The four-decade quest for synthesizing ambient-stable polymeric nitrogen,a promising high-energy-density material,remains an unsolved challenge in materials science.We develop a multi-stage computational strategy empl...The four-decade quest for synthesizing ambient-stable polymeric nitrogen,a promising high-energy-density material,remains an unsolved challenge in materials science.We develop a multi-stage computational strategy employing density functional tight-binding-based rapid screening combined with density functional theory refinement and global structure searching,effectively bridging computational efficiency with quantum accuracy.This integrated approach identifies four novel polymeric nitrogen phases(Fddd,P3221,I4m2,and𝑃P6522)that are thermodynamically stable at ambient pressure.Remarkably,the helical𝑃6522 configuration demonstrates exceptional thermal resilience up to 1500 K,representing a predicted polymeric nitrogen structure that maintains stability under both atmospheric pressure and high-temperature extremes.Our methodology establishes a paradigm-shifting framework for the accelerated discovery of metastable energetic materials,resolving critical bottlenecks in theoretical predictions while providing experimentally actionable targets for polymeric nitrogen synthesis.展开更多
The application of machine learning for pyrite discrimination establishes a robust foundation for constructing the ore-forming history of multi-stage deposits;however,published models face challenges related to limite...The application of machine learning for pyrite discrimination establishes a robust foundation for constructing the ore-forming history of multi-stage deposits;however,published models face challenges related to limited,imbalanced datasets and oversampling.In this study,the dataset was expanded to approximately 500 samples for each type,including 508 sedimentary,573 orogenic gold,548 sedimentary exhalative(SEDEX)deposits,and 364 volcanogenic massive sulfides(VMS)pyrites,utilizing random forest(RF)and support vector machine(SVM)methodologies to enhance the reliability of the classifier models.The RF classifier achieved an overall accuracy of 99.8%,and the SVM classifier attained an overall accuracy of 100%.The model was evaluated by a five-fold cross-validation approach with 93.8%accuracy for the RF and 94.9%for the SVM classifier.These results demonstrate the strong feasibility of pyrite classification,supported by a relatively large,balanced dataset and high accuracy rates.The classifier was employed to reveal the genesis of the controversial Keketale Pb-Zn deposit in NW China,which has been inconclusive among SEDEX,VMS,or a SEDEX-VMS transition.Petrographic investigations indicated that the deposit comprises early fine-grained layered pyrite(Py1)and late recrystallized pyrite(Py2).The majority voting classified Py1 as the VMS type,with an accuracy of RF and SVM being 72.2%and 75%,respectively,and confirmed Py2 as an orogenic type with 74.3% and 77.1%accuracy,respectively.The new findings indicated that the Keketale deposit originated from a submarine VMS mineralization system,followed by late orogenic-type overprinting of metamorphism and deformation,which is consistent with the geological and geochemical observations.This study further emphasizes the advantages of Machine learning(ML)methods in accurately and directly discriminating the deposit types and reconstructing the formation history of multi-stage deposits.展开更多
To achieve the target of carbon neutrality,it is crucial to develop an efficient and green synthesis methodology with good atomic economy to achieve sufficient utilization of energy and sustainable development.Photoin...To achieve the target of carbon neutrality,it is crucial to develop an efficient and green synthesis methodology with good atomic economy to achieve sufficient utilization of energy and sustainable development.Photoinduced electron transfer reversible addition-fragmentation chain-transfer(PET-RAFT)polymerization is a precise methodology for constructing polymers with well-defined structures.However,conventional semiconductor-mediated PET-RAFT polymerization still has considerable limitations in terms of efficiency as well as the polymerization environment.Herein,sulfur-doped carbonized polymer dots(CPDs)were hydrothermally synthesized for catalysis of aqueous PET-RAFT polymerization at unprecedented efficiency with a highest propagation rate of 5.05 h-1.The resulting polymers have well-controlled molecular weight and narrow molecular weight dispersion(Ð<1.10).Based on the optoelectronic characterizations,we obtained insights into the photoinduced electron transfer process and proposed the mechanism for CPD-mediated PET-RAFT polymerization.In addition,as-synthesized CPDs for PET-RAFT polymerization were also demonstrated to be suitable for a wide range of light sources(blue/green/solar irradiation),numerous monomers,low catalyst loading(low as 0.01 mg mL^(-1)),and multiple polar solvent environments,all of which allowed to achieve efficiencies much higher than those of existing semiconductor-mediated methods.Finally,the CPDs were confirmed to be non-cytotoxic and catalyzed PET-RAFT polymerization successfully in cell culture media,indicating broad prospects in biomedical fields.展开更多
The high proportion of uncertain distributed power sources and the access to large-scale random electric vehicle(EV)charging resources further aggravate the voltage fluctuation of the distribution network,and the exis...The high proportion of uncertain distributed power sources and the access to large-scale random electric vehicle(EV)charging resources further aggravate the voltage fluctuation of the distribution network,and the existing research has not deeply explored the EV active-reactive synergistic regulating characteristics,and failed to realize themulti-timescale synergistic control with other regulatingmeans,For this reason,this paper proposes amultilevel linkage coordinated optimization strategy to reduce the voltage deviation of the distribution network.Firstly,a capacitor bank reactive power compensation voltage control model and a distributed photovoltaic(PV)activereactive power regulationmodel are established.Additionally,an external characteristicmodel of EVactive-reactive power regulation is developed considering the four-quadrant operational characteristics of the EVcharger.Amultiobjective optimization model of the distribution network is then constructed considering the time-series coupling constraints of multiple types of voltage regulators.A multi-timescale control strategy is proposed by considering the impact of voltage regulators on active-reactive EV energy consumption and PV energy consumption.Then,a four-stage voltage control optimization strategy is proposed for various types of voltage regulators with multiple time scales.Themulti-objective optimization is solved with the improvedDrosophila algorithmto realize the power fluctuation control of the distribution network and themulti-stage voltage control optimization.Simulation results validate that the proposed voltage control optimization strategy achieves the coordinated control of decentralized voltage control resources in the distribution network.It effectively reduces the voltage deviation of the distribution network while ensuring the energy demand of EV users and enhancing the stability and economic efficiency of the distribution network.展开更多
Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to p...Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to prevent degradation and side reactions.In the contribution,histidine N-thiocarboxyanhydride(His-NTA)is directly synthesized in aqueous solution without protection.With the self-catalysis of the imidazole side group,the ring-closing reaction to form His-NTA does not require any activating reagent(e.g.,phosphorus tribromide),which is elucidated by density functional theory(DFT)calculations.His-NTA directly polymerizes into PHis bearing unprotected imidazole groups with designable molecular weights(4.2-7.7 kg/mol)and low dispersities(1.10-1.19).Kinetic experiments and Monte Carlo simulations reveal the elementary reactions and the relationship between the conversion of His-NTA and time during polymerization.Block copolymerization of His-NTA with sarcosine N-thiocarboxyanhydride(Sar-NTA)demonstrate versatile construction of functional polypept(o)ides.The triblock copoly(amino acid)PHis-b-PSar-b-PHis is capable to reversibly coordinate with transition metal ions(Fe^(2+),Co^(2+),Ni^(2+),Cu^(2+)and Zn^(2+))to form pH-sensitive hydrogels.展开更多
Incorporation of acetal groups in the backbone is a potent strategy to create polymers that are cleavable or degradable under acidic conditions.We report here an in-depth study on the ring-closing-opening copolymeriza...Incorporation of acetal groups in the backbone is a potent strategy to create polymers that are cleavable or degradable under acidic conditions.We report here an in-depth study on the ring-closing-opening copolymerization of o-phthalaldehyde(OPA)and epoxide using Lewis pair type two-component organocatalysts for producing acetal-functionalized polyether and polyurethane.Notably,triethylborane as the Lewis acid,in comparison with tri(n-butyl)borane,more effectively enhances the polymerization activity by mitigating borane-induced reduction of the aldehyde group into extra initiating(borinic ester)species.Density functional theory(DFT)calculations present comparable energy barriers of OPA-epoxide cross-propagation and epoxide self-propagation,which is consistent with the experimental finding that an alternating-rich copolymer comprising mostly OPA-epoxide units but also epoxide-epoxide linkages is produced.In particular,when epoxide is added in a large excess,the product becomes a polyether containing acetal functionalities in the central part of the backbone and thus being convertible into polyurethane with refined acid degradability.展开更多
As a powerful synthetic tool,ruthenium-catalyzed ring-opening metathesis polymerization(ROMP)has been widely utilized to prepare diverse heteroatom-containing polymers.In this contribution,we report the synthesis of t...As a powerful synthetic tool,ruthenium-catalyzed ring-opening metathesis polymerization(ROMP)has been widely utilized to prepare diverse heteroatom-containing polymers.In this contribution,we report the synthesis of the novel imine-based polymer through the copolymerization of cyclooctene with cyclic imine comonomer via ROMP.Because of the efficient hydrolysis reactions of the imine group,the generated copolymer can be easily degraded under mild condition.Moreover,the generated degradable product was the telechelic polymer bearing amine group,which was highly challenged for its direct synthesis.And this telechelic polymer could also be used for the further synthesis of new polymer through post-transformation.The introduction of imine unit in this work provides a new example of the degradable polymer synthesis.展开更多
Core-shell colloidal particles with a polymer layer have broad applications in different areas.Herein,we developed a two-step method combining aqueous surface-initiated photoinduced polymerization-induced self-assembl...Core-shell colloidal particles with a polymer layer have broad applications in different areas.Herein,we developed a two-step method combining aqueous surface-initiated photoinduced polymerization-induced self-assembly and photoinduced seeded reversible addition-fragmentation chain transfer(RAFT)polymerization to prepare a diverse set of core-shell colloidal particles with a well-defined polymer layer.Chemical compositions,structures,and thicknesses of polymer layers could be conveniently regulated by using different types of monomers and feed[monomer]/[chain transfer agent]ratios during seeded RAFT polymerization.展开更多
Although solid-state polymer electrolytes(SPEs)are expected to solve the safety hazards and limited energy density in the energy storage systems,they still encounter an inferior electrode/electrolyte interface when pr...Although solid-state polymer electrolytes(SPEs)are expected to solve the safety hazards and limited energy density in the energy storage systems,they still encounter an inferior electrode/electrolyte interface when prepared in an ex situ manner.Recently,in situ polymerization of SPEs favor high interfacial infiltrability,improved interface contact,and reduced interface resistance,owing to the formation of a"superconformal"interface between electrode and electrolyte.Especially,in situ strategies employing ring-opening polymerization(ROP)are emerging as dazzling stars,further enabling moderate polymerization conditions,controllable molecular structure,and reduced interfacial side reaction.As the main monomers that can be in situ polymerized via the ROP strategy,cyclic ethers have been used to construct the CE-SPEs with many merits,including good battery electrochemical performances and a simple assembly process.Here,as a systematic summarization of the existing reports,this review focuses on the polymerization mechanism of ROP,the design principles of CE-SPEs electrolytes,and the recent application of in situ CE-SPEs.In particular,this review thoroughly discusses the selection of different cyclic monomers,initiators and various modification approaches in in situ fabricating CE-SPEs.Ending with offering future challenges and perspectives,this review envisions shedding light on the profound understanding and scientific guidance for further development of high-performance in situ CE-SPEs.展开更多
Copolymers of fluoroethylene and vinyl ethers(FEVE)are soluble and curable at relatively low temperature,and are used as high-performance coatings and paints.Currently,most market-available FEVE products obtained thro...Copolymers of fluoroethylene and vinyl ethers(FEVE)are soluble and curable at relatively low temperature,and are used as high-performance coatings and paints.Currently,most market-available FEVE products obtained through solution polymerization contain a large fraction of organic solvent,and hence,volatile organic compound(VOC)emissions cause environmental issues.In this study,the emulsion copolymerization of chlorotrifluoroethylene(CTFE)and vinyl ethers using an environmentally friendly emulsification system to produce waterborne FEVE was investigated.In addition to mixed nonionic and ionic surfactants,macromolecular monomer with double bond and polyoxyethylene segments were used in the emulsification system.The effect of adding macromolecular monomer and polyoxyethylene segment length of the nonionic surfactant on emulsion copolymerization were analyzed.An optimized emulsifier system for FEVE is proposed,and the prepared FEVE latexes exhibit excellent storage stability and film formation ability.展开更多
Functional hyperbranched polymers,as an important class of materials,are widely applied in diverse areas.Therefore,the development of simple and efficient reactions to prepare hyperbranched polymers is of great signif...Functional hyperbranched polymers,as an important class of materials,are widely applied in diverse areas.Therefore,the development of simple and efficient reactions to prepare hyperbranched polymers is of great significance.In this work,trialdehydes,diamines,and trimethylsilyl cyanide could easily undergo multicomponent polymerization under mild conditions,producing hyperbranched poly(α-aminonitrile)s with high molecular weights(M_(w) up to 4.87×10^(4))in good yields(up to 85%).The hyperbranched poly(α-aminonitrile)s have good solubility in commonly used organic solvents,high thermal stability as well as morphological stability.Furthermore,due to the numerous aldehyde groups in their branched chains,these hb-poly(α-aminonitrile)s can undergo one-pot,two-step,four-component post-polymerization with high efficiency.This work not only confirms the efficiency of our established catalyst-free multicomponent polymerization of aldehydes,amines and trimethylsilyl cyanide,but also provides a versatile and powerful platform for the preparation of functional hyperbranched polymeric materials.展开更多
Solid polymer electrolytes(SPEs)have garnered considerable interest in the field of lithium metal batteries(LMBs)owing to their exceptional mechanical strength,excellent designability,and heightened safety characteris...Solid polymer electrolytes(SPEs)have garnered considerable interest in the field of lithium metal batteries(LMBs)owing to their exceptional mechanical strength,excellent designability,and heightened safety characteristics.However,their inherently low ion transport efficiency poses a major challenge for their application in LMBs.To address this issue,covalent organic framework(COF)with their ordered ion transport channels,chemical stability,large specific surface area,and designable multifunctional sites has shown promising potential to enhance lithium-ion conduction.Here,we prepared an anionic COF,Tp Pa-COOLi,which can catalyze the ring-opening copolymerization of cyclic lactone monomers for the in situ fabrication of SPEs.The design leverages the high specific surface area of COF to facilitate the absorption of polymerization precursor and catalyze the polymerization within the pores,forming additional COF-polymer junctions that enhance ion transport pathways.The partial exfoliation of COF achieved through these junctions improved its dispersion within the polymer matrix,preserving ion transport channels and facilitating ion transport across COF grain boundaries.By controlling variables to alter the crystallinity of Tp Pa-COOLi and the presence of-COOLi substituents,Tp Pa-COOLi with partial long-range order and-COOLi substituents exhibited superior electrochemical performance.This research demonstrates the potential in constructing high-performance SPEs for LMBs.展开更多
Although previous researchers have attempted to decipher ore genesis and mineralization in the Erdaokan Ag-Pb-Zn deposit,some uncertainties regarding the mineralization process and evolution of both ore-forming fluids...Although previous researchers have attempted to decipher ore genesis and mineralization in the Erdaokan Ag-Pb-Zn deposit,some uncertainties regarding the mineralization process and evolution of both ore-forming fluids and magnetite types still need to be addressed.In this study,we obtained new EPMA,LA-ICP-MS,and in situ Fe isotope data from magnetite from the Erdaokan deposit,in order to better understand the mineralization mechanism and evolution of both magnetite and the ore-forming fluids.Our results identified seven types of magnetite at Erdaokan:disseminated magnetite(Mag1),coarse-grained magnetite(Mag2a),radial magnetite(Mag2b),fragmented fine-grained magnetite(Mag2c),vermicular gel magnetite(Mag3a1 and Mag3a2),colloidal magnetite(Mag3b)and dark gray magnetite(Mag4).All of the magnetite types were hydrothermal in origin and generally low in Ti(<400 ppm)and Ni(<800 ppm),while being enriched in light Fe isotopes(δ^(56)Fe ranging from−1.54‰to−0.06‰).However,they exhibit different geochemical signatures and are thus classified into high-manganese magnetite(Mag1,MnO>5 wt%),low-silicon magnetite(Mag2a-c,SiO_(2)<1 wt%),high-silicon magnetite(Mag3a-b,SiO_(2)from 1 to 7 wt%)and high-silicon-manganese magnetite(Mag4,SiO_(2)>1 wt%,MnO>0.2 wt%),each being formed within distinct hydrothermal environments.Based on mineralogy,elemental geochemistry,Fe isotopes,temperature trends,TMg-mag and(Ti+V)vs.(Al+Mn)diagrams,we propose that the Erdaokan Ag-Pb-Zn deposit underwent multi-stage mineralization,which can be broken down into four stages and nine sub-stages.Mag1,Mag2a-c,Mag3a-b and Mag4 were formed during the first sub-stage of each of the four stages,respectively.Additionally,fluid mixing,cooling and depressurization boiling were identified as the main mechanisms for mineral precipitation.The enrichment of Ag was significantly enhanced by the superposition of multi-stage ore-forming hydrothermal fluids in the Erdaokan Ag-Pb-Zn deposit.展开更多
Chain-growth radical polymerization of vinyl monomers is essential for producing a wide range of materials with properties tailored to specific applications.However,the inherent resistance of the polymer's C―C ba...Chain-growth radical polymerization of vinyl monomers is essential for producing a wide range of materials with properties tailored to specific applications.However,the inherent resistance of the polymer's C―C backbone to degradation raises significant concerns regarding long-term environmental persistence,which also limits their potential in biomedical applications.To address these challenges,researchers have developed strategies to either degrade preexisting vinyl polymers or incorporate cleavable units into the backbone to modify them with enhanced degradability.This review explores the various approaches aimed at achieving backbone degradability in chain-growth radical polymerization of vinyl monomers,while also highlighting future research directions for the development of application-driven degradable vinyl polymers.展开更多
The preparation of polypeptide materials in continuous flow reactors shows great potential with improved reproducibility and scalability.However,conventional polypeptide synthesis from the polymerization of N-carboxya...The preparation of polypeptide materials in continuous flow reactors shows great potential with improved reproducibility and scalability.However,conventional polypeptide synthesis from the polymerization of N-carboxyanhydride(NCA)is conducted at relatively slow rates,requiring long tubing or ending up with low-molecular-weight polymers.Inspired by recent advances in accelerated NCA polymerization,we report the crown-ether-catalyzed,rapid synthesis of polypeptide materials in cosolvents in flow reactors.The incorporation of low-polarity dichloromethane and the use of catalysts enabled fast conversion of monomers in 30 min,yielding well-defined polypeptides(up to 30 k Da)through a 20-cm tubing reactor.Additionally,random or block copolypeptides were efficiently prepared by incorporating a second NCA monomer.We believe that this work highlights the accelerated polymerization design in flow polymerization processes,offering the continuous production of polypeptide materials.展开更多
Seismic data denoising is a critical process usually applied at various stages of the seismic processing workflow,as our ability to mitigate noise in seismic data affects the quality of our subsequent analyses.However...Seismic data denoising is a critical process usually applied at various stages of the seismic processing workflow,as our ability to mitigate noise in seismic data affects the quality of our subsequent analyses.However,finding an optimal balance between preserving seismic signals and effectively reducing seismic noise presents a substantial challenge.In this study,we introduce a multi-stage deep learning model,trained in a self-supervised manner,designed specifically to suppress seismic noise while minimizing signal leakage.This model operates as a patch-based approach,extracting overlapping patches from the noisy data and converting them into 1D vectors for input.It consists of two identical sub-networks,each configured differently.Inspired by the transformer architecture,each sub-network features an embedded block that comprises two fully connected layers,which are utilized for feature extraction from the input patches.After reshaping,a multi-head attention module enhances the model’s focus on significant features by assigning higher attention weights to them.The key difference between the two sub-networks lies in the number of neurons within their fully connected layers.The first sub-network serves as a strong denoiser with a small number of neurons,effectively attenuating seismic noise;in contrast,the second sub-network functions as a signal-add-back model,using a larger number of neurons to retrieve some of the signal that was not preserved in the output of the first sub-network.The proposed model produces two outputs,each corresponding to one of the sub-networks,and both sub-networks are optimized simultaneously using the noisy data as the label for both outputs.Evaluations conducted on both synthetic and field data demonstrate the model’s effectiveness in suppressing seismic noise with minimal signal leakage,outperforming some benchmark methods.展开更多
In recent years,cellulose-based fluorescent polymers have received considerable attention.However,conventional modification methods face challenges such as insolubility in most solvents,fluorescence instability,and en...In recent years,cellulose-based fluorescent polymers have received considerable attention.However,conventional modification methods face challenges such as insolubility in most solvents,fluorescence instability,and environmental risks.In this study,a novel biosynthesis strategy was developed to fabricate fluorescent cellulose by adding fluorescent glucose derivatives to a bacterial fermentation broth.The metabolic activity of bacteria is utilized to achieve in situ polymerization of glucose and its derivatives during the synthesis of bacterial cellulose.Owing to the structural similarity between triphenylamine-modified glucose(TPA-Glc N)and glucose monomers,the TPA-Glc N were efficiently assimilated by the bacterial cells and incorporated into the cellulose matrix,resulting in a uniform distribution of fluorescence.The fluorescence color and intensity of the obtained cellulose could be adjusted by varying the amount of the fluorescent glucose derivatives.Compared to the fluorescent cellulose synthesized through physical dyeing,the fluorescence of the products obtained by in situ polymerization showed higher intensity and stability.Furthermore,fluorescent bacterial cellulose can be hydrolyzed into nanocellulose-based ink,which demonstrates exceptional anti-counterfeiting capabilities under UV light.This biosynthesis method not only overcomes the limitations of traditional modification techniques but also highlights the potential of microbial systems as platforms for synthesizing functional polymers.展开更多
Exploration of new green polymerization strategies for the construction of conjugated polymers is important but challengeable.In this work,a multicomponent polymerization of acetylarenes,alkynones and ammonium acetate...Exploration of new green polymerization strategies for the construction of conjugated polymers is important but challengeable.In this work,a multicomponent polymerization of acetylarenes,alkynones and ammonium acetate for in situ construction of conjugated poly(triarylpyridine)s was developed.The polymerization reactions of diacetylarenes,aromatic dialkynones and NH_(4)OAc were performed in dimethylsulfoxide(DMSO)under heating in the presence of potassium tert-butoxide(t-BuOK),affording four conjugated poly(2,4,6-triarylpyridine)s(PTAPs)in satisfactory yields.The resulting PTAPs have good solubility in common organic solvents and high thermal stability with 5%weight loss temperatures reaching up to 460℃.They are also electrochemically active.The PTAPs incorporating tetraphenylethene units manifest aggregation-induced emission features.Moreover,through simply being doped into poly(vinyl alcohol)(PVA)matrix,the polymer and model compound containing triphenylamine moieties exhibit room-temperature phosphorescence properties with ultralong lifetimes up to 696.2 ms and high quantum yields up to 28.7%.This work not only provides a facile green synthetic route for conjugated polymers but also offers new insights into the design of advanced materials with unique photophysical properties.展开更多
Living cationic polymerization of 4-acetoxystyrene(STO)was conducted in CH_(2)Cl_(2) at-15℃ using a dicumyl chloride(DCC)/SnCl_(4)/nBu_(4)NBr initiating system.Impurity moisture initiation was inhibited by adding pro...Living cationic polymerization of 4-acetoxystyrene(STO)was conducted in CH_(2)Cl_(2) at-15℃ using a dicumyl chloride(DCC)/SnCl_(4)/nBu_(4)NBr initiating system.Impurity moisture initiation was inhibited by adding proton trap 2,6-di-tert-butylpyridine(DTBP),and the controlled initiation of DCC was confirmed by ^(1)H nuclear magnetic resonance(^(1)H-NMR)spectroscopy and matrix-assisted laser desorption ionization time-offlight mass(MALDI-TOF-MS)spectrometry.The polymerization kinetics were analyzed to for optimizing the polymerization rate.Allyl-telechelic PSTOs(allyl-PSTO-allyl)with molecular weight(Mn)range of 3540–7800 g/mol and narrow molecular weight dispersity(Mw/Mn)about 1.25 were prepared through nucleophilic substitution with allyltrimethylsilane(ATMS)at approximately 40%monomer conversion.The experimental results indicate that the substitution efficiency of ATMS increased with higher ATMS concentration,temperature,and extended reaction time.Nearly unity ally-functionality for allyl-PSTO-allyl was achieved by adding sufficient SnCl_(4) prior to the substitution.展开更多
This paper presents a new criterion for determining the unloading points quantitatively and consistently in a multi-stage triaxial test.The radial strain gradient(RSG)is first introduced as an arc tangent function of ...This paper presents a new criterion for determining the unloading points quantitatively and consistently in a multi-stage triaxial test.The radial strain gradient(RSG)is first introduced as an arc tangent function of the rate of change of radial strain to time.RSG is observed to correlate closely with the stress state of a compressed sample,and reaches a horizontal asymptote as approaching failure.For a given rock type,RSG value at peak stress is almost the same,irrespective of the porosity and permeability.These findings lead to the development of RSG criterion:Unloading points can be precisely determined at the time when RSG reaches a pre-determined value that is a little smaller than or equal to the RSG at peak stress.The RSG criterion is validated against other criteria and the single-stage triaxial test on various types of rocks.Failure envelopes from the RSG criterion match well with those from single-stage tests.A practical procedure is recommended to use the RSG criterion:an unconfined compression or single-stage test is first conducted to determine the RSG at peak stress for one sample,the unloading point is then selected to be a value close to the RSG at peak stress,and the multi-stage test is finally performed on another sample using the pre-selected RSG unloading criterion.Generally,the RSG criterion is applicable for any type of rocks,especially brittle rocks,where other criteria are not suitable.Further,it can be practically implemented on the most available rock mechanical testing instruments.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.11974154,and 12304278)the Taishan Scholars Special Funding for Construction Projects(Grant No.tstp20230622)+1 种基金the Natural Science Foundation of Shandong Province(Grant Nos.ZR2022MA004,ZR2023QA127,and ZR2024QA121)the Special Foundation of Yantai for Leading Talents above Provincial Level。
文摘The four-decade quest for synthesizing ambient-stable polymeric nitrogen,a promising high-energy-density material,remains an unsolved challenge in materials science.We develop a multi-stage computational strategy employing density functional tight-binding-based rapid screening combined with density functional theory refinement and global structure searching,effectively bridging computational efficiency with quantum accuracy.This integrated approach identifies four novel polymeric nitrogen phases(Fddd,P3221,I4m2,and𝑃P6522)that are thermodynamically stable at ambient pressure.Remarkably,the helical𝑃6522 configuration demonstrates exceptional thermal resilience up to 1500 K,representing a predicted polymeric nitrogen structure that maintains stability under both atmospheric pressure and high-temperature extremes.Our methodology establishes a paradigm-shifting framework for the accelerated discovery of metastable energetic materials,resolving critical bottlenecks in theoretical predictions while providing experimentally actionable targets for polymeric nitrogen synthesis.
基金the National Key Research and Development Program of China(2021YFC2900300)the Natural Science Foundation of Guangdong Province(2024A1515030216)+2 种基金MOST Special Fund from State Key Laboratory of Geological Processes and Mineral Resources,China University of Geosciences(GPMR202437)the Guangdong Province Introduced of Innovative R&D Team(2021ZT09H399)the Third Xinjiang Scientific Expedition Program(2022xjkk1301).
文摘The application of machine learning for pyrite discrimination establishes a robust foundation for constructing the ore-forming history of multi-stage deposits;however,published models face challenges related to limited,imbalanced datasets and oversampling.In this study,the dataset was expanded to approximately 500 samples for each type,including 508 sedimentary,573 orogenic gold,548 sedimentary exhalative(SEDEX)deposits,and 364 volcanogenic massive sulfides(VMS)pyrites,utilizing random forest(RF)and support vector machine(SVM)methodologies to enhance the reliability of the classifier models.The RF classifier achieved an overall accuracy of 99.8%,and the SVM classifier attained an overall accuracy of 100%.The model was evaluated by a five-fold cross-validation approach with 93.8%accuracy for the RF and 94.9%for the SVM classifier.These results demonstrate the strong feasibility of pyrite classification,supported by a relatively large,balanced dataset and high accuracy rates.The classifier was employed to reveal the genesis of the controversial Keketale Pb-Zn deposit in NW China,which has been inconclusive among SEDEX,VMS,or a SEDEX-VMS transition.Petrographic investigations indicated that the deposit comprises early fine-grained layered pyrite(Py1)and late recrystallized pyrite(Py2).The majority voting classified Py1 as the VMS type,with an accuracy of RF and SVM being 72.2%and 75%,respectively,and confirmed Py2 as an orogenic type with 74.3% and 77.1%accuracy,respectively.The new findings indicated that the Keketale deposit originated from a submarine VMS mineralization system,followed by late orogenic-type overprinting of metamorphism and deformation,which is consistent with the geological and geochemical observations.This study further emphasizes the advantages of Machine learning(ML)methods in accurately and directly discriminating the deposit types and reconstructing the formation history of multi-stage deposits.
基金supported by the National Natural Science Foundation of China(NSFC)under Grant No.22035001 and No.52233005.
文摘To achieve the target of carbon neutrality,it is crucial to develop an efficient and green synthesis methodology with good atomic economy to achieve sufficient utilization of energy and sustainable development.Photoinduced electron transfer reversible addition-fragmentation chain-transfer(PET-RAFT)polymerization is a precise methodology for constructing polymers with well-defined structures.However,conventional semiconductor-mediated PET-RAFT polymerization still has considerable limitations in terms of efficiency as well as the polymerization environment.Herein,sulfur-doped carbonized polymer dots(CPDs)were hydrothermally synthesized for catalysis of aqueous PET-RAFT polymerization at unprecedented efficiency with a highest propagation rate of 5.05 h-1.The resulting polymers have well-controlled molecular weight and narrow molecular weight dispersion(Ð<1.10).Based on the optoelectronic characterizations,we obtained insights into the photoinduced electron transfer process and proposed the mechanism for CPD-mediated PET-RAFT polymerization.In addition,as-synthesized CPDs for PET-RAFT polymerization were also demonstrated to be suitable for a wide range of light sources(blue/green/solar irradiation),numerous monomers,low catalyst loading(low as 0.01 mg mL^(-1)),and multiple polar solvent environments,all of which allowed to achieve efficiencies much higher than those of existing semiconductor-mediated methods.Finally,the CPDs were confirmed to be non-cytotoxic and catalyzed PET-RAFT polymerization successfully in cell culture media,indicating broad prospects in biomedical fields.
基金funded by the State Grid Corporation Science and Technology Project(5108-202218280A-2-391-XG).
文摘The high proportion of uncertain distributed power sources and the access to large-scale random electric vehicle(EV)charging resources further aggravate the voltage fluctuation of the distribution network,and the existing research has not deeply explored the EV active-reactive synergistic regulating characteristics,and failed to realize themulti-timescale synergistic control with other regulatingmeans,For this reason,this paper proposes amultilevel linkage coordinated optimization strategy to reduce the voltage deviation of the distribution network.Firstly,a capacitor bank reactive power compensation voltage control model and a distributed photovoltaic(PV)activereactive power regulationmodel are established.Additionally,an external characteristicmodel of EVactive-reactive power regulation is developed considering the four-quadrant operational characteristics of the EVcharger.Amultiobjective optimization model of the distribution network is then constructed considering the time-series coupling constraints of multiple types of voltage regulators.A multi-timescale control strategy is proposed by considering the impact of voltage regulators on active-reactive EV energy consumption and PV energy consumption.Then,a four-stage voltage control optimization strategy is proposed for various types of voltage regulators with multiple time scales.Themulti-objective optimization is solved with the improvedDrosophila algorithmto realize the power fluctuation control of the distribution network and themulti-stage voltage control optimization.Simulation results validate that the proposed voltage control optimization strategy achieves the coordinated control of decentralized voltage control resources in the distribution network.It effectively reduces the voltage deviation of the distribution network while ensuring the energy demand of EV users and enhancing the stability and economic efficiency of the distribution network.
基金financially supported by the National Natural Science Foundation of China(Nos.22271252 and 22201105)。
文摘Consisting of natural histidine residues,polyhistidine(PHis)simulates functional proteins.Traditional approaches towards PHis require the protection of imidazole groups before monomer synthesis and polymerization to prevent degradation and side reactions.In the contribution,histidine N-thiocarboxyanhydride(His-NTA)is directly synthesized in aqueous solution without protection.With the self-catalysis of the imidazole side group,the ring-closing reaction to form His-NTA does not require any activating reagent(e.g.,phosphorus tribromide),which is elucidated by density functional theory(DFT)calculations.His-NTA directly polymerizes into PHis bearing unprotected imidazole groups with designable molecular weights(4.2-7.7 kg/mol)and low dispersities(1.10-1.19).Kinetic experiments and Monte Carlo simulations reveal the elementary reactions and the relationship between the conversion of His-NTA and time during polymerization.Block copolymerization of His-NTA with sarcosine N-thiocarboxyanhydride(Sar-NTA)demonstrate versatile construction of functional polypept(o)ides.The triblock copoly(amino acid)PHis-b-PSar-b-PHis is capable to reversibly coordinate with transition metal ions(Fe^(2+),Co^(2+),Ni^(2+),Cu^(2+)and Zn^(2+))to form pH-sensitive hydrogels.
基金financially supported by the National Key R&D Program of China(No.2022YFC2805103)the National Natural Science Foundation of China(Nos.52022031 and 52263001)the Foundation from Qinghai Science and Technology Department(No.2022-ZJ-944Q)。
文摘Incorporation of acetal groups in the backbone is a potent strategy to create polymers that are cleavable or degradable under acidic conditions.We report here an in-depth study on the ring-closing-opening copolymerization of o-phthalaldehyde(OPA)and epoxide using Lewis pair type two-component organocatalysts for producing acetal-functionalized polyether and polyurethane.Notably,triethylborane as the Lewis acid,in comparison with tri(n-butyl)borane,more effectively enhances the polymerization activity by mitigating borane-induced reduction of the aldehyde group into extra initiating(borinic ester)species.Density functional theory(DFT)calculations present comparable energy barriers of OPA-epoxide cross-propagation and epoxide self-propagation,which is consistent with the experimental finding that an alternating-rich copolymer comprising mostly OPA-epoxide units but also epoxide-epoxide linkages is produced.In particular,when epoxide is added in a large excess,the product becomes a polyether containing acetal functionalities in the central part of the backbone and thus being convertible into polyurethane with refined acid degradability.
基金financially supported by National Key R&D Program of China(No.2021YFA1501700)CAS Project for Young Scientists in Basic Research(No.YSBR-094)+1 种基金Natural Science Foundation of Anhui Province(Nos.2308085Y35 and 2023AH030002)Hefei Natural Science Foundation(No.202304)。
文摘As a powerful synthetic tool,ruthenium-catalyzed ring-opening metathesis polymerization(ROMP)has been widely utilized to prepare diverse heteroatom-containing polymers.In this contribution,we report the synthesis of the novel imine-based polymer through the copolymerization of cyclooctene with cyclic imine comonomer via ROMP.Because of the efficient hydrolysis reactions of the imine group,the generated copolymer can be easily degraded under mild condition.Moreover,the generated degradable product was the telechelic polymer bearing amine group,which was highly challenged for its direct synthesis.And this telechelic polymer could also be used for the further synthesis of new polymer through post-transformation.The introduction of imine unit in this work provides a new example of the degradable polymer synthesis.
基金support from the Science and Technology Program of Guangzhou(No.2024A04J2821)the National Natural Science Foundation of China(Nos.52222301,22171055)the Guangdong Natural Science Foundation for Distinguished Young Scholar(No.2022B1515020078)。
文摘Core-shell colloidal particles with a polymer layer have broad applications in different areas.Herein,we developed a two-step method combining aqueous surface-initiated photoinduced polymerization-induced self-assembly and photoinduced seeded reversible addition-fragmentation chain transfer(RAFT)polymerization to prepare a diverse set of core-shell colloidal particles with a well-defined polymer layer.Chemical compositions,structures,and thicknesses of polymer layers could be conveniently regulated by using different types of monomers and feed[monomer]/[chain transfer agent]ratios during seeded RAFT polymerization.
基金supported by the National Natural Science Foundation of China(22022813)the Zhejiang Provincial Natural Science Foundation of China(LQ24B030002)the China Postdoctoral Science Foundation(2022M722729,2023T160571).
文摘Although solid-state polymer electrolytes(SPEs)are expected to solve the safety hazards and limited energy density in the energy storage systems,they still encounter an inferior electrode/electrolyte interface when prepared in an ex situ manner.Recently,in situ polymerization of SPEs favor high interfacial infiltrability,improved interface contact,and reduced interface resistance,owing to the formation of a"superconformal"interface between electrode and electrolyte.Especially,in situ strategies employing ring-opening polymerization(ROP)are emerging as dazzling stars,further enabling moderate polymerization conditions,controllable molecular structure,and reduced interfacial side reaction.As the main monomers that can be in situ polymerized via the ROP strategy,cyclic ethers have been used to construct the CE-SPEs with many merits,including good battery electrochemical performances and a simple assembly process.Here,as a systematic summarization of the existing reports,this review focuses on the polymerization mechanism of ROP,the design principles of CE-SPEs electrolytes,and the recent application of in situ CE-SPEs.In particular,this review thoroughly discusses the selection of different cyclic monomers,initiators and various modification approaches in in situ fabricating CE-SPEs.Ending with offering future challenges and perspectives,this review envisions shedding light on the profound understanding and scientific guidance for further development of high-performance in situ CE-SPEs.
基金financially supported by the joint lab of Shanghai Huayi 3F New Materials Co.,Ltd.Donghua University。
文摘Copolymers of fluoroethylene and vinyl ethers(FEVE)are soluble and curable at relatively low temperature,and are used as high-performance coatings and paints.Currently,most market-available FEVE products obtained through solution polymerization contain a large fraction of organic solvent,and hence,volatile organic compound(VOC)emissions cause environmental issues.In this study,the emulsion copolymerization of chlorotrifluoroethylene(CTFE)and vinyl ethers using an environmentally friendly emulsification system to produce waterborne FEVE was investigated.In addition to mixed nonionic and ionic surfactants,macromolecular monomer with double bond and polyoxyethylene segments were used in the emulsification system.The effect of adding macromolecular monomer and polyoxyethylene segment length of the nonionic surfactant on emulsion copolymerization were analyzed.An optimized emulsifier system for FEVE is proposed,and the prepared FEVE latexes exhibit excellent storage stability and film formation ability.
基金financially supported by the Scientific Research Start-up Fund Project of Anhui Polytechnic University for Introducing Talents(No.2022YQQ081)Natural Science Research Project of Anhui Educational Committee(No.2024AH050133)the National Natural Science Foundation of China(No.22001078).
文摘Functional hyperbranched polymers,as an important class of materials,are widely applied in diverse areas.Therefore,the development of simple and efficient reactions to prepare hyperbranched polymers is of great significance.In this work,trialdehydes,diamines,and trimethylsilyl cyanide could easily undergo multicomponent polymerization under mild conditions,producing hyperbranched poly(α-aminonitrile)s with high molecular weights(M_(w) up to 4.87×10^(4))in good yields(up to 85%).The hyperbranched poly(α-aminonitrile)s have good solubility in commonly used organic solvents,high thermal stability as well as morphological stability.Furthermore,due to the numerous aldehyde groups in their branched chains,these hb-poly(α-aminonitrile)s can undergo one-pot,two-step,four-component post-polymerization with high efficiency.This work not only confirms the efficiency of our established catalyst-free multicomponent polymerization of aldehydes,amines and trimethylsilyl cyanide,but also provides a versatile and powerful platform for the preparation of functional hyperbranched polymeric materials.
基金the National Natural Science Foundation of China(grant nos.52020105012 and 523B2025)the Innovation and Talent Recruitment Base of New Energy Chemistry and Device(B21003)the Analysis and Testing Center of HUST for the assistance in analysis and testing。
文摘Solid polymer electrolytes(SPEs)have garnered considerable interest in the field of lithium metal batteries(LMBs)owing to their exceptional mechanical strength,excellent designability,and heightened safety characteristics.However,their inherently low ion transport efficiency poses a major challenge for their application in LMBs.To address this issue,covalent organic framework(COF)with their ordered ion transport channels,chemical stability,large specific surface area,and designable multifunctional sites has shown promising potential to enhance lithium-ion conduction.Here,we prepared an anionic COF,Tp Pa-COOLi,which can catalyze the ring-opening copolymerization of cyclic lactone monomers for the in situ fabrication of SPEs.The design leverages the high specific surface area of COF to facilitate the absorption of polymerization precursor and catalyze the polymerization within the pores,forming additional COF-polymer junctions that enhance ion transport pathways.The partial exfoliation of COF achieved through these junctions improved its dispersion within the polymer matrix,preserving ion transport channels and facilitating ion transport across COF grain boundaries.By controlling variables to alter the crystallinity of Tp Pa-COOLi and the presence of-COOLi substituents,Tp Pa-COOLi with partial long-range order and-COOLi substituents exhibited superior electrochemical performance.This research demonstrates the potential in constructing high-performance SPEs for LMBs.
基金financially supported by the Heilongjiang Provincial Key R&D Program Project(No.GA21A204)Heilongjiang Provincial Natural Science Foundation of China(No.LH2022D031)the Research Project of Heilongjiang Province Bureau of Geology and Mineral Resources(No.HKY202302).
文摘Although previous researchers have attempted to decipher ore genesis and mineralization in the Erdaokan Ag-Pb-Zn deposit,some uncertainties regarding the mineralization process and evolution of both ore-forming fluids and magnetite types still need to be addressed.In this study,we obtained new EPMA,LA-ICP-MS,and in situ Fe isotope data from magnetite from the Erdaokan deposit,in order to better understand the mineralization mechanism and evolution of both magnetite and the ore-forming fluids.Our results identified seven types of magnetite at Erdaokan:disseminated magnetite(Mag1),coarse-grained magnetite(Mag2a),radial magnetite(Mag2b),fragmented fine-grained magnetite(Mag2c),vermicular gel magnetite(Mag3a1 and Mag3a2),colloidal magnetite(Mag3b)and dark gray magnetite(Mag4).All of the magnetite types were hydrothermal in origin and generally low in Ti(<400 ppm)and Ni(<800 ppm),while being enriched in light Fe isotopes(δ^(56)Fe ranging from−1.54‰to−0.06‰).However,they exhibit different geochemical signatures and are thus classified into high-manganese magnetite(Mag1,MnO>5 wt%),low-silicon magnetite(Mag2a-c,SiO_(2)<1 wt%),high-silicon magnetite(Mag3a-b,SiO_(2)from 1 to 7 wt%)and high-silicon-manganese magnetite(Mag4,SiO_(2)>1 wt%,MnO>0.2 wt%),each being formed within distinct hydrothermal environments.Based on mineralogy,elemental geochemistry,Fe isotopes,temperature trends,TMg-mag and(Ti+V)vs.(Al+Mn)diagrams,we propose that the Erdaokan Ag-Pb-Zn deposit underwent multi-stage mineralization,which can be broken down into four stages and nine sub-stages.Mag1,Mag2a-c,Mag3a-b and Mag4 were formed during the first sub-stage of each of the four stages,respectively.Additionally,fluid mixing,cooling and depressurization boiling were identified as the main mechanisms for mineral precipitation.The enrichment of Ag was significantly enhanced by the superposition of multi-stage ore-forming hydrothermal fluids in the Erdaokan Ag-Pb-Zn deposit.
基金funding from the National Natural Science Foundation of China(No.22401037)funding from JST CREST(No.JPMJCR23L1)。
文摘Chain-growth radical polymerization of vinyl monomers is essential for producing a wide range of materials with properties tailored to specific applications.However,the inherent resistance of the polymer's C―C backbone to degradation raises significant concerns regarding long-term environmental persistence,which also limits their potential in biomedical applications.To address these challenges,researchers have developed strategies to either degrade preexisting vinyl polymers or incorporate cleavable units into the backbone to modify them with enhanced degradability.This review explores the various approaches aimed at achieving backbone degradability in chain-growth radical polymerization of vinyl monomers,while also highlighting future research directions for the development of application-driven degradable vinyl polymers.
基金financially supported by the National Natural Science Foundation of China(No.22101194)Natural Science Foundation of Jiangsu Province(No.BK20210733)+3 种基金Suzhou Municipal Science and Technology Bureau(No.ZXL2021447)Collaborative Innovation Center of Suzhou Nano Science&Technologythe 111 ProjectJoint International Research Laboratory of Carbon-Based Functional Materials and Devices。
文摘The preparation of polypeptide materials in continuous flow reactors shows great potential with improved reproducibility and scalability.However,conventional polypeptide synthesis from the polymerization of N-carboxyanhydride(NCA)is conducted at relatively slow rates,requiring long tubing or ending up with low-molecular-weight polymers.Inspired by recent advances in accelerated NCA polymerization,we report the crown-ether-catalyzed,rapid synthesis of polypeptide materials in cosolvents in flow reactors.The incorporation of low-polarity dichloromethane and the use of catalysts enabled fast conversion of monomers in 30 min,yielding well-defined polypeptides(up to 30 k Da)through a 20-cm tubing reactor.Additionally,random or block copolypeptides were efficiently prepared by incorporating a second NCA monomer.We believe that this work highlights the accelerated polymerization design in flow polymerization processes,offering the continuous production of polypeptide materials.
基金supported by the King Abdullah University of Science and Technology(KAUST)。
文摘Seismic data denoising is a critical process usually applied at various stages of the seismic processing workflow,as our ability to mitigate noise in seismic data affects the quality of our subsequent analyses.However,finding an optimal balance between preserving seismic signals and effectively reducing seismic noise presents a substantial challenge.In this study,we introduce a multi-stage deep learning model,trained in a self-supervised manner,designed specifically to suppress seismic noise while minimizing signal leakage.This model operates as a patch-based approach,extracting overlapping patches from the noisy data and converting them into 1D vectors for input.It consists of two identical sub-networks,each configured differently.Inspired by the transformer architecture,each sub-network features an embedded block that comprises two fully connected layers,which are utilized for feature extraction from the input patches.After reshaping,a multi-head attention module enhances the model’s focus on significant features by assigning higher attention weights to them.The key difference between the two sub-networks lies in the number of neurons within their fully connected layers.The first sub-network serves as a strong denoiser with a small number of neurons,effectively attenuating seismic noise;in contrast,the second sub-network functions as a signal-add-back model,using a larger number of neurons to retrieve some of the signal that was not preserved in the output of the first sub-network.The proposed model produces two outputs,each corresponding to one of the sub-networks,and both sub-networks are optimized simultaneously using the noisy data as the label for both outputs.Evaluations conducted on both synthetic and field data demonstrate the model’s effectiveness in suppressing seismic noise with minimal signal leakage,outperforming some benchmark methods.
基金supported by the National Natural Science Foundation of China(No.22376111)Shandong Provincial Natural Science Foundation(No.ZR2024YQ026)+2 种基金for Excellent Young Scholars,Taishan Scholar Foundation of Shandong Province(No.tsqn202408237)Youth Innovation Team Project for Talent Introduction and Cultivation in Universities of Shandong Province(No.096-1622002)the Research Foundation for Distinguished Scholars of Qingdao Agricultural University(No.663-1117015)。
文摘In recent years,cellulose-based fluorescent polymers have received considerable attention.However,conventional modification methods face challenges such as insolubility in most solvents,fluorescence instability,and environmental risks.In this study,a novel biosynthesis strategy was developed to fabricate fluorescent cellulose by adding fluorescent glucose derivatives to a bacterial fermentation broth.The metabolic activity of bacteria is utilized to achieve in situ polymerization of glucose and its derivatives during the synthesis of bacterial cellulose.Owing to the structural similarity between triphenylamine-modified glucose(TPA-Glc N)and glucose monomers,the TPA-Glc N were efficiently assimilated by the bacterial cells and incorporated into the cellulose matrix,resulting in a uniform distribution of fluorescence.The fluorescence color and intensity of the obtained cellulose could be adjusted by varying the amount of the fluorescent glucose derivatives.Compared to the fluorescent cellulose synthesized through physical dyeing,the fluorescence of the products obtained by in situ polymerization showed higher intensity and stability.Furthermore,fluorescent bacterial cellulose can be hydrolyzed into nanocellulose-based ink,which demonstrates exceptional anti-counterfeiting capabilities under UV light.This biosynthesis method not only overcomes the limitations of traditional modification techniques but also highlights the potential of microbial systems as platforms for synthesizing functional polymers.
基金supported by the National Natural Science Foundation of China(No.22071166)the Priority Academic Program Development of Jiangsu High Education Institutions(PAPD).
文摘Exploration of new green polymerization strategies for the construction of conjugated polymers is important but challengeable.In this work,a multicomponent polymerization of acetylarenes,alkynones and ammonium acetate for in situ construction of conjugated poly(triarylpyridine)s was developed.The polymerization reactions of diacetylarenes,aromatic dialkynones and NH_(4)OAc were performed in dimethylsulfoxide(DMSO)under heating in the presence of potassium tert-butoxide(t-BuOK),affording four conjugated poly(2,4,6-triarylpyridine)s(PTAPs)in satisfactory yields.The resulting PTAPs have good solubility in common organic solvents and high thermal stability with 5%weight loss temperatures reaching up to 460℃.They are also electrochemically active.The PTAPs incorporating tetraphenylethene units manifest aggregation-induced emission features.Moreover,through simply being doped into poly(vinyl alcohol)(PVA)matrix,the polymer and model compound containing triphenylamine moieties exhibit room-temperature phosphorescence properties with ultralong lifetimes up to 696.2 ms and high quantum yields up to 28.7%.This work not only provides a facile green synthetic route for conjugated polymers but also offers new insights into the design of advanced materials with unique photophysical properties.
基金financially supported by the National Natural Science Foundation of China(No.52373011)。
文摘Living cationic polymerization of 4-acetoxystyrene(STO)was conducted in CH_(2)Cl_(2) at-15℃ using a dicumyl chloride(DCC)/SnCl_(4)/nBu_(4)NBr initiating system.Impurity moisture initiation was inhibited by adding proton trap 2,6-di-tert-butylpyridine(DTBP),and the controlled initiation of DCC was confirmed by ^(1)H nuclear magnetic resonance(^(1)H-NMR)spectroscopy and matrix-assisted laser desorption ionization time-offlight mass(MALDI-TOF-MS)spectrometry.The polymerization kinetics were analyzed to for optimizing the polymerization rate.Allyl-telechelic PSTOs(allyl-PSTO-allyl)with molecular weight(Mn)range of 3540–7800 g/mol and narrow molecular weight dispersity(Mw/Mn)about 1.25 were prepared through nucleophilic substitution with allyltrimethylsilane(ATMS)at approximately 40%monomer conversion.The experimental results indicate that the substitution efficiency of ATMS increased with higher ATMS concentration,temperature,and extended reaction time.Nearly unity ally-functionality for allyl-PSTO-allyl was achieved by adding sufficient SnCl_(4) prior to the substitution.
文摘This paper presents a new criterion for determining the unloading points quantitatively and consistently in a multi-stage triaxial test.The radial strain gradient(RSG)is first introduced as an arc tangent function of the rate of change of radial strain to time.RSG is observed to correlate closely with the stress state of a compressed sample,and reaches a horizontal asymptote as approaching failure.For a given rock type,RSG value at peak stress is almost the same,irrespective of the porosity and permeability.These findings lead to the development of RSG criterion:Unloading points can be precisely determined at the time when RSG reaches a pre-determined value that is a little smaller than or equal to the RSG at peak stress.The RSG criterion is validated against other criteria and the single-stage triaxial test on various types of rocks.Failure envelopes from the RSG criterion match well with those from single-stage tests.A practical procedure is recommended to use the RSG criterion:an unconfined compression or single-stage test is first conducted to determine the RSG at peak stress for one sample,the unloading point is then selected to be a value close to the RSG at peak stress,and the multi-stage test is finally performed on another sample using the pre-selected RSG unloading criterion.Generally,the RSG criterion is applicable for any type of rocks,especially brittle rocks,where other criteria are not suitable.Further,it can be practically implemented on the most available rock mechanical testing instruments.
