmaterials due to its excellent specific strength and corrosion resistance.However,issues such as uneven metal flow,stress concentration,and forming defects are prone to occur during their extrusion.This study focuses on an Al-Zn-Mg-Cu ultra-high-strength aluminum alloy profile with a double-U,multi-cavity thin-walled structure.Firstly,hot compression experiments were conducted at temperatures of 350○C,400○C,and 450○C,with strain rates of 0.01 and 1.0 s^(−1),to investigate the plastic deformation behavior of the material.Subsequently,a 3D coupled thermo-mechanical extrusion simulation model was established using Deform-3D to systematically analyze the influence of die structure and process parameters on metal flow velocity,effective stress/strain,and temperature distribution.The simulation revealed significant velocity differences,stress concentration,and uneven temperature distribution.Key parameters,including mesh density,extrusion ratio,die fillet,and bearing length,were optimized through full-factorial experiments.This optimization,combined with a stepped flow-guiding die design,effectively improved the metal flow pattern during extrusion.Trial production based on both the initial and optimized parameters were carried out.A comparative analysis demonstrates that the optimized scheme results in a final profile whose cross-section matches the target design closely,with complete filling of complex features and no obvious forming defects.This research provides a valuable reference for the extrusion process optimization and die design of complex-section profiles made from ultra-high-strength aluminum alloys.展开更多
In modern industrial production,foreign object detection in complex environments is crucial to ensure product quality and production safety.Detection systems based on deep-learning image processing algorithms often fa...In modern industrial production,foreign object detection in complex environments is crucial to ensure product quality and production safety.Detection systems based on deep-learning image processing algorithms often face challenges with handling high-resolution images and achieving accurate detection against complex backgrounds.To address these issues,this study employs the PatchCore unsupervised anomaly detection algorithm combined with data augmentation techniques to enhance the system’s generalization capability across varying lighting conditions,viewing angles,and object scales.The proposed method is evaluated in a complex industrial detection scenario involving the bogie of an electric multiple unit(EMU).A dataset consisting of complex backgrounds,diverse lighting conditions,and multiple viewing angles is constructed to validate the performance of the detection system in real industrial environments.Experimental results show that the proposed model achieves an average area under the receiver operating characteristic curve(AUROC)of 0.92 and an average F1 score of 0.85.Combined with data augmentation,the proposed model exhibits improvements in AUROC by 0.06 and F1 score by 0.03,demonstrating enhanced accuracy and robustness for foreign object detection in complex industrial settings.In addition,the effects of key factors on detection performance are systematically analyzed,providing practical guidance for parameter selection in real industrial applications.展开更多
Identifying the community structure of complex networks is crucial to extracting insights and understanding network properties.Although several community detection methods have been proposed,many are unsuitable for so...Identifying the community structure of complex networks is crucial to extracting insights and understanding network properties.Although several community detection methods have been proposed,many are unsuitable for social networks due to significant limitations.Specifically,most approaches depend mainly on user-user structural links while overlooking service-centric,semantic,and multi-attribute drivers of community formation,and they also lack flexible filtering mechanisms for large-scale,service-oriented settings.Our proposed approach,called community discovery-based service(CDBS),leverages user profiles and their interactions with consulted web services.The method introduces a novel similarity measure,global similarity interaction profile(GSIP),which goes beyond typical similarity measures by unifying user and service profiles for all attributes types into a coherent representation,thereby clarifying its novelty and contribution.It applies multiple filtering criteria related to user attributes,accessed services,and interaction patterns.Experimental comparisons against Louvain,Hierarchical Agglomerative Clustering,Label Propagation and Infomap show that CDBS reveals the higher performance as it achieves 0.74 modularity,0.13 conductance,0.77 coverage,and significantly fast response time of 9.8 s,even with 10,000 users and 400 services.Moreover,community discoverybased service consistently detects a larger number of communities with distinct topics of interest,underscoring its capacity to generate detailed and efficient structures in complex networks.These results confirm both the efficiency and effectiveness of the proposed method.Beyond controlled evaluation,communities discovery based service is applicable to targeted recommendations,group-oriented marketing,access control,and service personalization,where communities are shaped not only by user links but also by service engagement.展开更多
While biomaterials are endowed with sophisticated functions by the temporal dynamics and autonomy derived from non-equilibrium assemblies in biological systems,fabricating advanced materials counterparts with these fe...While biomaterials are endowed with sophisticated functions by the temporal dynamics and autonomy derived from non-equilibrium assemblies in biological systems,fabricating advanced materials counterparts with these features through kinetic control remains rare.Herein,we report a non-equilibrium hydrogel that exhibits autonomous time-dependent ultrabright fluorescence(quantum yield 0.90),achieved through the kinetically controlled incorporation of thermodynamic equilibrium host-vip complexes into a poly(2-hydroxyethyl methacrylate)(PHEMA)network.Transient complexes are programmed by coupling rapid assembly kinetics with the slow competitive binding of the polymer matrix.This kinetic mismatch converts a thermodynamic equilibrium supramolecular system into a non-equilibrium state,generating temporally dynamic fluorescence that cyclically shifts from yellow to green and self-reverts.The programmed temporal dynamics endow the hydrogel with high potential for information encryption applications.展开更多
Charge-transfer complexes(CTCs)have emerged as promising n-type organic thermoelectric(TE)materials due to their inherent high electrical conductivity and tunable transport polarities.In this study,we performed a comp...Charge-transfer complexes(CTCs)have emerged as promising n-type organic thermoelectric(TE)materials due to their inherent high electrical conductivity and tunable transport polarities.In this study,we performed a comprehensive first-principles investigation on the TE properties of nine CTCs comprised of 2,7-dialkyl[1]benzothieno[3,2-b][1]benzothiophenes(CnBTBT,n=4,8,12)as donors and fluorinated derivatives of tetracyanoquinodimethane(F_(m)TCNQ,m=0,2,4)as acceptors,aiming to identify high-performance n-type organic TE materials and elucidate the underlying structure-property relationships.Our calculation results,based on the Boltzmann transport equation and deformation potential theory,reveal that the length of the alkyl side chains and the number of fluorine substitutions significantly impact their electronic structures and TE properties.Notably,the CnBTBT-F_(m)TCNQ CTCs with shorter alkyl chains and more fluorine substitution demonstrate superior n-type characteristics,particularly C4BTBT-F4TCNQ,which achieves an excellent power factor of 671µW cm^(-1) K^(-2) at an optimal charge carrier concentration.Our findings not only clarify the critical role of molecular engineering in CTC-based TE materials but also provide valuable guidance for developing high-efficiency organic TE materials with versatile practical applications.展开更多
文摘Most previous land-surface model calibration studies have defined globalranges for their parameters to search for optimal parameter sets. Little work has been conducted tostudy the impacts of realistic versus global ranges as well as model complexities on the calibrationand uncertainty estimates. The primary purpose of this paper is to investigate these impacts byemploying Bayesian Stochastic Inversion (BSI) to the Chameleon Surface Model (CHASM). The CHASM wasdesigned to explore the general aspects of land-surface energy balance representation within acommon modeling framework that can be run from a simple energy balance formulation to a complexmosaic type structure. The BSI is an uncertainty estimation technique based on Bayes theorem,importance sampling, and very fast simulated annealing. The model forcing data and surface flux datawere collected at seven sites representing a wide range of climate and vegetation conditions. Foreach site, four experiments were performed with simple and complex CHASM formulations as well asrealistic and global parameter ranges. Twenty eight experiments were conducted and 50 000 parametersets were used for each run. The results show that the use of global and realistic ranges givessimilar simulations for both modes for most sites, but the global ranges tend to produce someunreasonable optimal parameter values. Comparison of simple and complex modes shows that the simplemode has more parameters with unreasonable optimal values. Use of parameter ranges and modelcomplexities have significant impacts on frequency distribution of parameters, marginal posteriorprobability density functions, and estimates of uncertainty of simulated sensible and latent heatfluxes. Comparison between model complexity and parameter ranges shows that the former has moresignificant impacts on parameter and uncertainty estimations.
基金Under the auspices of National Natural Science Foundation of China (No. 40925003, 40930528, 40801041)
文摘Severe water erosion is notorious for its harmful effects on land-water resources as well as local societies. The scale effects of water erosion, however, greatly exacerbate the difficulties of accurate erosion evaluation and hazard control in the real world. Analyzing the related scale issues is thus urgent for a better understanding of erosion variations as well as reducing such erosion. In this review article, water erosion dynamics across three spatial scales including plot, watershed, and regional scales were selected and discussed. For the study purposes and objectives, the advantages and disadvantages of these scales all demonstrate clear spatial-scale dependence. Plot scale studies are primarily focused on abundant data collection and mechanism discrimination of erosion generation, while watershed scale studies provide valuable information for watershed management and hazard control as well as the development of quantitatively distributed models. Regional studies concentrate more on large-scale erosion assessment, and serve policymakers and stakeholders in achieving the basis for regulatory policy for comprehensive land uses. The results of this study show that the driving forces and mechanisms of water erosion variations among the scales are quite different. As a result, several major aspects contributing to variations in water erosion across the scales are stressed: differences in the methodologies across various scales, different sink-source roles on water erosion processes, and diverse climatic zones and morphological regions. This variability becomes more complex in the context of accelerated global change. The changing climatic factors and earth surface features are considered the fourth key reason responsible for the increased variability of water erosion across spatial scales.
文摘Three copper(Ⅱ),nickel and cadmium(Ⅱ)complexes,namely[Cu_(2)(μ-H2dbda)2(phen)2]·2H_(2)O(1),[Ni(μ-H2dbda)(μ-bpb)(H_(2)O)2]n(2),and[Cd(μ-H2dbda)(μ-bpa)]n(3),have been constructed hydrothermally using H4dbda(4,4'-dihydroxy-[1,1'-biphenyl]-3,3'-dicarboxylic acid),phen(1,10-phenanthroline),bpb(1,4-bis(pyrid-4-yl)benzene),bpa(bis(4-pyridyl)amine),and copper,nickel and cadmium chlorides at 160℃.The products were isolated as stable crystalline solids and were characterized by IR spectra,elemental analyses,thermogravimetric analyses,and singlecrystal X-ray diffraction analyses.Single-crystal X-ray diffraction analyses revealed that three complexes crystallize in the monoclinic P21/n,tetragonal I42d,and orthorhombic P21212 space groups.The complexes exhibit molecular dimers(1)or 2D metal-organic networks(2 and 3).The catalytic performances in the Knoevenagel reaction of these complexes were investigated.Complex 1 exhibits an effective catalytic activity and excellent reusability as a heterogeneous catalyst in the Knoevenagel reaction at room temperature.CCDC:2463800,1;2463801,2;2463802,3.
文摘Three zinc(Ⅱ),nickel(Ⅱ),and cadmium(Ⅱ)complexes,namely[Zn(μ-Htpta)(py)_(2)]n(1),[Ni(H_(2)biim)2(H_(2)O)2][Ni(tpta)(H_(2)biim)2(H_(2)O)]2·3H_(2)O(2),and[Cd_(3)(μ4-tpta)2(μ-dpe)_(3)]_(n)(3),have been constructed hydrothermally at 160℃ using H_(3)tpta([1,1':3',1″-terphenyl]-4,4',5'-tricarboxylic acid),py(pyridine),H_(2)biim(2,2'-biimidazole),dpe(1,2-di(4-pyridyl)ethylene),and zinc,nickel and cadmium chlorides,resulting in the formation of stable crystalline solids which were subsequently analyzed using infrared spectroscopy,element analysis,thermogravimetric analysis,as well as structural analyses conducted via single-crystal X-ray diffraction.The findings from these single-crystal Xray diffraction studies indicate that complexes 1-3 form crystals within the monoclinic system P2_(1)/c space group(1)or triclinic system P1 space group(2 and 3),and possess 1D,0D,and 3D structures,respectively.Complex 1 demonstrated substantial catalytic efficiency and excellent reusability as a heterogeneous catalyst in the reaction of Knoevenagel condensation under ambient temperature conditions.In addition,complex 1 also showcased notable anti-wear performance when used in polyalphaolefin synthetic lubricants.CCDC:2449810,1;2449811,2;2449812,3.
文摘Six new lanthanide complexes:[Ln(3,4-DEOBA)3(4,4'-DM-2,2'-bipy)]2·2C_(2)H_(5)OH,[Ln=Dy(1),Eu(2),Tb(3),Sm(4),Ho(5),Gd(6);3,4-DEOBA-=3,4-diethoxybenzoate,4,4'-DM-2,2'-bipy=4,4'-dimethyl-2,2'-bipyridine]were successfully synthesized by the volatilization of the solution at room temperature.The crystal structures of six complexes were determined by single-crystal X-ray diffraction technology.The results showed that the complexes all have a binuclear structure,and the structures contain free ethanol molecules.Moreover,the coordination number of the central metal of each structural unit is eight.Adjacent structural units interact with each other through hydrogen bonds and further expand to form 1D chain-like and 2D planar structures.After conducting a systematic study on the luminescence properties of complexes 1-4,their emission and excitation spectra were obtained.Experimental results indicated that the fluorescence lifetimes of complexes 2 and 3 were 0.807 and 0.845 ms,respectively.The emission spectral data of complexes 1-4 were imported into the CIE chromaticity coordinate system,and their corre sponding luminescent regions cover the yellow light,red light,green light,and orange-red light bands,respectively.Within the temperature range of 299.15-1300 K,the thermal decomposition processes of the six complexes were comprehensively analyzed by using TG-DSC/FTIR/MS technology.The hypothesis of the gradual loss of ligand groups during the decomposition process was verified by detecting the escaped gas,3D infrared spectroscopy,and ion fragment information detected by mass spectrometry.The specific decomposition path is as follows:firstly,free ethanol molecules and neutral ligands are removed,and finally,acidic ligands are released;the final product is the corresponding metal oxide.CCDC:2430420,1;2430422,2;2430419,3;2430424,4;2430421,5;2430423,6.
文摘This paper reports the preparation of three di‑iron complexes containing a thiazole moiety.Esterification of complex[Fe_(2)(CO)_(6)(μ‑SCH_(2)CH(CH_(2)OH)S)](1)with 4‑methylthiazole‑5‑carboxylic acid gave the corresponding ester[Fe_(2)(CO)_(6)(μ‑tedt)](2),where tedt=SCH_(2)CH(CH_(2)OOC(5‑C_(3)HNSCH_(3)))S.Further reactions of complex 2 with tri(ptolyl)phosphine(tp)or tris(4‑fluorophenyl)phosphine(fp)gave the phosphine‑substituted derivatives[Fe_(2)(CO)_(5)(tp)(μ‑tedt)](3)and[Fe_(2)(CO)_(5)(fp)(μ‑tedt)](4).The structures of the newly prepared complexes were elucidated by elemental analysis,NMR,IR,and X‑ray photoelectron spectroscopy.Moreover,single‑crystal X‑ray diffraction analysis confirmed their molecular structures,showing that they contain a di‑iron core ligated by a bridged dithiolate bearing a thiazole moiety and terminal carbonyls.The electrochemical and electrocatalytic proton reduction were probed by cyclic voltammetry,revealing that three complexes can catalyze the reduction of protons to H_(2) under the electrochemical conditions.For comparison,complex 4 possessed the best efficiency with a turnover frequency of 23.5 s^(-1)at 10 mmol·L^(-1)HOAc concentration.In addition,the fungicidal activity of these complexes was also investigated in this study.CCDC:2477511,2;2477512,3;2477513,4.
文摘The complexes 1-4 of cyclobutanocucurbit[5]uril(CyB5Q[5])with Na^(+)/K^(+)have been synthesized and characterized by single-crystal X-ray diffraction.The results show that although the inorganic salts are used when the cations are the same and the anions are different,in complex 1,Na^(+)closes one port of CyB5Q[5]through Na—O seven coordination bonds to form a molecular bowl;in complex 3,Na^(+)completely closes the two ports of CyB5Q[5]to form a molecular capsule with six Na—O coordination bonds;in complexes 2 and 4,the two ports of CyB5Q[5]are completely closed to form K—O coordinated molecular capsules,but the K^(+)of complex 2 is six-coordinated and that of complex 4 is eight-/nine-coordinated.and complex 4 are connected by three oxygen bridges to form a 1D molecular chain.CCDC:2457122,1;2457121,2;2457400,3;2457120,4.
文摘A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.
基金funded by the projects of Tianjin North China Geological Exploration Bureau (HK2023–B01,HK2022–B08)China Geological Survey (DD20230576,DD20201152)。
文摘1.Objective Nigeria lies between the West African Craton and the Congo Craton,south of the Tuareg Shield(Ogunmola JK et al.,2015).The Nasarawa pegmatite field mainly comprises of the Precambrian Basement Complex(including Archean-Proterozoic migmatite,gneiss,schists and Pan-African “Older Granites”),Mesozoic alkaline ring complexes(“Younger Granites”) and sedimentary basins(Yang QD et al.,2023;Fig.1a).“Older Granites” are part of the Pan-African mobile belt;“Younger Granites” has significant peralkaline characteristics.“Younger Granites” has a wide distribution in the north-central region of Nigeria,including areas such as Kano,Jos-Bauchi,Mada,and Nasarawa,and the emplacement age gradually decreases from north to south from 213 Ma(Dutse complex) to 141 Ma(Afu complex)(Amuda AK et al.,2021).
基金Supported by the National Natural Science Foundation of China(No.82171073).
文摘Dear Editor,We present a case of acute zonal occult outer retinopathy(AZOOR)complex in a myopic patient with angioid streaks(ASs).A 19-year-old female has been experiencing visual field defects in her left eye for more than 3y.She was diagnosed with ASs and choroiditis at a local hospital.She has a seven-year history of bilateral high myopia.A fundus examination confirmed the presence of ASs and myopic fundus changes in both eyes.Multimodal imaging revealed an AZOOR complex in the left eye.
基金supported by the Shenzhen Medical Research Fund(Grant No.A2303049)Guangdong Basic and Applied Basic Research(Grant No.2023A1515010647)+1 种基金National Natural Science Foundation of China(Grant No.22004135)Shenzhen Science and Technology Program(Grant No.RCBS20210706092409020,GXWD20201231165807008,20200824162253002).
文摘Multi-organ-on-a-chip(MOOC)technology represents a pivotal direction in the organ-on-a-chip field,seeking to emulate the complex interactions of multiple human organs in vitro through microfluidic systems.This technology overcomes the limitations of traditional single-organ models,providing a novel platform for investigating complex disease mechanisms and evaluating drug efficacy and toxicity.Although it demonstrates broad application prospects,its development still faces critical bottlenecks,including inadequate physiological coupling between organs,short functional maintenance durations,and limited real-time monitoring capabilities.Contemporary research is advancing along three key directions,including functional coupling,sensor integration,and full-process automation systems,to propel the technology toward enhanced levels of physiological relevance and predictive accuracy.
文摘There have been active work to extend the Prolog style Horn Clause logic programming to non-Horn clauses.In this paper,we will analyze the complexities of several such extensions.The purpose is to understand the computational complexity of these inference systems.The analyses do not prove that any one system is better than the others all the time.But they do suggest that one system may be better than the others for some particular problems.We also discuss the effect of caching.
基金supported by the National Natural Science Foundation of China(22401151)the Basic Research Program of Jiangsu Province(BK20220408)+1 种基金the Innovation and Entrepreneurship Team of Jiangsu Province(JSSCTD202345)the Specially Appointed Professor Plan of Jiangsu Province。
文摘Herein,we report a novel,visible-light-induced approach for the selective construction of both gem-difluoroalkenes and trifluoromethyl alkanes from α-trifluoromethyl olefins using alcohol-derived N-alkoxyphthalimides as alkyl radical precursors.This strategy leverages Eosin Y as a photocatalyst in a defluorinative alkylation reaction and a catalyst-free electron donor-acceptor(EDA)complex-mediated hydroalkylation process.By modulating the reaction conditions,the desired products were selectively obtained with excellent chemo-selectivity and in high yields.The protocol accommodates a wide variety of substrates,including primary,secondary,and tertiary alcohols,as well as diverse α-trifluoromethyl styrenes,and is applicable to late-stage functionalization of natural products and bioactive molecules.
基金supported by the National Natural Science Foundation of China (Nos.81872823,82073782,and 82241002)the Key R&D Plan of Ganjiang New District of Jiangxi (No.2023010)。
文摘Cisplatin(CDDP)-based chemotherapy is an effective strategy for the treatment of advanced nasopharyngeal carcinoma(NPC).However,serious toxic side effects of CDDP limit patient tolerance and treatment compliance,which urgently needs to be addressed in clinical application.Liposomes have been considered ideal vehicles for reducing CDDP toxicity due to their high biocompatibility,low toxicity and passive targeting ability.Nevertheless,CDDP's poor water/lipid solubility usually results in a low liposome druglipid ratio,limiting tumor delivery ability.Herein,a CDDP-polyphenol complex liposome was designed to increase the drug loading capacity of CDDP to realize the reduction of toxicity and effective antitumor effect simultaneously.The complex was prepared via complexation reaction of different stoichiometric ratios of CDDP and polyphenolic substances(gallic acid,epigallocatechin gallate and tannic acid),followed by encapsulation of complex in liposomes to improve tumor targeting.Notably,the molecular interaction forces between CDDP and polyphenolic substances were intensively investigated through a binding force disruption assay.In vitro studies demonstrated that the optimal formulation of CDDP-epigallocatechin gallate complex liposome(CDDP-EGCG Lips) showed the highest CDDP encapsulation efficiency,favorable stability,pH-sensitive release,enhanced cellular uptake and apoptosis effect.In vivo studies revealed that CDDP-EGCG Lips retarded the elimination of CDDP to prolong their circulation time,inhibited the growth of tumors,and significantly reduced the toxic side effects compared to CDDP monotherapy.This delivery strategy holds great promise for improving the clinical use of platinum-based drugs.
基金supported by the Department of Science and Technology of Jilin Province(20220508112RC).The founders had no role in this study design,data collection,analysis,decision to publish,or preparation of the manuscript.
文摘Anthocyanin biosynthesis in plants is spatiotemporally controlled by a suite of transcription factors,with MYB proteins playing a key regulatory role.However,the evolution of the distinct roles of MYB paralogs remains poorly understood.Our previous studies have established GmMYBA2 and GmMYBA3 as the regulators of seed coat and floral anthocyanin production in soybean(Glycine max),respectively.In this study,we reveal the functional divergence of their paralog GmMYBA1 in orchestrating light-responsive anthocyanin biosynthesis in juvenile tissues and stems.In brief,hypocotyl/stem-and young leaf-predominant expression of GmMYBA1 correlates with photoprotective anthocyanin accumulation.Ectopic overexpression of GmMYBA1 induces systemic pigmentation across leaves,stems,and reproductive organs,whereas RNAi-mediated silencing of GmMYBA1 significantly reduces anthocyanin accumulation in the hypocotyl.Light-dark shift assays confirmed that GmMYBA1 is required for hypocotyl pigmentation,while dual-luciferase assays revealed the specific regulation of the GmMYBA paralogs by GmSTF1/2(soybean TGACG-motif binding factor 1/2).GmSTF1/2 both activate GmMYBA1,with only GmSTF2 weakly inducing GmMYBA2 and neither affecting GmMYBA3.Further investigation indicated that the differential transactivation of GmMYBA promoters largely resulted from their cis-element difference,suggesting regulatory divergence as a driver of MYB paralog diversification.Our findings position GmMYBA1 as the central MYB activator integrating light signaling with anthocyanin biosynthesis,with paralog specialization reflecting evolutionary subfunctionalization post-gene duplication.
基金supported by the National Key Research and Development Program of China(Grant No.2023YFB3710805).
文摘Ultra-high-strength aluminumalloy profile is an ideal choice for aerospace structuralmaterials due to its excellent specific strength and corrosion resistance.However,issues such as uneven metal flow,stress concentration,and forming defects are prone to occur during their extrusion.This study focuses on an Al-Zn-Mg-Cu ultra-high-strength aluminum alloy profile with a double-U,multi-cavity thin-walled structure.Firstly,hot compression experiments were conducted at temperatures of 350○C,400○C,and 450○C,with strain rates of 0.01 and 1.0 s^(−1),to investigate the plastic deformation behavior of the material.Subsequently,a 3D coupled thermo-mechanical extrusion simulation model was established using Deform-3D to systematically analyze the influence of die structure and process parameters on metal flow velocity,effective stress/strain,and temperature distribution.The simulation revealed significant velocity differences,stress concentration,and uneven temperature distribution.Key parameters,including mesh density,extrusion ratio,die fillet,and bearing length,were optimized through full-factorial experiments.This optimization,combined with a stepped flow-guiding die design,effectively improved the metal flow pattern during extrusion.Trial production based on both the initial and optimized parameters were carried out.A comparative analysis demonstrates that the optimized scheme results in a final profile whose cross-section matches the target design closely,with complete filling of complex features and no obvious forming defects.This research provides a valuable reference for the extrusion process optimization and die design of complex-section profiles made from ultra-high-strength aluminum alloys.
文摘In modern industrial production,foreign object detection in complex environments is crucial to ensure product quality and production safety.Detection systems based on deep-learning image processing algorithms often face challenges with handling high-resolution images and achieving accurate detection against complex backgrounds.To address these issues,this study employs the PatchCore unsupervised anomaly detection algorithm combined with data augmentation techniques to enhance the system’s generalization capability across varying lighting conditions,viewing angles,and object scales.The proposed method is evaluated in a complex industrial detection scenario involving the bogie of an electric multiple unit(EMU).A dataset consisting of complex backgrounds,diverse lighting conditions,and multiple viewing angles is constructed to validate the performance of the detection system in real industrial environments.Experimental results show that the proposed model achieves an average area under the receiver operating characteristic curve(AUROC)of 0.92 and an average F1 score of 0.85.Combined with data augmentation,the proposed model exhibits improvements in AUROC by 0.06 and F1 score by 0.03,demonstrating enhanced accuracy and robustness for foreign object detection in complex industrial settings.In addition,the effects of key factors on detection performance are systematically analyzed,providing practical guidance for parameter selection in real industrial applications.
文摘Identifying the community structure of complex networks is crucial to extracting insights and understanding network properties.Although several community detection methods have been proposed,many are unsuitable for social networks due to significant limitations.Specifically,most approaches depend mainly on user-user structural links while overlooking service-centric,semantic,and multi-attribute drivers of community formation,and they also lack flexible filtering mechanisms for large-scale,service-oriented settings.Our proposed approach,called community discovery-based service(CDBS),leverages user profiles and their interactions with consulted web services.The method introduces a novel similarity measure,global similarity interaction profile(GSIP),which goes beyond typical similarity measures by unifying user and service profiles for all attributes types into a coherent representation,thereby clarifying its novelty and contribution.It applies multiple filtering criteria related to user attributes,accessed services,and interaction patterns.Experimental comparisons against Louvain,Hierarchical Agglomerative Clustering,Label Propagation and Infomap show that CDBS reveals the higher performance as it achieves 0.74 modularity,0.13 conductance,0.77 coverage,and significantly fast response time of 9.8 s,even with 10,000 users and 400 services.Moreover,community discoverybased service consistently detects a larger number of communities with distinct topics of interest,underscoring its capacity to generate detailed and efficient structures in complex networks.These results confirm both the efficiency and effectiveness of the proposed method.Beyond controlled evaluation,communities discovery based service is applicable to targeted recommendations,group-oriented marketing,access control,and service personalization,where communities are shaped not only by user links but also by service engagement.
基金supported by the National Natural Science Foundation of China(22025503,22220102004,22401093)the Science and Technology Commission of Shanghai Municipality(24DX1400200)+2 种基金the Innovation Program of Shanghai Municipal Education Commission(2023ZKZD40)the Programme of Introducing Talents of Discipline to Universities(B16017)the China Postdoctoral Science Foundation(2023M741167,GZB20230211,2024T170273)。
文摘While biomaterials are endowed with sophisticated functions by the temporal dynamics and autonomy derived from non-equilibrium assemblies in biological systems,fabricating advanced materials counterparts with these features through kinetic control remains rare.Herein,we report a non-equilibrium hydrogel that exhibits autonomous time-dependent ultrabright fluorescence(quantum yield 0.90),achieved through the kinetically controlled incorporation of thermodynamic equilibrium host-vip complexes into a poly(2-hydroxyethyl methacrylate)(PHEMA)network.Transient complexes are programmed by coupling rapid assembly kinetics with the slow competitive binding of the polymer matrix.This kinetic mismatch converts a thermodynamic equilibrium supramolecular system into a non-equilibrium state,generating temporally dynamic fluorescence that cyclically shifts from yellow to green and self-reverts.The programmed temporal dynamics endow the hydrogel with high potential for information encryption applications.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Science(No.XDB0520000)the National Natural Science Foundation of China(Nos.52273170 and 52394271)the National Key R&D Program of China(No.2022YFA1203200).
文摘Charge-transfer complexes(CTCs)have emerged as promising n-type organic thermoelectric(TE)materials due to their inherent high electrical conductivity and tunable transport polarities.In this study,we performed a comprehensive first-principles investigation on the TE properties of nine CTCs comprised of 2,7-dialkyl[1]benzothieno[3,2-b][1]benzothiophenes(CnBTBT,n=4,8,12)as donors and fluorinated derivatives of tetracyanoquinodimethane(F_(m)TCNQ,m=0,2,4)as acceptors,aiming to identify high-performance n-type organic TE materials and elucidate the underlying structure-property relationships.Our calculation results,based on the Boltzmann transport equation and deformation potential theory,reveal that the length of the alkyl side chains and the number of fluorine substitutions significantly impact their electronic structures and TE properties.Notably,the CnBTBT-F_(m)TCNQ CTCs with shorter alkyl chains and more fluorine substitution demonstrate superior n-type characteristics,particularly C4BTBT-F4TCNQ,which achieves an excellent power factor of 671µW cm^(-1) K^(-2) at an optimal charge carrier concentration.Our findings not only clarify the critical role of molecular engineering in CTC-based TE materials but also provide valuable guidance for developing high-efficiency organic TE materials with versatile practical applications.
