Membrane permeability and intracellular diffusion of fluorescent probes determine staining selectivity of intracellular substructures.However,the relationship between the molecular structure of fluorescent probes and ...Membrane permeability and intracellular diffusion of fluorescent probes determine staining selectivity of intracellular substructures.However,the relationship between the molecular structure of fluorescent probes and their membrane permeability and intracellular distribution is poorly understood.In this paper,we reported a series of 1,8-naphthalimide dyes and carried out cell imaging experiments,and found that the presence of amino hydrogen in these dyes played a crucial role in their cell membrane permeability and intracellular distribution.The secondary amino group containing compounds 1-4 show excellent membrane permeability and strong fluorescence in living cells.While the tertiary amine containing dyes 5 and 6 can hardly permeate the cell membrane though they show extremely similar structure with compounds 2-4.Compound 1 can selectively image lipid droplets by selecting the wavelength of excitation light.With the specificity for lysosomes,2 and 4 have been used in long-term time-lapses imaging of lysosomal dynamics and tracking the process of lysosome-lysosome interaction,fusion and movement.The effect of hydrogen-containing amino substituent on the cell membrane permeability of fluorescent molecules is promising for the development of better biocompatible probes.展开更多
A series of fluorescent chemosensors 1-3 were synthesized to detect transition metal ions. At the room temperature, fluorescence intensities of these chemosensors in acetonitrile without transition metal ions were fou...A series of fluorescent chemosensors 1-3 were synthesized to detect transition metal ions. At the room temperature, fluorescence intensities of these chemosensors in acetonitrile without transition metal ions were found to be very weak, due to the process of the efficient intramolecular photoinduced electron transfer （PET）. However, after addition of the transition metal ions, the chemoscnsor 1-3 exhibits obvious fluorescence enhancement. Moreover, the intensity of the fluorescence emission of chemosensors increases significantly in the presence of Zn^2＋ and Cd^2＋. The fluorescent chemosensors with different polyamine as receptors show diverse affinity abilities to the transition metal ions and signal the receptor-metal ion interaction by the intensity change of fluorescence emission.展开更多
A series of fluorescent siloxane-polyurethanes（HPMS-PUs） containing an amino-functionalized,1 8-naphthalimide,fluorescent monomer（AABD） as a chain extender were synthesized.The properties of the HPMS-PUs were inve...A series of fluorescent siloxane-polyurethanes（HPMS-PUs） containing an amino-functionalized,1 8-naphthalimide,fluorescent monomer（AABD） as a chain extender were synthesized.The properties of the HPMS-PUs were investigated by UV–vis and fluorescence spectroscopies,thermogravimetric analysis and thermal migration behavior.The maximum absorption and emission wavelengths of HPMS-PUs showed a red shift of about 4 nm and a blue shift of about 9 nm,respectively,compared to those of AABD.The Stokes shifts of AABD and HPMS-PU2 were 3514 and 2931 cm 1,respectively.The quantum yield of HPMS-PU2 was 0.79,which was six times higher than that of AABD.Concentration self-quenching was observed in both AABD and HPMS-PUs.The fluorescence of HPMS-PUs was quite stable with respect to both temperature and fluorescence quencher effects.The thermal stability of HPMS-PUs increased with AABD content.The fluorophore units in the HPMS-PUs did not readily migrate.展开更多
4-Amino-1,8-naphthalimide(ANI) represents a valuable fluorophore from which a large number of probes have been derived in order to meet the requirements from the fields of biological sensing and imaging. In this revie...4-Amino-1,8-naphthalimide(ANI) represents a valuable fluorophore from which a large number of probes have been derived in order to meet the requirements from the fields of biological sensing and imaging. In this review, the major progresses of ANI-based fluorescent probes in the past decade have been highlighted and categorized into three trends. The future development of ANI probes is also expected. This review provides a great deal of references and illuminating comments which will be helpful for the researchers designing and using fluorescent probes.展开更多
The molecular geometries, frontier molecular orbital properties, and absorption and emission properties of three 4-phenoxy-1,8-naphthalimide derivatives, namely 4-phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（1）,4-...The molecular geometries, frontier molecular orbital properties, and absorption and emission properties of three 4-phenoxy-1,8-naphthalimide derivatives, namely 4-phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（1）,4-（2-tert-butylphenoxy）-N-（2-hydroxyethyl）-1,8-naphthalimide（2）, and 4-[2,4-di（tert-butyl）]phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（3）, are investigated by density functional theory（DFT） and time-dependent density functional theory（TD-DFT） calculations in conjunction with polarizable continuum models（PCMs）. Four functionals and ten basis sets are employed for 1 to calculate the electron transition energies, which were compared with the experimental observations. Our results reveal that the B3LYP/6-311＋G（d,p） method is the best choice to reproduce the experimental spectra. Moreover, the effects of substituents on the molecular geometries, electronic structures, absorption and emission spectra are also studied at the B3LYP/6-311＋G（d,p） level. We find that the gap between the highest occupied molecular orbital（HOMO） and the lowest unoccupied molecular orbital（LUMO） decreases with increasing the number of tert-butyl substituents onto the phenoxy groups, suggesting red-shift of the absorption and emission bands. This is related to the increase of conjugation from 1 to 2 and 3. Our calculations are in good agreement with the experimental results.展开更多
A new 3,4-disubstituted-l,8-naphthalimide derivative H1 was designed and synthesized as a selective fluorescent probe for Cu2＋ over miscellaneous metM ions in aqueous media. Upon mixing with Cup-＋ in CH3OH：H2O （1...A new 3,4-disubstituted-l,8-naphthalimide derivative H1 was designed and synthesized as a selective fluorescent probe for Cu2＋ over miscellaneous metM ions in aqueous media. Upon mixing with Cup-＋ in CH3OH：H2O （1：1, volume ratio）, the increase of fluorescence intensity and a bathochromic shift of absorbance of H1 could be observed with a notable color response （changing from yellow to pink）, htrthermore, Cu2＋ coordinates to the probe H1 and a 1：1 metal-ligand complex was formed.展开更多
A novel 1,8-naphthalimide-based OFF-ON type fluorogenic sydnone(Naph-Syd) is designed as bioorthogonal probe for imaging.Sydnone moiety efficiently quenches the native fluorescence of 1,8-naphthalimide,which can be re...A novel 1,8-naphthalimide-based OFF-ON type fluorogenic sydnone(Naph-Syd) is designed as bioorthogonal probe for imaging.Sydnone moiety efficiently quenches the native fluorescence of 1,8-naphthalimide,which can be restored with the enhancement of about 300-fold,after reacting with strained cyclooctynes to form pyrazole products(Naph-Pyr).The second-order rate constant of this bioorthogonal cycloaddition can be up to 2.5 L mol^-1s^-1,which benefits imaging of biomolecules at low concentrations in cellular environment.展开更多
The halogen as a kind of alkylating reagent is used to introduce new group to realize the fluorescence sensors efficient of metal ion detection. The substituent at C-4 position was double bromine, which defined that t...The halogen as a kind of alkylating reagent is used to introduce new group to realize the fluorescence sensors efficient of metal ion detection. The substituent at C-4 position was double bromine, which defined that the halogen as an alkylating reagent should be further researched and detected for Hg2＋. Therefore, the N-n-butyl-4-[di（bromoethyl）]amino-1,8-naphthalimide has been synthesized to detect some metal ions. The title compound has been prepared via substitute reaction and was characterized by IR, 1H NMR, 13 C NMR, and MS. It crystallizes in triclinic, space group P1 with a = 9.0071（18）, b = 9.804（2）, c = 13.073（3）A, α = 73.17（3）, β = 71.73（3）, γ = 62.95（3）°, Z = 2, V = 961.5（3） A3, Dc = 1.666 g/cm3, F（000） = 484, μ（Mo Kα） = 4.232 mm-1, R = 0.0429 and w R = 0.1004. The presence of intermolecular hydrogen bonds as well as π-π stacking interaction led to the stability of the compound. The fluorescence intensity was obviously lower than that of other ions when Hg2＋ was added with the concentration of 1 × 10^-5 mol·L-1.展开更多
Two 1,8-naphthalimide derivatives of 7H-benzimidazo[2,1,-a]benz[de] isoquino- lin-7-one（1） and 4-bromo-7H-benzimidazo[2,1,-a]benz[de]isoquinolin-7-one（2） have been synthesized and characterized by elemental analys...Two 1,8-naphthalimide derivatives of 7H-benzimidazo[2,1,-a]benz[de] isoquino- lin-7-one（1） and 4-bromo-7H-benzimidazo[2,1,-a]benz[de]isoquinolin-7-one（2） have been synthesized and characterized by elemental analysis, IR, 1H NMR, UV-Vis and fluorescence spectra. For the two compounds, density functional theory（DFT） calculations of the structures and natural population atomic charge analysis have been performed at the B3LYP/6-311G＊＊ level of theory. Based on Onsager reaction filed model and by using TD-DFT method at the B3LYP/6-311G＊＊ level, electron spectra of 1 and 2 with solvent effect in CHCl3 solvent have been predicted, which are in agreement with the experimental ones. Comparative studies on 1 and 2 indicate that introducing an electron-withdrawing group of Br into the 4-position of naphthalene ring in 2 does not significantly make the molecular geometry of 2 different from that of 1, but evidently changes the atomic charge redistribution, moves the positive-negative charges center and then changes the dipole moment in 2. Additionally, for compound 2, the existence of Br atom has also influenced the peak intensity and peak locations in both electron and fluorescence spectra.展开更多
目的探讨炎调方调过Fas/Caspase-8信号通路减轻脓毒症急性胃肠损伤小鼠炎症的机制。方法取70只BALB/c小鼠随机分为空白组、假手术组和造模小鼠组。通过盲肠结扎穿孔术(cecum ligation and puncture,CLP)构建脓毒症急性胃肠损伤小鼠模型...目的探讨炎调方调过Fas/Caspase-8信号通路减轻脓毒症急性胃肠损伤小鼠炎症的机制。方法取70只BALB/c小鼠随机分为空白组、假手术组和造模小鼠组。通过盲肠结扎穿孔术(cecum ligation and puncture,CLP)构建脓毒症急性胃肠损伤小鼠模型,将造模成功的小鼠随机分为模型组,炎调方低、中、高剂量组,ROCK抑制剂组。苏木素-伊红(HE)染色观察小鼠回肠组织病理学改变;ELISA法检测各组小鼠血清IL-17、IL-23水平;蛋白印迹法检测回肠组织Fas/Caspase-8信号通路蛋白Fas、FADD和Caspase-8的相对表达;TUNEL染色法检测回肠组织细胞凋亡情况。结果与空白组相比,模型组小鼠回肠组织肠黏膜萎缩明显、绒毛排列杂乱,可见断裂、脱落,上皮细胞细胞坏死脱落,炎症细胞浸润明显,小鼠血清中IL-17、IL-23水平升高(P<0.05),回肠组织中Fas、FADD和Caspase-8蛋白的表达升高(P<0.05),肠上皮细胞呈现明显的凋亡现象(P<0.05)。与模型组相比,炎调方组小鼠的回肠组织病理学改变均得到不同程度的改善,血清中IL-17、IL-23水平降低(P<0.05),且回肠组织中Fas、FADD和Caspase-8蛋白的表达降低(P<0.05),肠上皮细胞凋亡减少(P<0.05)。结论炎调方可以减轻肠黏膜组织损伤和肠道组织炎症反应,可能是通过调控Fas/Caspase-8信号通路抑制脓毒症急性胃肠损伤小鼠的肠上皮细胞凋亡来发挥作用的。展开更多
A series of new fluorescent chemosensors 5a--5e, composed of two aminonaphthalimide fluorophores and 2,6-bis（（N-aminoalkyl）aminocarboxy）pyridines, were prepared, characterized, and their fluorescent properties to-...A series of new fluorescent chemosensors 5a--5e, composed of two aminonaphthalimide fluorophores and 2,6-bis（（N-aminoalkyl）aminocarboxy）pyridines, were prepared, characterized, and their fluorescent properties to- wards heavy and transition metal （HTM） ions were investigated. Chemosensors 5e--Se exhibited high selectivity and sensitivity for Cu2＋ ion over other HTM ions with fluorescent quenching （green to colourless）. It clearly demonstrated that the length of the linkers （diamines） between the aminonaphthalimides and 2,6-dicarboxypyridine of 5a--Se was very important for their sensitivity and selectivity for Cu2~ ion over other HTM ions.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22278394,22078314 and 21908216)Dalian Institute of Chemical Physics(Nos.DICPI202227 and DICPI202142).
文摘Membrane permeability and intracellular diffusion of fluorescent probes determine staining selectivity of intracellular substructures.However,the relationship between the molecular structure of fluorescent probes and their membrane permeability and intracellular distribution is poorly understood.In this paper,we reported a series of 1,8-naphthalimide dyes and carried out cell imaging experiments,and found that the presence of amino hydrogen in these dyes played a crucial role in their cell membrane permeability and intracellular distribution.The secondary amino group containing compounds 1-4 show excellent membrane permeability and strong fluorescence in living cells.While the tertiary amine containing dyes 5 and 6 can hardly permeate the cell membrane though they show extremely similar structure with compounds 2-4.Compound 1 can selectively image lipid droplets by selecting the wavelength of excitation light.With the specificity for lysosomes,2 and 4 have been used in long-term time-lapses imaging of lysosomal dynamics and tracking the process of lysosome-lysosome interaction,fusion and movement.The effect of hydrogen-containing amino substituent on the cell membrane permeability of fluorescent molecules is promising for the development of better biocompatible probes.
基金supported by the National Natural Science Foundation of China(No.20332020,No.20472079).
文摘A series of fluorescent chemosensors 1-3 were synthesized to detect transition metal ions. At the room temperature, fluorescence intensities of these chemosensors in acetonitrile without transition metal ions were found to be very weak, due to the process of the efficient intramolecular photoinduced electron transfer （PET）. However, after addition of the transition metal ions, the chemoscnsor 1-3 exhibits obvious fluorescence enhancement. Moreover, the intensity of the fluorescence emission of chemosensors increases significantly in the presence of Zn^2＋ and Cd^2＋. The fluorescent chemosensors with different polyamine as receptors show diverse affinity abilities to the transition metal ions and signal the receptor-metal ion interaction by the intensity change of fluorescence emission.
基金Financial support from the 863 program (No. 2011AA02A204)
文摘A series of fluorescent siloxane-polyurethanes（HPMS-PUs） containing an amino-functionalized,1 8-naphthalimide,fluorescent monomer（AABD） as a chain extender were synthesized.The properties of the HPMS-PUs were investigated by UV–vis and fluorescence spectroscopies,thermogravimetric analysis and thermal migration behavior.The maximum absorption and emission wavelengths of HPMS-PUs showed a red shift of about 4 nm and a blue shift of about 9 nm,respectively,compared to those of AABD.The Stokes shifts of AABD and HPMS-PU2 were 3514 and 2931 cm 1,respectively.The quantum yield of HPMS-PU2 was 0.79,which was six times higher than that of AABD.Concentration self-quenching was observed in both AABD and HPMS-PUs.The fluorescence of HPMS-PUs was quite stable with respect to both temperature and fluorescence quencher effects.The thermal stability of HPMS-PUs increased with AABD content.The fluorophore units in the HPMS-PUs did not readily migrate.
基金supported by the National Natural Science Foundation of China (Nos. 21421005, 21576040 and 21776037)
文摘4-Amino-1,8-naphthalimide(ANI) represents a valuable fluorophore from which a large number of probes have been derived in order to meet the requirements from the fields of biological sensing and imaging. In this review, the major progresses of ANI-based fluorescent probes in the past decade have been highlighted and categorized into three trends. The future development of ANI probes is also expected. This review provides a great deal of references and illuminating comments which will be helpful for the researchers designing and using fluorescent probes.
基金supported by the Scientific Research Fund of Hubei Provincial Education Department(No.Q20122909)the Open Fund of Key Laboratory of Biologic Resources Protection and Utilization of Hubei Province(No.PKLHB1314)the First-class Discipline of Forestry in Hubei Minzu University
文摘The molecular geometries, frontier molecular orbital properties, and absorption and emission properties of three 4-phenoxy-1,8-naphthalimide derivatives, namely 4-phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（1）,4-（2-tert-butylphenoxy）-N-（2-hydroxyethyl）-1,8-naphthalimide（2）, and 4-[2,4-di（tert-butyl）]phenoxy-N-（2-hydroxyethyl）-1,8-naphthalimide（3）, are investigated by density functional theory（DFT） and time-dependent density functional theory（TD-DFT） calculations in conjunction with polarizable continuum models（PCMs）. Four functionals and ten basis sets are employed for 1 to calculate the electron transition energies, which were compared with the experimental observations. Our results reveal that the B3LYP/6-311＋G（d,p） method is the best choice to reproduce the experimental spectra. Moreover, the effects of substituents on the molecular geometries, electronic structures, absorption and emission spectra are also studied at the B3LYP/6-311＋G（d,p） level. We find that the gap between the highest occupied molecular orbital（HOMO） and the lowest unoccupied molecular orbital（LUMO） decreases with increasing the number of tert-butyl substituents onto the phenoxy groups, suggesting red-shift of the absorption and emission bands. This is related to the increase of conjugation from 1 to 2 and 3. Our calculations are in good agreement with the experimental results.
文摘A new 3,4-disubstituted-l,8-naphthalimide derivative H1 was designed and synthesized as a selective fluorescent probe for Cu2＋ over miscellaneous metM ions in aqueous media. Upon mixing with Cup-＋ in CH3OH：H2O （1：1, volume ratio）, the increase of fluorescence intensity and a bathochromic shift of absorbance of H1 could be observed with a notable color response （changing from yellow to pink）, htrthermore, Cu2＋ coordinates to the probe H1 and a 1：1 metal-ligand complex was formed.
基金financially supported by the National Natural Science Foundation of China (No.21803030)the National Thousand Young Talents Program+1 种基金the Jiangsu Specially-Appointed Professor Planthe NSF of Jiangsu Province (No.BK20170631) in China
文摘A novel 1,8-naphthalimide-based OFF-ON type fluorogenic sydnone(Naph-Syd) is designed as bioorthogonal probe for imaging.Sydnone moiety efficiently quenches the native fluorescence of 1,8-naphthalimide,which can be restored with the enhancement of about 300-fold,after reacting with strained cyclooctynes to form pyrazole products(Naph-Pyr).The second-order rate constant of this bioorthogonal cycloaddition can be up to 2.5 L mol^-1s^-1,which benefits imaging of biomolecules at low concentrations in cellular environment.
基金supported by the National Natural Science Foundation of China(No.31572042)the Research Science Foundation in Technology Innovation of Harbin(No.2015RAYXJ010)
文摘The halogen as a kind of alkylating reagent is used to introduce new group to realize the fluorescence sensors efficient of metal ion detection. The substituent at C-4 position was double bromine, which defined that the halogen as an alkylating reagent should be further researched and detected for Hg2＋. Therefore, the N-n-butyl-4-[di（bromoethyl）]amino-1,8-naphthalimide has been synthesized to detect some metal ions. The title compound has been prepared via substitute reaction and was characterized by IR, 1H NMR, 13 C NMR, and MS. It crystallizes in triclinic, space group P1 with a = 9.0071（18）, b = 9.804（2）, c = 13.073（3）A, α = 73.17（3）, β = 71.73（3）, γ = 62.95（3）°, Z = 2, V = 961.5（3） A3, Dc = 1.666 g/cm3, F（000） = 484, μ（Mo Kα） = 4.232 mm-1, R = 0.0429 and w R = 0.1004. The presence of intermolecular hydrogen bonds as well as π-π stacking interaction led to the stability of the compound. The fluorescence intensity was obviously lower than that of other ions when Hg2＋ was added with the concentration of 1 × 10^-5 mol·L-1.
基金Supported by Doctor Foundation of Shandong Province(No.BS2010CL021)Natural Science Foundation of Shandong Province(ZR2009AL020)Jiangsu Key Laboratory for Chemistry of Low-dimensional Materials P.R.China(JSKC12106 and JSKC12107)
文摘Two 1,8-naphthalimide derivatives of 7H-benzimidazo[2,1,-a]benz[de] isoquino- lin-7-one（1） and 4-bromo-7H-benzimidazo[2,1,-a]benz[de]isoquinolin-7-one（2） have been synthesized and characterized by elemental analysis, IR, 1H NMR, UV-Vis and fluorescence spectra. For the two compounds, density functional theory（DFT） calculations of the structures and natural population atomic charge analysis have been performed at the B3LYP/6-311G＊＊ level of theory. Based on Onsager reaction filed model and by using TD-DFT method at the B3LYP/6-311G＊＊ level, electron spectra of 1 and 2 with solvent effect in CHCl3 solvent have been predicted, which are in agreement with the experimental ones. Comparative studies on 1 and 2 indicate that introducing an electron-withdrawing group of Br into the 4-position of naphthalene ring in 2 does not significantly make the molecular geometry of 2 different from that of 1, but evidently changes the atomic charge redistribution, moves the positive-negative charges center and then changes the dipole moment in 2. Additionally, for compound 2, the existence of Br atom has also influenced the peak intensity and peak locations in both electron and fluorescence spectra.
文摘目的探讨炎调方调过Fas/Caspase-8信号通路减轻脓毒症急性胃肠损伤小鼠炎症的机制。方法取70只BALB/c小鼠随机分为空白组、假手术组和造模小鼠组。通过盲肠结扎穿孔术(cecum ligation and puncture,CLP)构建脓毒症急性胃肠损伤小鼠模型,将造模成功的小鼠随机分为模型组,炎调方低、中、高剂量组,ROCK抑制剂组。苏木素-伊红(HE)染色观察小鼠回肠组织病理学改变;ELISA法检测各组小鼠血清IL-17、IL-23水平;蛋白印迹法检测回肠组织Fas/Caspase-8信号通路蛋白Fas、FADD和Caspase-8的相对表达;TUNEL染色法检测回肠组织细胞凋亡情况。结果与空白组相比,模型组小鼠回肠组织肠黏膜萎缩明显、绒毛排列杂乱,可见断裂、脱落,上皮细胞细胞坏死脱落,炎症细胞浸润明显,小鼠血清中IL-17、IL-23水平升高(P<0.05),回肠组织中Fas、FADD和Caspase-8蛋白的表达升高(P<0.05),肠上皮细胞呈现明显的凋亡现象(P<0.05)。与模型组相比,炎调方组小鼠的回肠组织病理学改变均得到不同程度的改善,血清中IL-17、IL-23水平降低(P<0.05),且回肠组织中Fas、FADD和Caspase-8蛋白的表达降低(P<0.05),肠上皮细胞凋亡减少(P<0.05)。结论炎调方可以减轻肠黏膜组织损伤和肠道组织炎症反应,可能是通过调控Fas/Caspase-8信号通路抑制脓毒症急性胃肠损伤小鼠的肠上皮细胞凋亡来发挥作用的。
文摘A series of new fluorescent chemosensors 5a--5e, composed of two aminonaphthalimide fluorophores and 2,6-bis（（N-aminoalkyl）aminocarboxy）pyridines, were prepared, characterized, and their fluorescent properties to- wards heavy and transition metal （HTM） ions were investigated. Chemosensors 5e--Se exhibited high selectivity and sensitivity for Cu2＋ ion over other HTM ions with fluorescent quenching （green to colourless）. It clearly demonstrated that the length of the linkers （diamines） between the aminonaphthalimides and 2,6-dicarboxypyridine of 5a--Se was very important for their sensitivity and selectivity for Cu2~ ion over other HTM ions.
