Aerogels with regularly porous structure and uniformly distributed conductive networks have received extensive attention in wearable electronic sensors,electromagnetic shielding,and so on.However,the poor mechanical p...Aerogels with regularly porous structure and uniformly distributed conductive networks have received extensive attention in wearable electronic sensors,electromagnetic shielding,and so on.However,the poor mechanical properties of the emerging nanofibers-based aerogels are limited in practical applications.In this work,we developed a synchronous deprotonation–protonation method in the KOH/dimethyl sulfoxide(DMSO)system at room temperature for achieving chitin cross-linked aramid nanofibers(CANFs)rather than chitin nanofibers(ChNFs)and aramid nanofibers(ANFs)separately by using chitin and aramid pulp as raw materials.After freeze-drying process,the cross-linked chitin/aramid nanofibers(CA)aerogel exhibited the synergetic properties of ChNF and ANF by the dual-nanofiber compensation strategy.The mechanical stress of CA aerogel was 170 kPa at 80%compressive strain,increased by 750%compared with pure ChNF aerogel.Similarly,the compressibility of CA aerogel was somewhat improved compared to ANF aerogel.The enhancement verified that the crosslinking reaction between ANF and ChNF during the synchronous deprotonation process was formed.Afterwards,the conductive aerogels with uniform porous structure(CA-M)were successfully obtained by vacuum impregnating CA aerogels in Ti_(3)C_(2)T_(x) MXene solution,displaying low thermal conductivity(0.01 W/(m·K)),high electromagnetic interference(EMI)shielding effectiveness(SE)(75 dB),flame retardant,and heat insulation.Meanwhile,the as-obtained CA-M aerogels were also applied as a pressure sensor with excellent compression cycle stability and superior human motion monitoring capabilities.As a result,the dual-nanofiber based conductive aerogels have great potentials in flexible/wearable electronics,EMI shielding,flame retardant,and heat insulation.展开更多
Two rosamine-based pH probes 1a and 1b with pyronine-phenol skeleton were designed and synthesized by a simple one-step reaction, pH titration experiments showed that probes 1a and 1b exhibit near OFF-ON fluorescence ...Two rosamine-based pH probes 1a and 1b with pyronine-phenol skeleton were designed and synthesized by a simple one-step reaction, pH titration experiments showed that probes 1a and 1b exhibit near OFF-ON fluorescence responses around 550--750 nm towards the hydrogen ions. The pKa of the probe 1a is 8.29, while that of the probe lb increases to 12.1 because of the hydrogen bond inside it. Selective and competitive experiments indicated that both common ions and amino acids did not interfere their emission with hydrogen ions. Moreover, confocal fluorescent imaging showed that the probe la could be served as mitochondria biomarker in HeLa and Ges-1 cells.展开更多
Quinolones are the subject of much research as antibacterial compounds and as a new class of antitumor agents.The protonation(P) and deprotonation(D) sites and conformations of quinolone were investigated.The proton a...Quinolones are the subject of much research as antibacterial compounds and as a new class of antitumor agents.The protonation(P) and deprotonation(D) sites and conformations of quinolone were investigated.The proton affinity(PA) on each of the possible sites in 4-oxo-1,4-dihydroquinoline has been calculated by the restricted Hartree-Fock(HF) and density functional theory(DFT) methods with the basis set 6-311G**.The O-site of protonation was found to be strongly favored over the N-site for the studied compound in the gas phase.Deprotonation takes place in quinolone by detachment of the N-H and COOH protons.The PA of the simple quinolone molecule was used to characterize quinolone reactivity with DNA binding sites.The relative stabilities of the syn and anti conformations were investigated at the B3LYP/6-311G** level of theory;the syn form was shown to be slightly more stable.Its conformation seems to be intrastabilized by hydrogen-bonds consisting of a hydroxyl proton with the O10 atom as the acceptor.We computed and discussed the charge-density distribution and electrostatic potential to explain the reactivity of quinolone.展开更多
The detection of hydrogen sulfide(H_(2)S)is essential because of its toxicity and abundance in the environment.Hence,there is an urgent requisite to develop a highly sensitive and economical H_(2)S detection system.He...The detection of hydrogen sulfide(H_(2)S)is essential because of its toxicity and abundance in the environment.Hence,there is an urgent requisite to develop a highly sensitive and economical H_(2)S detection system.Herein,a zinc phthalocyanine(ZnPc)thin film-based K+-exchanged optical waveguide(OWG)gas sensor was developed for H_(2)S detection by using spin coating.The sensor showed excellent H_(2)S sensing performance at room temperature with a wide linear range(0.1 ppm 500 ppm),reproducibility,stability,and a low detection limit of 0.1ppm.The developed sensor showed a significant prospect in the development of cost-effective and highly sensitive H_(2)S gas sensors.展开更多
利用可再生电力将二氧化碳转化为高附加值产品的电催化二氧化碳还原反应(CO_(2)RR)是一项具有革命性潜力的技术,因而备受关注.其中,一氧化碳被视为CO_(2)RR中最具经济效益的产物之一,可直接利用费托合成工艺将其用于合成醛、酮、烃类等...利用可再生电力将二氧化碳转化为高附加值产品的电催化二氧化碳还原反应(CO_(2)RR)是一项具有革命性潜力的技术,因而备受关注.其中,一氧化碳被视为CO_(2)RR中最具经济效益的产物之一,可直接利用费托合成工艺将其用于合成醛、酮、烃类等产品.酞菁钴(CoPc)作为单位点催化剂,因其高原子利用率和高催化选择性能,在二氧化碳转化为一氧化碳过程中具有很大优势.然而,CoPc无法为CO_(2)RR中的质子化过程提供足够质子,导致其在工业大电流密度下的效率较低.因此,探索一种能够解决CO_(2)RR中质子供给不足问题的高效电催化剂对于提升CO_(2)RR的性能至关重要.本文设计了具有增强质子供给作用的缺陷碳纳米管(d-CNT),将其作为导电载体分散CoPc,用于制备CoPc/d-CNT电催化剂.通过引入富缺陷的碳纳米管(d-CNT),加速水解离进而增加CO_(2)RR的质子供给量.X射线光电子能谱、X射线吸收近边光谱和扩展X射线吸收精细结构谱结果表明,CoPc/d-CNT成功合成,同时保留了CoPc完整的Co-N4配位结构.透射电镜、粉末X射线衍射谱和拉曼光谱共同表明,d-CNT表面缺陷相对于商用CNT明显增加.动力学实验和原位衰减全反射表面增强红外吸收光谱研究表明,含大量缺陷的d-CNT具有加速水解离的能力,显著提高了二氧化碳还原反应过程中的质子供给,从而促进了CoPc_上CO_(2)活化生成*COOH.同时,密度泛函理论计算结果表明,d-CNT表面缺陷位点上从吸附水(*H2O)到质子水(H3O+)的吉布斯自由能为0.74 eV,远低于CNT(超过2 eV),表明d-CNT促进了水解过程和质子传递,再次证实了d-CNT降低了水分子解离的势垒.通过实验和理论的共同验证,阐明了d-CNT中的缺陷能够促进水解离,改善CO_(2)RR反应过程中质子供给,增强CoPc高效催化CO_(2)RR的能力.因此,CoPc/d-CNT混合材料表现出较好的催化性能.在电流密度为500 mA cm^(-2)的流动电池中,CoPc/d-CNT的CO法拉第效率(FECO)高达96%.相对而言,CoPc/CNT在200 mA cm^(-2)时FECO已经下降到90%以下.此外,在150 mA cm^(-2)的电流密度下,CoPc/d-CNT能够在20 h内维持FECO超过90%.综上,本文通过引入具有水解离能力的缺陷碳位点,解决了单位点催化剂CoPc在CO_(2)RR中质子供给不足的问题,为设计高性能催化剂提供了新见解.展开更多
The isomerization of hydrofluorocyclopentenes promoted by fluoride anion was investigated. It was found that two processes were responsible for interconversion of the isomers: an allylic syn-addition/elimination of fl...The isomerization of hydrofluorocyclopentenes promoted by fluoride anion was investigated. It was found that two processes were responsible for interconversion of the isomers: an allylic syn-addition/elimination of fluoride anion that does not change the mutual positions of hydrogen atoms but is responsible for transfers of fluorine atoms, and a fluoride anion-assisted deprotonation/protonation which does not change the mutual positions of fluorine atoms but is responsible for transfers of hydrogen atoms. In the deprotonation, HF can easily capture excess fluoride anion to form HF2- anion which can probably inhibit the protonation.展开更多
Nanopore detection is a hot issue in current research.One of the challenges is how to slow down the transport velocity of nanoparticles in nanopores.In this paper,we propose a functional group modified nanopore.That m...Nanopore detection is a hot issue in current research.One of the challenges is how to slow down the transport velocity of nanoparticles in nanopores.In this paper,we propose a functional group modified nanopore.That means a polyelectrolyte brush layer is grafted on the surface of the nanopore to change the surface charge properties.The existing studies generally set the charge density of the brush layer to a fixed value.On the contrary,in this paper,we consider an essential property of the brush layer:the volume charge density is adjustable with pH.Thus,the charge property of the brush layer will change with the local H+concentration.Based on this,we established a mathematical model to study the transport of nanoparticles in polyelectrolyte brush layer modified nanopores.We found that pH can effectively adjust the charge density and even the polarity of the brush layer.A larger pH can reduce the transport velocity of nanoparticles and improve the blockade degree of ion current.The grafting density does not change the polarity of the brush charge.The larger the grafting density,the greater the charge density of the brush layer,and the blockade degree of ion current is also more obvious.The polyelectrolyte brush layer modified nanopores in this paper can effectively reduce the nanoparticle transport velocity and retain the essential ion current characteristics,such as ion current blockade and enhancement.展开更多
Azo-salicylaldehyde Schiff base-typed receptors containing an acidic H-bond donor moiety were syn-thesized and characterized. The UV-Vis data indicate that these receptors could act as selective col-orimetric sensors ...Azo-salicylaldehyde Schiff base-typed receptors containing an acidic H-bond donor moiety were syn-thesized and characterized. The UV-Vis data indicate that these receptors could act as selective col-orimetric sensors for basic anions and acidic species hydrogen sulfate by different color changes in a water-containing medium. The experiment of Brφnsted acid-base reaction by adding the sodium hy-droxide or perchloric acid revealed that the mechanism of recognition of anions might be deprotona-tion/protonation of the OH fragments by interacting with different anions and that the deprotona-tion/protonation process is fully reversible. The deprotonation/protonation of the receptors is respon-sible for the dramatic color change.展开更多
基金supported by the Science and Technology Commission of Shanghai Municipality(No.20230742300).
文摘Aerogels with regularly porous structure and uniformly distributed conductive networks have received extensive attention in wearable electronic sensors,electromagnetic shielding,and so on.However,the poor mechanical properties of the emerging nanofibers-based aerogels are limited in practical applications.In this work,we developed a synchronous deprotonation–protonation method in the KOH/dimethyl sulfoxide(DMSO)system at room temperature for achieving chitin cross-linked aramid nanofibers(CANFs)rather than chitin nanofibers(ChNFs)and aramid nanofibers(ANFs)separately by using chitin and aramid pulp as raw materials.After freeze-drying process,the cross-linked chitin/aramid nanofibers(CA)aerogel exhibited the synergetic properties of ChNF and ANF by the dual-nanofiber compensation strategy.The mechanical stress of CA aerogel was 170 kPa at 80%compressive strain,increased by 750%compared with pure ChNF aerogel.Similarly,the compressibility of CA aerogel was somewhat improved compared to ANF aerogel.The enhancement verified that the crosslinking reaction between ANF and ChNF during the synchronous deprotonation process was formed.Afterwards,the conductive aerogels with uniform porous structure(CA-M)were successfully obtained by vacuum impregnating CA aerogels in Ti_(3)C_(2)T_(x) MXene solution,displaying low thermal conductivity(0.01 W/(m·K)),high electromagnetic interference(EMI)shielding effectiveness(SE)(75 dB),flame retardant,and heat insulation.Meanwhile,the as-obtained CA-M aerogels were also applied as a pressure sensor with excellent compression cycle stability and superior human motion monitoring capabilities.As a result,the dual-nanofiber based conductive aerogels have great potentials in flexible/wearable electronics,EMI shielding,flame retardant,and heat insulation.
基金This work was financially supported by the National Natural Science Foundation of China （51273136）, Natural Science Fund of Jiangsu Province （BK20151262）, a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions （PAPD）, the Project of Scientific and Technologic Infrastructure of Suzhou （SZS201708） and Collaborative Innovation Center of Radiological Medicine of Jiangsu Higher Education Institutions.
文摘Two rosamine-based pH probes 1a and 1b with pyronine-phenol skeleton were designed and synthesized by a simple one-step reaction, pH titration experiments showed that probes 1a and 1b exhibit near OFF-ON fluorescence responses around 550--750 nm towards the hydrogen ions. The pKa of the probe 1a is 8.29, while that of the probe lb increases to 12.1 because of the hydrogen bond inside it. Selective and competitive experiments indicated that both common ions and amino acids did not interfere their emission with hydrogen ions. Moreover, confocal fluorescent imaging showed that the probe la could be served as mitochondria biomarker in HeLa and Ges-1 cells.
基金supported by the Deanship of Scientific Research (DSR)King Abdulaziz University,Jeddah (19/130/1431)
文摘Quinolones are the subject of much research as antibacterial compounds and as a new class of antitumor agents.The protonation(P) and deprotonation(D) sites and conformations of quinolone were investigated.The proton affinity(PA) on each of the possible sites in 4-oxo-1,4-dihydroquinoline has been calculated by the restricted Hartree-Fock(HF) and density functional theory(DFT) methods with the basis set 6-311G**.The O-site of protonation was found to be strongly favored over the N-site for the studied compound in the gas phase.Deprotonation takes place in quinolone by detachment of the N-H and COOH protons.The PA of the simple quinolone molecule was used to characterize quinolone reactivity with DNA binding sites.The relative stabilities of the syn and anti conformations were investigated at the B3LYP/6-311G** level of theory;the syn form was shown to be slightly more stable.Its conformation seems to be intrastabilized by hydrogen-bonds consisting of a hydroxyl proton with the O10 atom as the acceptor.We computed and discussed the charge-density distribution and electrostatic potential to explain the reactivity of quinolone.
基金This work was supported by the National Natural Science Foundation of China(Grant No.21765021).
文摘The detection of hydrogen sulfide(H_(2)S)is essential because of its toxicity and abundance in the environment.Hence,there is an urgent requisite to develop a highly sensitive and economical H_(2)S detection system.Herein,a zinc phthalocyanine(ZnPc)thin film-based K+-exchanged optical waveguide(OWG)gas sensor was developed for H_(2)S detection by using spin coating.The sensor showed excellent H_(2)S sensing performance at room temperature with a wide linear range(0.1 ppm 500 ppm),reproducibility,stability,and a low detection limit of 0.1ppm.The developed sensor showed a significant prospect in the development of cost-effective and highly sensitive H_(2)S gas sensors.
文摘利用可再生电力将二氧化碳转化为高附加值产品的电催化二氧化碳还原反应(CO_(2)RR)是一项具有革命性潜力的技术,因而备受关注.其中,一氧化碳被视为CO_(2)RR中最具经济效益的产物之一,可直接利用费托合成工艺将其用于合成醛、酮、烃类等产品.酞菁钴(CoPc)作为单位点催化剂,因其高原子利用率和高催化选择性能,在二氧化碳转化为一氧化碳过程中具有很大优势.然而,CoPc无法为CO_(2)RR中的质子化过程提供足够质子,导致其在工业大电流密度下的效率较低.因此,探索一种能够解决CO_(2)RR中质子供给不足问题的高效电催化剂对于提升CO_(2)RR的性能至关重要.本文设计了具有增强质子供给作用的缺陷碳纳米管(d-CNT),将其作为导电载体分散CoPc,用于制备CoPc/d-CNT电催化剂.通过引入富缺陷的碳纳米管(d-CNT),加速水解离进而增加CO_(2)RR的质子供给量.X射线光电子能谱、X射线吸收近边光谱和扩展X射线吸收精细结构谱结果表明,CoPc/d-CNT成功合成,同时保留了CoPc完整的Co-N4配位结构.透射电镜、粉末X射线衍射谱和拉曼光谱共同表明,d-CNT表面缺陷相对于商用CNT明显增加.动力学实验和原位衰减全反射表面增强红外吸收光谱研究表明,含大量缺陷的d-CNT具有加速水解离的能力,显著提高了二氧化碳还原反应过程中的质子供给,从而促进了CoPc_上CO_(2)活化生成*COOH.同时,密度泛函理论计算结果表明,d-CNT表面缺陷位点上从吸附水(*H2O)到质子水(H3O+)的吉布斯自由能为0.74 eV,远低于CNT(超过2 eV),表明d-CNT促进了水解过程和质子传递,再次证实了d-CNT降低了水分子解离的势垒.通过实验和理论的共同验证,阐明了d-CNT中的缺陷能够促进水解离,改善CO_(2)RR反应过程中质子供给,增强CoPc高效催化CO_(2)RR的能力.因此,CoPc/d-CNT混合材料表现出较好的催化性能.在电流密度为500 mA cm^(-2)的流动电池中,CoPc/d-CNT的CO法拉第效率(FECO)高达96%.相对而言,CoPc/CNT在200 mA cm^(-2)时FECO已经下降到90%以下.此外,在150 mA cm^(-2)的电流密度下,CoPc/d-CNT能够在20 h内维持FECO超过90%.综上,本文通过引入具有水解离能力的缺陷碳位点,解决了单位点催化剂CoPc在CO_(2)RR中质子供给不足的问题,为设计高性能催化剂提供了新见解.
文摘The isomerization of hydrofluorocyclopentenes promoted by fluoride anion was investigated. It was found that two processes were responsible for interconversion of the isomers: an allylic syn-addition/elimination of fluoride anion that does not change the mutual positions of hydrogen atoms but is responsible for transfers of fluorine atoms, and a fluoride anion-assisted deprotonation/protonation which does not change the mutual positions of fluorine atoms but is responsible for transfers of hydrogen atoms. In the deprotonation, HF can easily capture excess fluoride anion to form HF2- anion which can probably inhibit the protonation.
基金funded by National Natural Science Foundation of China(Nos.52075138 and 61964006)Hainan Provincial Natural Science Foundation(No.2019RC032)Hainan Province Science and Technology Special Fund(No.ZDYF2022SHFZ033)。
文摘Nanopore detection is a hot issue in current research.One of the challenges is how to slow down the transport velocity of nanoparticles in nanopores.In this paper,we propose a functional group modified nanopore.That means a polyelectrolyte brush layer is grafted on the surface of the nanopore to change the surface charge properties.The existing studies generally set the charge density of the brush layer to a fixed value.On the contrary,in this paper,we consider an essential property of the brush layer:the volume charge density is adjustable with pH.Thus,the charge property of the brush layer will change with the local H+concentration.Based on this,we established a mathematical model to study the transport of nanoparticles in polyelectrolyte brush layer modified nanopores.We found that pH can effectively adjust the charge density and even the polarity of the brush layer.A larger pH can reduce the transport velocity of nanoparticles and improve the blockade degree of ion current.The grafting density does not change the polarity of the brush charge.The larger the grafting density,the greater the charge density of the brush layer,and the blockade degree of ion current is also more obvious.The polyelectrolyte brush layer modified nanopores in this paper can effectively reduce the nanoparticle transport velocity and retain the essential ion current characteristics,such as ion current blockade and enhancement.
基金the National Natural Science Foundation of China (Grant Nos. 20371040 & 20671077)the Natural Science Foundation of Gansu Province (Grant No. 3YS051-A25-01)the Key Project of Chinese Ministry of Education (Grant No. 205161)
文摘Azo-salicylaldehyde Schiff base-typed receptors containing an acidic H-bond donor moiety were syn-thesized and characterized. The UV-Vis data indicate that these receptors could act as selective col-orimetric sensors for basic anions and acidic species hydrogen sulfate by different color changes in a water-containing medium. The experiment of Brφnsted acid-base reaction by adding the sodium hy-droxide or perchloric acid revealed that the mechanism of recognition of anions might be deprotona-tion/protonation of the OH fragments by interacting with different anions and that the deprotona-tion/protonation process is fully reversible. The deprotonation/protonation of the receptors is respon-sible for the dramatic color change.
