Porphyrins and methyl viologen(MV;) are widely used as a photosensitizer and an electron acceptor respectively in photoinduced electron transfer systems. Literatures covered numerous examples of photochemical studies ...Porphyrins and methyl viologen(MV;) are widely used as a photosensitizer and an electron acceptor respectively in photoinduced electron transfer systems. Literatures covered numerous examples of photochemical studies of porphyrins covalently linked to various electron acceptor units, such as viologen, which functioned as both a photosensitizer and an electron acceptor in the same molecule. However, the length of the linked chain between porphyrin and viologen is very important. To improve the rate of photoin-展开更多
This study developed a method on detecting methyl viologen(paraquat)using a CdTe-paper-based visual sensor.The CdTe Qdots were immobilized on the paper using glycerin.The volume percentages of CdTe in glycerin were op...This study developed a method on detecting methyl viologen(paraquat)using a CdTe-paper-based visual sensor.The CdTe Qdots were immobilized on the paper using glycerin.The volume percentages of CdTe in glycerin were optimized to be 50%.The sensing principle is that the methyl viologen quenches the fluorescence intensity of CdTe Qdots in a concentration dependent manner.The sensor is linearly response to the logarithm concentration of the methyl viologen in the range from 0.39μmol/L to 3.89 mmol/L with a detection limit of 0.16μmol/L and the corre-lation coefficient R^(2) of 0.99.Three parallel experiments at the methyl viologen concentration of 38.89μmol/L give a relative error of 2.45%,which indicates a good reproducibility.The sensor is not disturbed by other pestisides in-cluding omethoate,anilofos,machete and glyphosate isopropylamine salt.The advantages of this sensor are dis-posable,stable,convenient,and easy to operate.展开更多
By introducing a host molecule cucurbit[8]uril(CB[8]) into a charge transfer system containing an amphiphile 1-[11-(naphthalene-2-ylmethoxy)-11-oxoundecyl]pyridinium(NP) and an electron-deficient molecule methyl violo...By introducing a host molecule cucurbit[8]uril(CB[8]) into a charge transfer system containing an amphiphile 1-[11-(naphthalene-2-ylmethoxy)-11-oxoundecyl]pyridinium(NP) and an electron-deficient molecule methyl viologen(MV), a novel and anisotropic ternary building block was constructed by hostguest interactions, thereby leading to the morphology transformation of the final assemblies from thinfilms(NP/MV complexes) into diamond-like structures(NP/MV/CB[8] complexes). These intriguing assemblies were firstly discovered and were similar with the shape of well-known metal organic frameworks(MOFs), but just comprised three small organic molecules without metal ions. This finding can enrich the shape of current supramolecular assemblies and thus contributing to more potential applications in material science.展开更多
The use of nanotechnology in drug delivery is a rapidly expanding field. Biodegradable or nontoxic nanomaterials have the most promising application potentials in nanomedicine.
In DMSO/water(4:1),photolysis of the dihydroxy-Sn(IV)-rnesoporphyrin dimethyl ester (SnP)/methyl viologen(MV^(2+))/ethylene diamine tetraacetic acid(EDTA)ternary system produces methyl viologen cation radical with a q...In DMSO/water(4:1),photolysis of the dihydroxy-Sn(IV)-rnesoporphyrin dimethyl ester (SnP)/methyl viologen(MV^(2+))/ethylene diamine tetraacetic acid(EDTA)ternary system produces methyl viologen cation radical with a quantum yield of 0.67,much higher than that of systems with other metal complexes of rnesoporphyrin dimethyl ester.Neither EDTA nor MV^(2+) quenches the stationary fluorescence of SnP,implying that the reaction does not take place at the singlet state.With flash photolysis we obtain the T-T absorption spectrum of SnP(λ_(max)-440 nm).By following the decay of this absorption,the triplet life time of SnP is estimated to be 41 μs.The life time is related to the concentration of either MV^(2+) or EDTA.Good linear relationships are obtained by plotting τ_0/τ vs.the concentration of MV^(2+) or EDTA(Stern-Volmer plot),from which we determine the quenching constants:k_q(MV^(2+))=5.5×10~7 mol^(-7) s^(-1);kq(EDTA)=2.7×10~7 mol^(-1),s^(-1).The data suggests that upon photolysis of the above ternary system,both oxidative quenching and reductive quenching of the triplet state of the sensitizer are occurring.From the measured phosphorescence spectrum(λ_(max) 704nm)and the ground state redox potentials (E_(1/2)^(red)～-0.84V,E_(1/2)^(ox)～ Ag/AgCl,KCl(sat.)),we obtain the redox potential of triplet SnP to be E (P^+/P)～-0.33 V, E(P/P-)～+0.92 V.Matching this data with the redox potential of MV^(2+) and EDTA,we establish the fact that during the photolysis of the SnP/MV^(2+)/EDTA ternary system,both oxidative and reductive quenching are thermodynamically favorable processes.This is also the reason why the SnP sensitized reaction is much more efficient relative to other mesoporphyrin derivatives.展开更多
The use of nanotechnology in drug delivery is a rapidly expanding field. Biodegradable or nontoxic nanomaterials have the most promising application potentials in nanomedicine. Herein, we report a novel core-shell nan...The use of nanotechnology in drug delivery is a rapidly expanding field. Biodegradable or nontoxic nanomaterials have the most promising application potentials in nanomedicine. Herein, we report a novel core-shell nanoparticle with double shell coatings (silica and poly(D,L-lactide-co-glycolide) (PLGA)) with the total shell thickness of (8.7 ± 1.3) nm. The outer shell of PLGA is biodegradable and used for controlled and sustained release, and the inner shell of silica is mesoporous for the preservation of the chemical radiation therapeutic of methyl viologen (MV), an oxidant that produces reactive oxygen species during cancer radiation therapy. The dissolution time course data and transmission electron microscopy images showed that the novel nanoparticles (Au@SiO2&PLGA) have been successfully prepared, and silica and PLGA coated well the gold (Au) template surfaces. Nano- capsules (MV@SiO2&PLGA) were obtained after the gold templates were dissolved using sodium cyanide. The sustained release property was characterized through detecting fluorescence quenching time course of fluorescent isothiocyanate after mixing with MV@SiO2&PLGA nanocapsules that encapsulate MV molecules. The sustained release of MV molecules could be extended to approximately four weeks. This novel delivery system has high potential in future application for the delivery of therapeutic drugs, particularly for the treatment of cancer by radiation therapy.展开更多
Viologens (<i>N,N'</i>-dimethyl-4,4-bipyridinium) are advanced functional materials, found important applications in electrochromic devices, molecular machines, organic batteries, and carbohydrate oxid...Viologens (<i>N,N'</i>-dimethyl-4,4-bipyridinium) are advanced functional materials, found important applications in electrochromic devices, molecular machines, organic batteries, and carbohydrate oxidation catalysts in alkaline fuel. In this article, we investigated the design, synthesis and photophysical properties of <i>N,N'</i>-dimethyl-2,5-Bis(pyridinium)oxadiazole <b>4</b> and its precursor 2,5- Bis(pyridine)oxadiazole<b> 2</b>. The crystal structure and photophysical properties of viologen <b>4</b> and precursor <b>2</b> have been determined. The viologen molecule <b>4</b> crystallized in monoclinic form, space group <i>P</i>2<sub>1</sub>/<i>n</i> with four molecules in unit cell. Precursor molecule <b>2</b> also crystalized in monoclinic form, space group <i>C</i>2/<i>c</i> with four molecules in unit cell. From X-rd data, we found three cations in the molecular structure of viologen molecule <b>4</b>, which is unusual in viologens. In the three-dimensional molecular packing diagram of molecule <b>4</b>, the three cations and iodate anions are stabilized by C···C, C···I, N···I, N···H, H···I, N—H···I and C—H···I. The dihedral angle between planes having oxadiazole and two benzene rings are 5°and 8°, suggesting the molecule <b>4</b> is a slightly strained one. The molecular structure of precursor molecule <b>2</b> stabilized by C···C and N···H short contacts between the molecules. The molecule <b>4</b> displayed strong absorbance at 315 nm and emissions between 390 - 410 nm.展开更多
基金Supported by the National Natural Science Foundation of China
文摘Porphyrins and methyl viologen(MV;) are widely used as a photosensitizer and an electron acceptor respectively in photoinduced electron transfer systems. Literatures covered numerous examples of photochemical studies of porphyrins covalently linked to various electron acceptor units, such as viologen, which functioned as both a photosensitizer and an electron acceptor in the same molecule. However, the length of the linked chain between porphyrin and viologen is very important. To improve the rate of photoin-
基金supported by the National Natural Science Foundation of China(Nos.21273059,21003032)the State Key Laboratory of Urban Water Resource and Environment(Harbin Institute of Tech-nology)(No.2014DX09)+1 种基金the Fundamental Research Funds for the Central Universities(No.HIT.KISTP.201407)Harbin Science and Technology Research Council(No.2014RFXXJ063).
文摘This study developed a method on detecting methyl viologen(paraquat)using a CdTe-paper-based visual sensor.The CdTe Qdots were immobilized on the paper using glycerin.The volume percentages of CdTe in glycerin were optimized to be 50%.The sensing principle is that the methyl viologen quenches the fluorescence intensity of CdTe Qdots in a concentration dependent manner.The sensor is linearly response to the logarithm concentration of the methyl viologen in the range from 0.39μmol/L to 3.89 mmol/L with a detection limit of 0.16μmol/L and the corre-lation coefficient R^(2) of 0.99.Three parallel experiments at the methyl viologen concentration of 38.89μmol/L give a relative error of 2.45%,which indicates a good reproducibility.The sensor is not disturbed by other pestisides in-cluding omethoate,anilofos,machete and glyphosate isopropylamine salt.The advantages of this sensor are dis-posable,stable,convenient,and easy to operate.
基金the financial supports from the National Natural Science Foundation of China (Nos. 31860516, 21662009, 21702037)Frontiers Science Center for Asymmetric Synthesis and Medicinal Molecules, Department of Education, Guizhou Province [Qianjiaohe KY No. (2020)004]Program of Introducing Talents of Discipline to Universities of China (111 Program, No. D20023)。
文摘By introducing a host molecule cucurbit[8]uril(CB[8]) into a charge transfer system containing an amphiphile 1-[11-(naphthalene-2-ylmethoxy)-11-oxoundecyl]pyridinium(NP) and an electron-deficient molecule methyl viologen(MV), a novel and anisotropic ternary building block was constructed by hostguest interactions, thereby leading to the morphology transformation of the final assemblies from thinfilms(NP/MV complexes) into diamond-like structures(NP/MV/CB[8] complexes). These intriguing assemblies were firstly discovered and were similar with the shape of well-known metal organic frameworks(MOFs), but just comprised three small organic molecules without metal ions. This finding can enrich the shape of current supramolecular assemblies and thus contributing to more potential applications in material science.
基金supported by NSFC (no. 30700151)Academic Innovation Incubation Program from UESTC (no. Y02018023601062)in part by the Fujii-Otsuka International Scientific Exchange Fund from Tokushima University of Japan (795001002b)
文摘The use of nanotechnology in drug delivery is a rapidly expanding field. Biodegradable or nontoxic nanomaterials have the most promising application potentials in nanomedicine.
文摘In DMSO/water(4:1),photolysis of the dihydroxy-Sn(IV)-rnesoporphyrin dimethyl ester (SnP)/methyl viologen(MV^(2+))/ethylene diamine tetraacetic acid(EDTA)ternary system produces methyl viologen cation radical with a quantum yield of 0.67,much higher than that of systems with other metal complexes of rnesoporphyrin dimethyl ester.Neither EDTA nor MV^(2+) quenches the stationary fluorescence of SnP,implying that the reaction does not take place at the singlet state.With flash photolysis we obtain the T-T absorption spectrum of SnP(λ_(max)-440 nm).By following the decay of this absorption,the triplet life time of SnP is estimated to be 41 μs.The life time is related to the concentration of either MV^(2+) or EDTA.Good linear relationships are obtained by plotting τ_0/τ vs.the concentration of MV^(2+) or EDTA(Stern-Volmer plot),from which we determine the quenching constants:k_q(MV^(2+))=5.5×10~7 mol^(-7) s^(-1);kq(EDTA)=2.7×10~7 mol^(-1),s^(-1).The data suggests that upon photolysis of the above ternary system,both oxidative quenching and reductive quenching of the triplet state of the sensitizer are occurring.From the measured phosphorescence spectrum(λ_(max) 704nm)and the ground state redox potentials (E_(1/2)^(red)～-0.84V,E_(1/2)^(ox)～ Ag/AgCl,KCl(sat.)),we obtain the redox potential of triplet SnP to be E (P^+/P)～-0.33 V, E(P/P-)～+0.92 V.Matching this data with the redox potential of MV^(2+) and EDTA,we establish the fact that during the photolysis of the SnP/MV^(2+)/EDTA ternary system,both oxidative and reductive quenching are thermodynamically favorable processes.This is also the reason why the SnP sensitized reaction is much more efficient relative to other mesoporphyrin derivatives.
基金supported by the National Natural Science Foundation of China (Grant No. 30700151)Fujii-Otsuka International Scientific Exchange Fund from Tokushima University of Japan (Grant No.795001002b)Innovative Talent Incubation Program for Youth from University of Elec-tronic Science and Technology of China (Grant No. Y02018023601062)
文摘The use of nanotechnology in drug delivery is a rapidly expanding field. Biodegradable or nontoxic nanomaterials have the most promising application potentials in nanomedicine. Herein, we report a novel core-shell nanoparticle with double shell coatings (silica and poly(D,L-lactide-co-glycolide) (PLGA)) with the total shell thickness of (8.7 ± 1.3) nm. The outer shell of PLGA is biodegradable and used for controlled and sustained release, and the inner shell of silica is mesoporous for the preservation of the chemical radiation therapeutic of methyl viologen (MV), an oxidant that produces reactive oxygen species during cancer radiation therapy. The dissolution time course data and transmission electron microscopy images showed that the novel nanoparticles (Au@SiO2&PLGA) have been successfully prepared, and silica and PLGA coated well the gold (Au) template surfaces. Nano- capsules (MV@SiO2&PLGA) were obtained after the gold templates were dissolved using sodium cyanide. The sustained release property was characterized through detecting fluorescence quenching time course of fluorescent isothiocyanate after mixing with MV@SiO2&PLGA nanocapsules that encapsulate MV molecules. The sustained release of MV molecules could be extended to approximately four weeks. This novel delivery system has high potential in future application for the delivery of therapeutic drugs, particularly for the treatment of cancer by radiation therapy.
文摘Viologens (<i>N,N'</i>-dimethyl-4,4-bipyridinium) are advanced functional materials, found important applications in electrochromic devices, molecular machines, organic batteries, and carbohydrate oxidation catalysts in alkaline fuel. In this article, we investigated the design, synthesis and photophysical properties of <i>N,N'</i>-dimethyl-2,5-Bis(pyridinium)oxadiazole <b>4</b> and its precursor 2,5- Bis(pyridine)oxadiazole<b> 2</b>. The crystal structure and photophysical properties of viologen <b>4</b> and precursor <b>2</b> have been determined. The viologen molecule <b>4</b> crystallized in monoclinic form, space group <i>P</i>2<sub>1</sub>/<i>n</i> with four molecules in unit cell. Precursor molecule <b>2</b> also crystalized in monoclinic form, space group <i>C</i>2/<i>c</i> with four molecules in unit cell. From X-rd data, we found three cations in the molecular structure of viologen molecule <b>4</b>, which is unusual in viologens. In the three-dimensional molecular packing diagram of molecule <b>4</b>, the three cations and iodate anions are stabilized by C···C, C···I, N···I, N···H, H···I, N—H···I and C—H···I. The dihedral angle between planes having oxadiazole and two benzene rings are 5°and 8°, suggesting the molecule <b>4</b> is a slightly strained one. The molecular structure of precursor molecule <b>2</b> stabilized by C···C and N···H short contacts between the molecules. The molecule <b>4</b> displayed strong absorbance at 315 nm and emissions between 390 - 410 nm.
