利用密度泛函理论(DFT),在B3LYP/cc-pVDZ水平上,对三过氧化三丙酮(Triacetone triperoxide,TATP)及其质子化离子[TATP+H]+进行了构型优化和质子亲和势(Proton Affinity,PA)计算,研究结果表明,PA(TATP)=866.73kJ/mol大于PA(H2O)=691.0kJ/...利用密度泛函理论(DFT),在B3LYP/cc-pVDZ水平上,对三过氧化三丙酮(Triacetone triperoxide,TATP)及其质子化离子[TATP+H]+进行了构型优化和质子亲和势(Proton Affinity,PA)计算,研究结果表明,PA(TATP)=866.73kJ/mol大于PA(H2O)=691.0kJ/mol,TATP与H3O+可发生质子转移反应.在自行研制的质子转移反应质谱(Proton transfer reaction mass spectrometry,PTR-MS)装置上,研究了TATP与H3O+反应生成的特征离子.当漂移管中E/N=1.4×10-15V.cm2时,在荷质比m/z=91,75,74,59,43等处观察到了产物离子.降低E/N至0.5×10-15V.cm2后,在m/z=223处观察到了质子化产物离子([TATP+H]+),验证了计算结果;结合[TATP+H]+的构型,分析了TATP质子转移反应产物离子可能的归属及其形成过程.结合PTR-MS漂移管内E/N的改变引起m/z=223,91,43等离子的变化特征,可实现TATP的准确识别和快速定量检测,检测下限达到5.0×10-10mol/L(±50%).展开更多
为了研究氘化对三过氧化三丙酮(TATP)化学键振动性质以及热分解行为的影响,分别以丙酮和丙酮-d_(6)为原料,过氧化氢为氧化剂,硫酸为催化剂,制备了TATP和氘代三过氧化三丙酮(TATP-d_(18))。采用核磁共振波谱、傅里叶变换红外光谱和差示...为了研究氘化对三过氧化三丙酮(TATP)化学键振动性质以及热分解行为的影响,分别以丙酮和丙酮-d_(6)为原料,过氧化氢为氧化剂,硫酸为催化剂,制备了TATP和氘代三过氧化三丙酮(TATP-d_(18))。采用核磁共振波谱、傅里叶变换红外光谱和差示扫描量热法对TATP和TATP-d_(18)进行表征,使用Kissinger法、Ozawa法和Friedman法计算得到了TATP和TATP-d_(18)的非等温反应动力学参数。结果表明,TATP-d_(18)分子中各化学键的振动频率相比于TATP表现出不同程度的红移现象,C—H(D)键伸缩振动频率之比(ν_(C—H)/ν_(C—D))约为1.36;由Kissinger法、Ozawa法和Friedman法所得TATP-d_(18)的表观活化能(E_(K)=80.54 k J·mol^(-1),E_(O)=83.56 k J·mol^(-1),E_(F)=72.27 k J·mol^(-1))均高于这3种方法计算得到的TATP的表观活化能(E_(K)=67.91 k J·mol^(-1),E_(O)=71.01 k J·mol^(-1),E_(F)=63.79 k J·mol^(-1)),这表明TATP-d_(18)具有更高的热稳定性;计算所得的TATP与TATP-d_(18)的热爆炸临界温度分别为402.37 K和423.46 K,这也证实了TATP-d_(18)具有更高的热稳定性;计算得到了TATP和TATP-d_(18)的非等温分解过程热力学参数,证明了TATP和TATP-d_(18)不会自发发生热爆炸。展开更多
The design of zero-background fluorescent sensing materials with specific functionalities is of great significance.Here,a special Eu-MOF with nonfluorescent emission was designed and driven by H_(2)O-induced cascade r...The design of zero-background fluorescent sensing materials with specific functionalities is of great significance.Here,a special Eu-MOF with nonfluorescent emission was designed and driven by H_(2)O-induced cascade reaction through modulating the number of hydroxyl groups in ligands to enhance the signal-to-noise ratio,sensitivity,and reaction speed toward triacetone triperoxide(TATP).It is found that only when the ligand was selected as 2,5-dihydroxyterephthalic acid(DHTA),and with the introduction of H_(2)O,the intramolecular hydrogen bond could be changed to a weaker intermolecular hydrogen bond,which would be interrupted and oxidized from the original enol structure to ketone,producing the fluorescence turn-on response toward TATP.The special Eu-MOF exhibited a high-performance sensing for TATP,with fast response(<1 s),low limit of detection(LOD,36.1 nM),superior selectivity even in the presence of 28 kinds of interferents,including the very similar hydrogen peroxide,strong robustness,and a practical detecting ability of 5 pg airborne TATP particle.Furthermore,we validated the practical feasibility of the specific Eu-MOF by integrating a sensing chip into a portable detector,thereby confirming that this MOF exhibits considerable potential for trace-level TATP detection in real-world application scenarios.The present nonfluorescent MOF design strategy and the elaborate modulation of the conformation in MOF structure would provide a new pathway for the exploration of novel functional MOFs as well as high-performance sensing methodologies.展开更多
文摘利用密度泛函理论(DFT),在B3LYP/cc-pVDZ水平上,对三过氧化三丙酮(Triacetone triperoxide,TATP)及其质子化离子[TATP+H]+进行了构型优化和质子亲和势(Proton Affinity,PA)计算,研究结果表明,PA(TATP)=866.73kJ/mol大于PA(H2O)=691.0kJ/mol,TATP与H3O+可发生质子转移反应.在自行研制的质子转移反应质谱(Proton transfer reaction mass spectrometry,PTR-MS)装置上,研究了TATP与H3O+反应生成的特征离子.当漂移管中E/N=1.4×10-15V.cm2时,在荷质比m/z=91,75,74,59,43等处观察到了产物离子.降低E/N至0.5×10-15V.cm2后,在m/z=223处观察到了质子化产物离子([TATP+H]+),验证了计算结果;结合[TATP+H]+的构型,分析了TATP质子转移反应产物离子可能的归属及其形成过程.结合PTR-MS漂移管内E/N的改变引起m/z=223,91,43等离子的变化特征,可实现TATP的准确识别和快速定量检测,检测下限达到5.0×10-10mol/L(±50%).
文摘为了研究氘化对三过氧化三丙酮(TATP)化学键振动性质以及热分解行为的影响,分别以丙酮和丙酮-d_(6)为原料,过氧化氢为氧化剂,硫酸为催化剂,制备了TATP和氘代三过氧化三丙酮(TATP-d_(18))。采用核磁共振波谱、傅里叶变换红外光谱和差示扫描量热法对TATP和TATP-d_(18)进行表征,使用Kissinger法、Ozawa法和Friedman法计算得到了TATP和TATP-d_(18)的非等温反应动力学参数。结果表明,TATP-d_(18)分子中各化学键的振动频率相比于TATP表现出不同程度的红移现象,C—H(D)键伸缩振动频率之比(ν_(C—H)/ν_(C—D))约为1.36;由Kissinger法、Ozawa法和Friedman法所得TATP-d_(18)的表观活化能(E_(K)=80.54 k J·mol^(-1),E_(O)=83.56 k J·mol^(-1),E_(F)=72.27 k J·mol^(-1))均高于这3种方法计算得到的TATP的表观活化能(E_(K)=67.91 k J·mol^(-1),E_(O)=71.01 k J·mol^(-1),E_(F)=63.79 k J·mol^(-1)),这表明TATP-d_(18)具有更高的热稳定性;计算所得的TATP与TATP-d_(18)的热爆炸临界温度分别为402.37 K和423.46 K,这也证实了TATP-d_(18)具有更高的热稳定性;计算得到了TATP和TATP-d_(18)的非等温分解过程热力学参数,证明了TATP和TATP-d_(18)不会自发发生热爆炸。
基金supported by the National Key Research and Devel-opment Program of China(2022YFA1205500)the National Natural Science Foundation of China(22174159)+2 种基金and the Key Research Project of Chinese Academy of Sciences under Grant Number.KGFZD-145-25-21-01,the Tianshan Talents Plan(2022TSYCCX0074)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(2022441)the Natural Science Foundation of Xinjiang Uygur Autonomous Region(2025D01E54).
文摘The design of zero-background fluorescent sensing materials with specific functionalities is of great significance.Here,a special Eu-MOF with nonfluorescent emission was designed and driven by H_(2)O-induced cascade reaction through modulating the number of hydroxyl groups in ligands to enhance the signal-to-noise ratio,sensitivity,and reaction speed toward triacetone triperoxide(TATP).It is found that only when the ligand was selected as 2,5-dihydroxyterephthalic acid(DHTA),and with the introduction of H_(2)O,the intramolecular hydrogen bond could be changed to a weaker intermolecular hydrogen bond,which would be interrupted and oxidized from the original enol structure to ketone,producing the fluorescence turn-on response toward TATP.The special Eu-MOF exhibited a high-performance sensing for TATP,with fast response(<1 s),low limit of detection(LOD,36.1 nM),superior selectivity even in the presence of 28 kinds of interferents,including the very similar hydrogen peroxide,strong robustness,and a practical detecting ability of 5 pg airborne TATP particle.Furthermore,we validated the practical feasibility of the specific Eu-MOF by integrating a sensing chip into a portable detector,thereby confirming that this MOF exhibits considerable potential for trace-level TATP detection in real-world application scenarios.The present nonfluorescent MOF design strategy and the elaborate modulation of the conformation in MOF structure would provide a new pathway for the exploration of novel functional MOFs as well as high-performance sensing methodologies.
