This work presents an encryptionmodel based onGenerativeAdversarialNetworks(GANs).Encryption of RTF-8 data is realized by dynamically generating decimal numbers that lead to the encryption and decryption of alphabetic...This work presents an encryptionmodel based onGenerativeAdversarialNetworks(GANs).Encryption of RTF-8 data is realized by dynamically generating decimal numbers that lead to the encryption and decryption of alphabetic strings in integer representation by simple addition rules,the modulus of the dimension of the considered alphabet.The binary numbers for the private dynamic keys correspond to the binary numbers of public reference keys,as defined by a specific GAN configuration.For reversible encryption with a bijective mapping between dynamic and reference keys,as defined by the GAN encryptor,secure text encryption can be achieved by transferring a GANencrypted public key along with the encrypted text from a sender to a receiver.Using the technique described above,secure text mail transfer can be realized through component-wise encryption and decryption of text mail strings,with total key sizes of up to 108 bits that define random decimal numbers generated by the GAN.From the present model,we assert that encrypted texts can be transmitted more efficiently and securely than with RSA encryption,given an additional security component that users of the specific configuration of the GAN encryption model are unaware of the GAN encryptor circuit and configuration,respectively.展开更多
Co_(3)O_(4)possesses both direct and indirect oxidation effects and is considered as a promising catalyst for the oxidation of 5-hydroxymethylfurfural(HMF).However,the enrichment and activation effects of Co_(3)O_(4)o...Co_(3)O_(4)possesses both direct and indirect oxidation effects and is considered as a promising catalyst for the oxidation of 5-hydroxymethylfurfural(HMF).However,the enrichment and activation effects of Co_(3)O_(4)on OH-and HMF are weak,which limits its further application.Metal defect engineering can regulate the electronic structure,optimize the adsorption of intermediates,and improve the catalytic activity by breaking the symmetry of the material,which is rarely involved in the upgrading of biomass.In this work,we prepare Co_(3)O_(4)with metal defects and load the precious metal platinum at the defect sites(PtVco).The results of in-situ characterizatio ns,electrochemical measurements,and theoretical calculations indicate that the reduction of Co-Co coordination number and the formation of Pt-Co bond induce the decrease of electron filling in the antibonding orbitals of Co element.The resulting upward shift of the d-band center of Co combined with the characteristic adsorption of Pt species synergically enhances the enrichment and activation of organic molecules and OH species,thus exhibiting excellent HMF oxidation activity(including a lower onset potential(1.14 V)and 19 times higher current density than pure Co_(3)O_(4)at 1.35 V).In summary,this work explores the adsorption enhancement mechanism of metal defect sites modified by precious metal in detail,provides a new option for improving the HMF oxidation activity of cobalt-based materials,broadens the application field of metal defect based materials,and gives an innovative guidance for the functional utilization of metal defect sites in biomass conversion.展开更多
α,α-Difluoro-β-aminophosphonates can be looked as structural analogies withα-amino acids,which have attracted great attention in biological and medicinal chemistry during the past decades.Furthermore,these compoun...α,α-Difluoro-β-aminophosphonates can be looked as structural analogies withα-amino acids,which have attracted great attention in biological and medicinal chemistry during the past decades.Furthermore,these compounds also belong to an important type of organic building blocks for the rapid synthesis of difluoromethylenephosphonate-containing molecules.Thus,the preparation and application ofα,α-difluoro-β-aminophosphonates are hot research topics in organic phosphine chemistry.A comprehensive summary of the literature reports related toα,α-difluoro-β-aminophosphonates in recent years is presented.And aspects of synthesis and applications ofα,α-difluoro-β-aminophosphonates are discussed,in order to provide critical guidance for the further development of reactions and applications for the synthesis of difluoromethylenephosphonate derivatives.展开更多
The premature decay of electrochemical nitrogen reduction reaction(eNRR)performance at low electrode potentials remains a major obstacle to practical applications,which is primarily attributed to the competition from ...The premature decay of electrochemical nitrogen reduction reaction(eNRR)performance at low electrode potentials remains a major obstacle to practical applications,which is primarily attributed to the competition from the hydrogen evolution reaction(HER).A new paradigm capable of transcending current selectivity constraints is urgently required to advance eNRR toward industrial implementation.In this work,we propose two practical selectivity descriptors(ΔΔG andΔU)based on a systematic investigation of the potential-dependent competition between eNRR and HER on confined dual-atom catalysts.The descriptorΔΔG(G_(N_(2))-ΔG_(H))identifies the potential range where N_(2)adsorption dominates over H adsorption,whileΔU(U_(cross)-U_(eNRR))specifies the potential range to trigger direct eNRR,offering a quantitative benchmark for rational catalyst design.Ideal catalysts should maintain N_(2)-preferential adsorption across a broad potential window to facilitate direct eNRR.Guided by this insight,we demonstrate that confined dual-atom configurations with optimized interatomic distances can simultaneously achieve both overwhelming N_(2)adsorption and sufficient activation,thereby overcoming the conventional selectivity limitations.This strategy enables ammonia synthesis with industrially relevant production rates and current density even at elevated potentials.Our mechanistic insights not only elucidate the root causes of performance limitations in eNRR but also offer a rational design framework for developing high-performance catalysts across a broad range of electrochemical transformations.展开更多
Here we report a comprehensive study on the synthesis and characterization of dimethylarsinate-functionalized phosphomolybdates(V),[RPMo_(6)^(Ⅴ)O_(15)(OH)_(3){AsO_(2)(CH_(3))_(2)}_(3)]^(2-)(R=H,HO,CH_(3),HO_(2)CCH_(2...Here we report a comprehensive study on the synthesis and characterization of dimethylarsinate-functionalized phosphomolybdates(V),[RPMo_(6)^(Ⅴ)O_(15)(OH)_(3){AsO_(2)(CH_(3))_(2)}_(3)]^(2-)(R=H,HO,CH_(3),HO_(2)CCH_(2),HO_(2)CC_(2)H_(4),C_(6)H_(5),4-FC_(6)H_(4),4-F_(3)COC_(6)H_(4))and the monoanionic mixed-valent heptamolybdate[HOMo^(Ⅵ)Mo_(6)^(Ⅴ)O_(15)(OH)_(3){AsO_(2)(CH_(3))_(2)}_(3)]^(-).These nine novel polyanions feature a reduced,cyclic hexanuclear{Mo_(6)^(Ⅴ)O_(24)}core,decorated peripherally by three dimethylarsinate ligands and centrally by six different organophosphonate groups including fluorinated ones,as well as phosphate and phosphite.The polyanions were synthesized under simple one-pot aqueous solution conditions and characterized(i)in the solid state by single-crystal and powder XRD,TGA,elemental analysis,(ii)in solution by multinuclear(^(1)H,^(31)P,^(19)F,^(13)C)NMR,and(iii)in the gas phase by ESI mass spectrometry.展开更多
It is tough,but worth it,to break the simple and inflexible structure of high symmetry and low energy,such as the cuboid topology of polyoxopalladates(POPs).In this work,the heterometal-templated scaffold of arsenopal...It is tough,but worth it,to break the simple and inflexible structure of high symmetry and low energy,such as the cuboid topology of polyoxopalladates(POPs).In this work,the heterometal-templated scaffold of arsenopalladates has afforded three nanocubes of[M^(Ⅳ)Pd_(12)O_(8)(AsO_(4))_(8)]^(12-)(M=Sn^(Ⅳ),Ce^(Ⅳ),and Pb^(Ⅳ))and the long-sought nanostar of[Pb^(Ⅳ)Pd_(15)O_(10)(AsO_(4))_(10)]^(16-).The appropriate charge and radius of Pb^(Ⅳ) satisfied the uncommon host-vip assembly of both cubic and star archetypes simultaneously.More than that is the successful preparation of the methylphosphonate-capped[Pd_(15)O_(10)(MePO_(3))_(10)]^(10-)POP for the first time.According to the adjustable heterometals and heterogroups,the as-made POPs represent ideal subjects to reveal structure-dependent antitumor activity.It turns out that ROS-induced apoptosis mediated by arsenate functions is mainly responsible for the significant inhibition against cancers of different types,which heralds the design philosophy of POP-based antitumor metallodrugs of the next generation.展开更多
The discovery of efficient catalysts with suitable electronic states for CO_(2)activation is critical for advancing CO_(2)electrochemical reduction(CO_(2)ER).However,due to chemical inertness of CO_(2),seldom material...The discovery of efficient catalysts with suitable electronic states for CO_(2)activation is critical for advancing CO_(2)electrochemical reduction(CO_(2)ER).However,due to chemical inertness of CO_(2),seldom materials exhibit such characteristics without modification.Herein,we employ density functional theory(DFT)computations to demonstrate that an intrinsic antiferromagnetic Mn_(2)B_(7)monolayer characterized by alternating spin alignment prevents the complete filling of either spin-up or spin-down orbitals.This unique electronic structure provides unpaired electrons to activate CO_(2)and facilitate its conversion.As a result,Mn_(2)B_(7)monolayer exhibits superior catalytic selectivity toward CH_(4)and CH_(3)CH_(2)OH production,with low limiting potentials(-0.43 and-0.45 V)and kinetic energy barriers(<1.0 eV),significantly outperforming nonmagnetic Fe_(2)B_(7),Ru_(2)B_(7),and Os_(2)B_(7)monolayers.This study demonstrates the crucial role of adjacent antiferromagnetic unpaired electrons in CO_(2)adsorption,activation,and conversion,providing new insights into the design of highly efficient CO_(2)ER catalysts.展开更多
Two-dimensional materials offer a promising platform for the next generation of(opto-)electronic devices and other high technology applications.One of the most exciting characteristics of 2D crystals is the ability to...Two-dimensional materials offer a promising platform for the next generation of(opto-)electronic devices and other high technology applications.One of the most exciting characteristics of 2D crystals is the ability to tune their properties via controllable introduction of defects.However,the search space for such structures is enormous,and ab-initio computations prohibitively expensive.We propose a machine learning approach for rapid estimation of the properties of 2D material given the lattice structure and defect configuration.The method suggests a way to represent configuration of 2D materials with defects that allows a neural network to train quickly and accurately.We compare our methodology with the state-of-the-art approaches and demonstrate at least 3.7 times energy prediction error drop.Also,our approach is an order of magnitude more resource-efficient than its contenders both for the training and inference part.展开更多
文摘This work presents an encryptionmodel based onGenerativeAdversarialNetworks(GANs).Encryption of RTF-8 data is realized by dynamically generating decimal numbers that lead to the encryption and decryption of alphabetic strings in integer representation by simple addition rules,the modulus of the dimension of the considered alphabet.The binary numbers for the private dynamic keys correspond to the binary numbers of public reference keys,as defined by a specific GAN configuration.For reversible encryption with a bijective mapping between dynamic and reference keys,as defined by the GAN encryptor,secure text encryption can be achieved by transferring a GANencrypted public key along with the encrypted text from a sender to a receiver.Using the technique described above,secure text mail transfer can be realized through component-wise encryption and decryption of text mail strings,with total key sizes of up to 108 bits that define random decimal numbers generated by the GAN.From the present model,we assert that encrypted texts can be transmitted more efficiently and securely than with RSA encryption,given an additional security component that users of the specific configuration of the GAN encryption model are unaware of the GAN encryptor circuit and configuration,respectively.
基金financially supported by the Natural Science Foundation of Shandong Province(ZR2023QB235,ZR202111240183,ZR2021QF120)the Postdoctoral Science Foundation of China(2022M711956)the Taishan Scholar Program of Shandong Province(tsqnz20231216).
文摘Co_(3)O_(4)possesses both direct and indirect oxidation effects and is considered as a promising catalyst for the oxidation of 5-hydroxymethylfurfural(HMF).However,the enrichment and activation effects of Co_(3)O_(4)on OH-and HMF are weak,which limits its further application.Metal defect engineering can regulate the electronic structure,optimize the adsorption of intermediates,and improve the catalytic activity by breaking the symmetry of the material,which is rarely involved in the upgrading of biomass.In this work,we prepare Co_(3)O_(4)with metal defects and load the precious metal platinum at the defect sites(PtVco).The results of in-situ characterizatio ns,electrochemical measurements,and theoretical calculations indicate that the reduction of Co-Co coordination number and the formation of Pt-Co bond induce the decrease of electron filling in the antibonding orbitals of Co element.The resulting upward shift of the d-band center of Co combined with the characteristic adsorption of Pt species synergically enhances the enrichment and activation of organic molecules and OH species,thus exhibiting excellent HMF oxidation activity(including a lower onset potential(1.14 V)and 19 times higher current density than pure Co_(3)O_(4)at 1.35 V).In summary,this work explores the adsorption enhancement mechanism of metal defect sites modified by precious metal in detail,provides a new option for improving the HMF oxidation activity of cobalt-based materials,broadens the application field of metal defect based materials,and gives an innovative guidance for the functional utilization of metal defect sites in biomass conversion.
文摘α,α-Difluoro-β-aminophosphonates can be looked as structural analogies withα-amino acids,which have attracted great attention in biological and medicinal chemistry during the past decades.Furthermore,these compounds also belong to an important type of organic building blocks for the rapid synthesis of difluoromethylenephosphonate-containing molecules.Thus,the preparation and application ofα,α-difluoro-β-aminophosphonates are hot research topics in organic phosphine chemistry.A comprehensive summary of the literature reports related toα,α-difluoro-β-aminophosphonates in recent years is presented.And aspects of synthesis and applications ofα,α-difluoro-β-aminophosphonates are discussed,in order to provide critical guidance for the further development of reactions and applications for the synthesis of difluoromethylenephosphonate derivatives.
基金supported by the Taishan Scholar Program of Shandong Province(tsqn202507090)Postdoctoral Fellowship Program of China Postdoctoral Science Foundation(CPSF)(GZB20250022)+1 种基金Natural Science Foundation of Shandong Province(ZR2025QC1086)Young Talents Project at Ocean University of China。
文摘The premature decay of electrochemical nitrogen reduction reaction(eNRR)performance at low electrode potentials remains a major obstacle to practical applications,which is primarily attributed to the competition from the hydrogen evolution reaction(HER).A new paradigm capable of transcending current selectivity constraints is urgently required to advance eNRR toward industrial implementation.In this work,we propose two practical selectivity descriptors(ΔΔG andΔU)based on a systematic investigation of the potential-dependent competition between eNRR and HER on confined dual-atom catalysts.The descriptorΔΔG(G_(N_(2))-ΔG_(H))identifies the potential range where N_(2)adsorption dominates over H adsorption,whileΔU(U_(cross)-U_(eNRR))specifies the potential range to trigger direct eNRR,offering a quantitative benchmark for rational catalyst design.Ideal catalysts should maintain N_(2)-preferential adsorption across a broad potential window to facilitate direct eNRR.Guided by this insight,we demonstrate that confined dual-atom configurations with optimized interatomic distances can simultaneously achieve both overwhelming N_(2)adsorption and sufficient activation,thereby overcoming the conventional selectivity limitations.This strategy enables ammonia synthesis with industrially relevant production rates and current density even at elevated potentials.Our mechanistic insights not only elucidate the root causes of performance limitations in eNRR but also offer a rational design framework for developing high-performance catalysts across a broad range of electrochemical transformations.
文摘Here we report a comprehensive study on the synthesis and characterization of dimethylarsinate-functionalized phosphomolybdates(V),[RPMo_(6)^(Ⅴ)O_(15)(OH)_(3){AsO_(2)(CH_(3))_(2)}_(3)]^(2-)(R=H,HO,CH_(3),HO_(2)CCH_(2),HO_(2)CC_(2)H_(4),C_(6)H_(5),4-FC_(6)H_(4),4-F_(3)COC_(6)H_(4))and the monoanionic mixed-valent heptamolybdate[HOMo^(Ⅵ)Mo_(6)^(Ⅴ)O_(15)(OH)_(3){AsO_(2)(CH_(3))_(2)}_(3)]^(-).These nine novel polyanions feature a reduced,cyclic hexanuclear{Mo_(6)^(Ⅴ)O_(24)}core,decorated peripherally by three dimethylarsinate ligands and centrally by six different organophosphonate groups including fluorinated ones,as well as phosphate and phosphite.The polyanions were synthesized under simple one-pot aqueous solution conditions and characterized(i)in the solid state by single-crystal and powder XRD,TGA,elemental analysis,(ii)in solution by multinuclear(^(1)H,^(31)P,^(19)F,^(13)C)NMR,and(iii)in the gas phase by ESI mass spectrometry.
基金financially supported by the National Natural Science Foundation of China(No.22001066)the Science and Technology Innovation Program of Hunan Province(2022RC1115)+2 种基金the Natural Science Foundation of Hunan Province(2022JJ20007)the National Natural Science Foundation of China(No.22175046)Guangzhou Science and Technology Project(202201010466)for support.
文摘It is tough,but worth it,to break the simple and inflexible structure of high symmetry and low energy,such as the cuboid topology of polyoxopalladates(POPs).In this work,the heterometal-templated scaffold of arsenopalladates has afforded three nanocubes of[M^(Ⅳ)Pd_(12)O_(8)(AsO_(4))_(8)]^(12-)(M=Sn^(Ⅳ),Ce^(Ⅳ),and Pb^(Ⅳ))and the long-sought nanostar of[Pb^(Ⅳ)Pd_(15)O_(10)(AsO_(4))_(10)]^(16-).The appropriate charge and radius of Pb^(Ⅳ) satisfied the uncommon host-vip assembly of both cubic and star archetypes simultaneously.More than that is the successful preparation of the methylphosphonate-capped[Pd_(15)O_(10)(MePO_(3))_(10)]^(10-)POP for the first time.According to the adjustable heterometals and heterogroups,the as-made POPs represent ideal subjects to reveal structure-dependent antitumor activity.It turns out that ROS-induced apoptosis mediated by arsenate functions is mainly responsible for the significant inhibition against cancers of different types,which heralds the design philosophy of POP-based antitumor metallodrugs of the next generation.
基金support from the Youth Development Foundation of Jilin Province(No.20230508183RC)the National Natural Science Foundation of China(Nos.22403014 and 21673036)+1 种基金the China Postdoctoral Science Foundation(Nos.2023M730539 and 2024T170121)the Fundamental Research Funds for the Central Universities(Nos.2412022ZD050 and 2412023QD012).
文摘The discovery of efficient catalysts with suitable electronic states for CO_(2)activation is critical for advancing CO_(2)electrochemical reduction(CO_(2)ER).However,due to chemical inertness of CO_(2),seldom materials exhibit such characteristics without modification.Herein,we employ density functional theory(DFT)computations to demonstrate that an intrinsic antiferromagnetic Mn_(2)B_(7)monolayer characterized by alternating spin alignment prevents the complete filling of either spin-up or spin-down orbitals.This unique electronic structure provides unpaired electrons to activate CO_(2)and facilitate its conversion.As a result,Mn_(2)B_(7)monolayer exhibits superior catalytic selectivity toward CH_(4)and CH_(3)CH_(2)OH production,with low limiting potentials(-0.43 and-0.45 V)and kinetic energy barriers(<1.0 eV),significantly outperforming nonmagnetic Fe_(2)B_(7),Ru_(2)B_(7),and Os_(2)B_(7)monolayers.This study demonstrates the crucial role of adjacent antiferromagnetic unpaired electrons in CO_(2)adsorption,activation,and conversion,providing new insights into the design of highly efficient CO_(2)ER catalysts.
文摘Two-dimensional materials offer a promising platform for the next generation of(opto-)electronic devices and other high technology applications.One of the most exciting characteristics of 2D crystals is the ability to tune their properties via controllable introduction of defects.However,the search space for such structures is enormous,and ab-initio computations prohibitively expensive.We propose a machine learning approach for rapid estimation of the properties of 2D material given the lattice structure and defect configuration.The method suggests a way to represent configuration of 2D materials with defects that allows a neural network to train quickly and accurately.We compare our methodology with the state-of-the-art approaches and demonstrate at least 3.7 times energy prediction error drop.Also,our approach is an order of magnitude more resource-efficient than its contenders both for the training and inference part.
