B3LYP/6-311＋＋G level were employed to obtain the optimized geometries and calculated frequency of HCOCl and HOCl complexes.Five stable isomers were obtained,and the one with ClO-H…O=C hydrogen bond was the most sta...B3LYP/6-311＋＋G level were employed to obtain the optimized geometries and calculated frequency of HCOCl and HOCl complexes.Five stable isomers were obtained,and the one with ClO-H…O=C hydrogen bond was the most stable among five stable isomers,the BSSE and ZPE corrected interaction energy were of-11.92 kJ/mol.The formation of hydrogen bonds made the H―O stretching modes of complexes red-shifted relative to that of the monomer.At 298.15 K and standard state,the formations of stable complexes were an exothermic and non-spontaneous process.展开更多
The vibrational dynamics of HOCl and HOBr between bending and OC1/OBr stretching coordinates with anharmonieity and Fermi coupling is studied with the classical dynamical potential approach. The quantal vibrational dy...The vibrational dynamics of HOCl and HOBr between bending and OC1/OBr stretching coordinates with anharmonieity and Fermi coupling is studied with the classical dynamical potential approach. The quantal vibrational dynamics is mostly mapped out by the classical nonlinear variables such as fixed points, except for the state energies, which are quantized. This approach is global in the sense that the focus is on a set of levels instead of individual ones. The dynamics of HOBr is demonstrated to be less complicated. The localized modes along the OCl/OBr stretching coordinates are also shown to have O-Br bonds more prone to dissociation.展开更多
Fluorescent probes have been widely employed in biological imaging and sensing.However,it is always a challenge to design probes with high sensitivity.In this work,based on rhodamine skeleton,we developed a general st...Fluorescent probes have been widely employed in biological imaging and sensing.However,it is always a challenge to design probes with high sensitivity.In this work,based on rhodamine skeleton,we developed a general strategy to construct sensitivity-enhanced fluorescent probe with the help of theoretical calculation for the first time.As a proof of concept,we synthesized a series of HOCl probes.Experiment results showed that with the C-9 of pyronin moiety of rhodamine stabilized by an electron donor group,probe DQF-S exhibited an importantly enhanced sensitivity(LOD:0.2 nmol/L)towards HOCl together with fast response time(<10 s).Moreover,due to the breaking symmetrical electron distribution by another electron donor group,the novel rhodamine probe DQF-S displayed a far red to near-infrared emission(>650 nm)and large Stokes shift.Bioimaging studies indicated that DQF-S can not only effectively detect basal HOCl in various types of cells,but also be successfully applied to image tumor tissue in vivo.These results demonstrate the potential of our design as a useful strategy to develop excellent fluorescent probes for bioimaging.展开更多
The reactive oxygen species(ROS) are tightly associated with endoplasmic reticulum(ER) stress.Thus,the deep and visual insight of aberrant ROS fluctuations in the ER can help us better investigate the ER stress-associ...The reactive oxygen species(ROS) are tightly associated with endoplasmic reticulum(ER) stress.Thus,the deep and visual insight of aberrant ROS fluctuations in the ER can help us better investigate the ER stress-associated pathology.In this work,a fluorescent probe ERC for HOCI detection in the ER based on phenothiazine-derived coumarin platform was developed.In the presence of HOCI,ERC exhibited an emission change from 609 nm to 503 nm within seconds.It also showed high sensitivity(0.44 μmol/L)and superb photostability.Significantly,ERC displayed low cytotoxicity,good cell membrane permeability,and appreciable ER-targetability.Ultimately,the probe was successfully utilized to image exogenous and endogenous HOCl in living cells and reveal the HOCI burst in cisplatin-treated cancer cells.展开更多
基金Supported by Key Natural Science Program of the Education Department of Sichuan Province(07ZB080)Scientific Research Foundation for Masters of Xichang College~~
文摘B3LYP/6-311＋＋G level were employed to obtain the optimized geometries and calculated frequency of HCOCl and HOCl complexes.Five stable isomers were obtained,and the one with ClO-H…O=C hydrogen bond was the most stable among five stable isomers,the BSSE and ZPE corrected interaction energy were of-11.92 kJ/mol.The formation of hydrogen bonds made the H―O stretching modes of complexes red-shifted relative to that of the monomer.At 298.15 K and standard state,the formations of stable complexes were an exothermic and non-spontaneous process.
基金Project supported by the Research Foundation from Ministry of Education of China (Grant No. 306020)the Specialized Research Fund for the Doctoral Program of Higher Education, China (Grant No. 20060003050)the National Natural Science Foundation of China (Grant No. 20373030)
文摘The vibrational dynamics of HOCl and HOBr between bending and OC1/OBr stretching coordinates with anharmonieity and Fermi coupling is studied with the classical dynamical potential approach. The quantal vibrational dynamics is mostly mapped out by the classical nonlinear variables such as fixed points, except for the state energies, which are quantized. This approach is global in the sense that the focus is on a set of levels instead of individual ones. The dynamics of HOBr is demonstrated to be less complicated. The localized modes along the OCl/OBr stretching coordinates are also shown to have O-Br bonds more prone to dissociation.
基金the National Natural Science Foundation of China(Nos.21877029,21735001)the National Key R&D Program of China(No.2019YFA0210103)+1 种基金the National Postdoctoral Program for Innovative Talents(No.BX20190110)the China Postdoctoral Science Foundation(No.2019M662758)。
文摘Fluorescent probes have been widely employed in biological imaging and sensing.However,it is always a challenge to design probes with high sensitivity.In this work,based on rhodamine skeleton,we developed a general strategy to construct sensitivity-enhanced fluorescent probe with the help of theoretical calculation for the first time.As a proof of concept,we synthesized a series of HOCl probes.Experiment results showed that with the C-9 of pyronin moiety of rhodamine stabilized by an electron donor group,probe DQF-S exhibited an importantly enhanced sensitivity(LOD:0.2 nmol/L)towards HOCl together with fast response time(<10 s).Moreover,due to the breaking symmetrical electron distribution by another electron donor group,the novel rhodamine probe DQF-S displayed a far red to near-infrared emission(>650 nm)and large Stokes shift.Bioimaging studies indicated that DQF-S can not only effectively detect basal HOCl in various types of cells,but also be successfully applied to image tumor tissue in vivo.These results demonstrate the potential of our design as a useful strategy to develop excellent fluorescent probes for bioimaging.
基金This work was supported by the Hubei Provincial Department of Education Science and Technology Research Projects(No.Q20182704).
文摘The reactive oxygen species(ROS) are tightly associated with endoplasmic reticulum(ER) stress.Thus,the deep and visual insight of aberrant ROS fluctuations in the ER can help us better investigate the ER stress-associated pathology.In this work,a fluorescent probe ERC for HOCI detection in the ER based on phenothiazine-derived coumarin platform was developed.In the presence of HOCI,ERC exhibited an emission change from 609 nm to 503 nm within seconds.It also showed high sensitivity(0.44 μmol/L)and superb photostability.Significantly,ERC displayed low cytotoxicity,good cell membrane permeability,and appreciable ER-targetability.Ultimately,the probe was successfully utilized to image exogenous and endogenous HOCl in living cells and reveal the HOCI burst in cisplatin-treated cancer cells.
