Energy raolved mass spectra (ERMS) of 2, 3-DNT and 3, 5-DNT isomers was mported. The fragmentation of this pair of DNTisomers was studied by ERMS in electron impact (EI),and their breakdown curves were discussed , T...Energy raolved mass spectra (ERMS) of 2, 3-DNT and 3, 5-DNT isomers was mported. The fragmentation of this pair of DNTisomers was studied by ERMS in electron impact (EI),and their breakdown curves were discussed , These nitraromaic isomers can be characterized according to the differences between their ERMS in MS/MS展开更多
The cis and trans isomers separation of 2-butene-1,4-diol and lafutidine were studied by HPLC on two kinds of chiral columns: (S,S)-Whelk-O 1 and ChiraSpher. The isomers of 2-butene-1,4-diol can be separated on both c...The cis and trans isomers separation of 2-butene-1,4-diol and lafutidine were studied by HPLC on two kinds of chiral columns: (S,S)-Whelk-O 1 and ChiraSpher. The isomers of 2-butene-1,4-diol can be separated on both chiral columns while the isomers of lafutidine can only be resolved on ChiraSpher column. The influence of different type and amount of mobile phase modifier on the isomers separation was extensively studied. The resolution of cis and trans isomers of 2-butene-1,4-diol was 2.61on (S,S)-Whelk-O 1 column with hexane-ethanol (97:3, v/v) as the mobile phase. The resolution of lafutidine was 1.89 on ChiraSpher column with hexane-ethanol-THF-diethylamine (92:3:5:0.1, v/v/v/v) as the mobile phase. LC-MS methods were developed to identify the isomer peaks.展开更多
The aromaticity of all possible substituted fullerene isomers of C18N2, C18B2, C18BN, and their molecular ions which originate from the C20 （Ih） cage were studied by the topological resonance energy （TRE） and the ...The aromaticity of all possible substituted fullerene isomers of C18N2, C18B2, C18BN, and their molecular ions which originate from the C20 （Ih） cage were studied by the topological resonance energy （TRE） and the percentage topological resonance energy methods. The relationship between the aromaticity of C18BxNy isomers and the sites where the heteroatoms dope at the C20 （Ih） cage is discussed. Calculation results show that at the neutral and cationic states all the isomers are predicted to be antiaromatic with negative TREs, but their polyvalent anions are predicted to be aromatic with positive TREs. The most stable isomer is formed by heteroatom doping at the 1,11-sites in C18N2. C18B2, and C18BN. Heterofullerenes are more aromatic than C20. The stability order in the neutral states is C18N2〉C18BN〉C18B2〉C20. The stability order in closed-shell is C18B2^8- 〉C20^6- 〉C18BN^6- 〉C18N2^4-. This predicts theoretically that their polyvalent anions have high aromaticity.展开更多
Increasing interest has been paid to the development of earth‐abundant metal complexes as promising surrogates of platinum for the electrocatalytically and photocatalytically driven hydrogen evolution reaction.In thi...Increasing interest has been paid to the development of earth‐abundant metal complexes as promising surrogates of platinum for the electrocatalytically and photocatalytically driven hydrogen evolution reaction.In this work,we report on molecular H2‐evolving catalysts based on two octahedral complexes of cobalt thiosemicarbazide,fac‐[Co(Htsc)3]Cl3·3H2O(C1,Htsc=thiosemicarbazide)and mer‐[Co(Htsc)3]Cl3·4H2O(C2),which have facial(fac)and meridional(mer)geometry,respectively.Electrochemical studies confirmed that both C1and C2are active electrocatalysts in MeOH solution using acetic acid as the proton source,with the same overpotential of^640mV and TOF of^210s–1.The complex C1also exhibits electrocatalytic activity for hydrogen evolution reaction in aqueous media free of organic solvent with a moderate overpotential(560mV).Visible light‐driven hydrogen evolution experiments were carried out in combination with fluorescein as photosensitizer and triethylamine as sacrificial reductant in homogeneous environments.Our studies showed that both C1and C2can be used as efficient proton‐reduction catalysts in purely aqueous solution and have the same photocatalytic activities.A TOF of125h–1with a TON of900for photocatalytic H2generation using C1and C2in water were achieved for the noble‐metal‐free homogeneous system.It should be noted that this is the first reported study investigating the effect on the catalytic hydrogen production performance of using fac‐and mer‐isomers of molecular catalysts.展开更多
Configuration-constrained potential-energy-surface calculations are performed to investigate high-K isomers in97Y,130Ba,176Yb,177Lu,and178Hf that were observed to have increased electric quadrupole moments but decreas...Configuration-constrained potential-energy-surface calculations are performed to investigate high-K isomers in97Y,130Ba,176Yb,177Lu,and178Hf that were observed to have increased electric quadrupole moments but decreased charge radii relative to the states on which they are built.Taking into account the efects of deformation change and unpaired protons,our calculations can reproduce the enhancement of electric quadrupole moments for the isomers in97Y,130Ba,176Yb,177Lu and the Kπ=8 isomer in178Hf,and can reproduce the reduction of charge radii for the Kπ=27/2 isomer in97Y and the Kπ=16+isomer in178Hf.展开更多
Recent experiments open up the possibility to investigate oblate rotation-aligned states and prolate high-K isomers in neutron-rich tungsten isotopes.In the present work,we perform the projected-shell-model calculatio...Recent experiments open up the possibility to investigate oblate rotation-aligned states and prolate high-K isomers in neutron-rich tungsten isotopes.In the present work,we perform the projected-shell-model calculations for A ～ 190 tungsten nuclei.The 190 W results are compared with experimental data.The observed 8 + isomer is assigned as a two-quasiproton K π = 8 + configuration.Low-lying high-K four-quasiparticle states are predicted.Of particular interest is the prediction of the K π = 20 + state in 190,192 W,which may form a long-lived spin trap.In competition with the prolate high-K states,rotational alignment leads to near-yrast collective oblate rotation.展开更多
基金Financial support fromthe National Natural Science Foundation of China(20401012),the Key Project of Chinese Ministry of Education (Grant 205008)and Tianjin Normal University.
文摘Energy raolved mass spectra (ERMS) of 2, 3-DNT and 3, 5-DNT isomers was mported. The fragmentation of this pair of DNTisomers was studied by ERMS in electron impact (EI),and their breakdown curves were discussed , These nitraromaic isomers can be characterized according to the differences between their ERMS in MS/MS
文摘The cis and trans isomers separation of 2-butene-1,4-diol and lafutidine were studied by HPLC on two kinds of chiral columns: (S,S)-Whelk-O 1 and ChiraSpher. The isomers of 2-butene-1,4-diol can be separated on both chiral columns while the isomers of lafutidine can only be resolved on ChiraSpher column. The influence of different type and amount of mobile phase modifier on the isomers separation was extensively studied. The resolution of cis and trans isomers of 2-butene-1,4-diol was 2.61on (S,S)-Whelk-O 1 column with hexane-ethanol (97:3, v/v) as the mobile phase. The resolution of lafutidine was 1.89 on ChiraSpher column with hexane-ethanol-THF-diethylamine (92:3:5:0.1, v/v/v/v) as the mobile phase. LC-MS methods were developed to identify the isomer peaks.
文摘The aromaticity of all possible substituted fullerene isomers of C18N2, C18B2, C18BN, and their molecular ions which originate from the C20 （Ih） cage were studied by the topological resonance energy （TRE） and the percentage topological resonance energy methods. The relationship between the aromaticity of C18BxNy isomers and the sites where the heteroatoms dope at the C20 （Ih） cage is discussed. Calculation results show that at the neutral and cationic states all the isomers are predicted to be antiaromatic with negative TREs, but their polyvalent anions are predicted to be aromatic with positive TREs. The most stable isomer is formed by heteroatom doping at the 1,11-sites in C18N2. C18B2, and C18BN. Heterofullerenes are more aromatic than C20. The stability order in the neutral states is C18N2〉C18BN〉C18B2〉C20. The stability order in closed-shell is C18B2^8- 〉C20^6- 〉C18BN^6- 〉C18N2^4-. This predicts theoretically that their polyvalent anions have high aromaticity.
基金supported by the National Natural Science Foundation of China (21641011, 21773313)the Natural Science Foundation of Fujian Province (2015J01053, 2016J01060)+1 种基金Program for New Century Excellent Talents in Fujian Province UniversityPromotion Program for Young and Middle-aged Teacher in Science, Technology Research of Huaqiao University (ZQN-PY104)~~
文摘Increasing interest has been paid to the development of earth‐abundant metal complexes as promising surrogates of platinum for the electrocatalytically and photocatalytically driven hydrogen evolution reaction.In this work,we report on molecular H2‐evolving catalysts based on two octahedral complexes of cobalt thiosemicarbazide,fac‐[Co(Htsc)3]Cl3·3H2O(C1,Htsc=thiosemicarbazide)and mer‐[Co(Htsc)3]Cl3·4H2O(C2),which have facial(fac)and meridional(mer)geometry,respectively.Electrochemical studies confirmed that both C1and C2are active electrocatalysts in MeOH solution using acetic acid as the proton source,with the same overpotential of^640mV and TOF of^210s–1.The complex C1also exhibits electrocatalytic activity for hydrogen evolution reaction in aqueous media free of organic solvent with a moderate overpotential(560mV).Visible light‐driven hydrogen evolution experiments were carried out in combination with fluorescein as photosensitizer and triethylamine as sacrificial reductant in homogeneous environments.Our studies showed that both C1and C2can be used as efficient proton‐reduction catalysts in purely aqueous solution and have the same photocatalytic activities.A TOF of125h–1with a TON of900for photocatalytic H2generation using C1and C2in water were achieved for the noble‐metal‐free homogeneous system.It should be noted that this is the first reported study investigating the effect on the catalytic hydrogen production performance of using fac‐and mer‐isomers of molecular catalysts.
基金supported by the National Natural Science Foundation of China (Grant Nos. 11205120 and 11235001)the National Key Basic Research Program of China (Grant No. 2013CB834400)
文摘Configuration-constrained potential-energy-surface calculations are performed to investigate high-K isomers in97Y,130Ba,176Yb,177Lu,and178Hf that were observed to have increased electric quadrupole moments but decreased charge radii relative to the states on which they are built.Taking into account the efects of deformation change and unpaired protons,our calculations can reproduce the enhancement of electric quadrupole moments for the isomers in97Y,130Ba,176Yb,177Lu and the Kπ=8 isomer in178Hf,and can reproduce the reduction of charge radii for the Kπ=27/2 isomer in97Y and the Kπ=16+isomer in178Hf.
基金supported by the National Natural Science Foundation of China (Grant No. 10975006)
文摘Recent experiments open up the possibility to investigate oblate rotation-aligned states and prolate high-K isomers in neutron-rich tungsten isotopes.In the present work,we perform the projected-shell-model calculations for A ～ 190 tungsten nuclei.The 190 W results are compared with experimental data.The observed 8 + isomer is assigned as a two-quasiproton K π = 8 + configuration.Low-lying high-K four-quasiparticle states are predicted.Of particular interest is the prediction of the K π = 20 + state in 190,192 W,which may form a long-lived spin trap.In competition with the prolate high-K states,rotational alignment leads to near-yrast collective oblate rotation.
