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1.
Ariel Carreño-Montero Luis A. Maldonado María Isabel Chávez Simón Hernández-Ortega Guillermo Delgado 《Tetrahedron letters》2019,60(48):151282
The synthesis of ethyl (2′-hydroxy-4′,5′-methylendioxophenyl)acetate, a fragment of the antihyperglycemic natural coumarin subcoriacin, is reported. We found an expeditious route to the title compound in five steps. Final metal catalyzed acid ethanolysis of the vinylic 1,1-methylthio methylsulfoxide derivative afforded the required aryl acetic ester, but in the absence of metal catalyst, an unexpected Pummerer rearrangement produced the 2,3-dimethylthiofuran derivative as the major product. This last result provides an alternative entry to 2,3-dimethlythiobenzofurans. 相似文献
2.
Dr. Andy Hernández Montoto Dr. Antoni Llopis-Lorente Mónica Gorbe José M. Terrés Dr. Roberto Cao-Milán Dr. Borja Díaz de Greñu Dr. María Alfonso Dr. Javier Ibañez Prof. María D. Marcos Dr. Mar Orzáez Dr. Reynaldo Villalonga Prof. Ramón Martínez-Máñez Dr. Félix Sancenón 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(36):8471-8478
Janus gold nanostar–mesoporous silica nanoparticle ( AuNSt–MSNP ) nanodevices able to release an entrapped payload upon irradiation with near infrared (NIR) light were prepared and characterized. The AuNSt surface was functionalized with a thiolated photolabile molecule ( 5 ), whereas the mesoporous silica face was loaded with a model drug (doxorubicin) and capped with proton-responsive benzimidazole-β-cyclodextrin supramolecular gatekeepers ( N 1 ). Upon irradiation with NIR-light, the photolabile compound 5 photodissociated, resulting in the formation of succinic acid, which induced the opening of the gatekeeper and cargo delivery. In the overall mechanism, the gold surface acts as a photochemical transducer capable of transforming the NIR-light input into a chemical messenger (succinic acid) that opens the supramolecular nanovalve. The prepared hybrid nanoparticles were non-cytotoxic to HeLa cells, until they were irradiated with a NIR laser, which led to intracellular doxorubicin release and hyperthermia. This induced a remarkable reduction in HeLa cells viability. 相似文献
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Beatriz Pelado Dr. Fawzi Abou‐Chahine Joaquín Calbo Dr. Rubén Caballero Dr. Pilar de la Cruz Dr. José M. Junquera‐Hernández Prof. Enrique Ortí Prof. Nikolai V. Tkachenko Prof. Fernando Langa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5814-5825
The role of π‐conjugated molecular bridges in through‐space and through‐bond electron transfer is studied by comparing two porphyrin–fullerene donor–acceptor (D–A) dyads. One dyad, ZnP–Ph–C60 (ZnP=zinc porphyrin), incorporates a phenyl bridge between D and A and behaves very similarly to analogous dyads studied previously. The second dyad, ZnP–EDOTV–C60, introduces an additional 3,4‐ethylenedioxythienylvinylene (EDOTV) unit into the conjugated bridge, which increases the distance between D and A, but, at the same time, provides increased electronic communication between them. Two essential outcomes that result from the introduction of the EDOTV unit in the bridge are as follows: 1) faster charge recombination, which indicates enhanced electronic coupling between the charge‐separated and ground electronic states; and 2) the disappearance of the intramolecular exciplex, which mediates photoinduced charge separation in the ZnP–Ph–C60 dyad. The latter can be interpreted as a gradual decrease in electronic coupling between locally excited singlet states of D and A when introducing the EDOTV unit into the D–A bridge. 相似文献
5.
Pingping Hu Dr. Manfred Erwin Schuster Dr. Zhiwei Huang Fei Xu Dr. Shifeng Jin Yaxin Chen Prof. Weiming Hua Prof. Dang Sheng Su Prof. Xingfu Tang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9619-9623
The identification of catalytically active sites (CASs) in heterogeneous catalysis is of vital importance to design and develop improved catalysts, but remains a great challenge. The CASs have been identified in the low‐temperature selective catalytic reduction of nitrogen oxides by ammonia (SCR) over a hollandite manganese oxide (HMO) catalyst with a rod‐shaped morphology and one‐dimensional tunnels. Electron microscopy and synchrotron X‐ray diffraction determine the surface and crystal structures of the one‐dimensional HMO rods closed by {100} side facets and {001} top facets. A combination of X‐ray absorption spectra, molecular probes with potassium and nitric oxide, and catalytic tests reveals that the CASs are located on the {100} side facets of the HMO rods rather than on the top facets or in the tunnels, and hence semi‐tunnel structural motifs on the {100} facets are evidenced to be the CASs of the SCR reaction. This work paves the way to further investigate the intrinsic mechanisms of SCR reactions. 相似文献
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Biodistribution study of free and microencapsulated 6‐methylcoumarin in Wistar rats by HPLC 下载免费PDF全文
Aura Rocío Hernández Luis Fernando Ospina Diana Marcela Aragón 《Biomedical chromatography : BMC》2015,29(2):176-181
A sensitive, specific and reproducible HPLC method has been developed and validated for the quantitative determination of 6‐methylcoumarin (6MC) in plasma and other tissues in Wistar rats. A C18 column was used with UV detection at 321 nm and a gradient system consisting of methanol‐deionized water was used as mobile phase. The retention time for 6MC was 14.921 min and no interfering peaks were observed for any of the matrices. Linear relationships (r2 > 0.997) were obtained between the peak height ratios and the corresponding biological sample concentrations over the range 0.4–12.8 µg/mL. Precision and accuracy were evaluated; the coefficient of variation and the relative error for all of the organs were <2 and 7%, respectively. The limit of quantitation was 0.20 µg/mL for the heart and 0.30 µg/mL for the other tissues evaluated. This HPLC method was successfully used in the determination of 6MC in the biodistribution study after administration of 200 mg/kg of both 6MC‐free and 6MC‐loaded polymeric microparticles. In this study, extensive 6MC was found, in both free and microencapsulated forms, in all the organs tested. The 6MC‐free showed a range of between 1.7 and 11.5 µg/g, while the microencapsulated 6MC showed concentrations of between 6.35 and 17.7 µg/g, suggesting that 6MC improved absorption rate. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
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9.
Can a Six‐Letter Alphabet Increase the Likelihood of Photochemical Assault to the Genetic Code? 下载免费PDF全文
Brennan Ashwood Marvin Pollum Prof. Dr. Carlos E. Crespo‐Hernández 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(46):16648-16656
In 2014, two unnatural nucleosides, d5SICS and dNaM, were shown to selectively base pair and replicate with high fidelity in a modified strain of E. coli, thus effectively expanding its genetic alphabet from four to six letters. More recently, a significant reduction in cell proliferation was reported in cells cultured with d5SICS, and putatively with dNaM, upon exposure to brief periods of near‐visible radiation. The photosensitizing properties of the lowest‐energy excited triplet state of both d5SICS and dNaM were implicated in their cytotoxicity. Importantly, however, the excited‐state mechanisms by which near‐visible excitation populates the triplet states of d5SICS and dNaM are currently unknown. In this study, steady‐state and time‐resolved spectroscopies are combined with quantum‐chemical calculations in order to reveal the excited‐state relaxation mechanisms leading to efficient population of the triplet states in these unnatural nucleosides in solution. It is shown that excitation of d5SICS or dNaM with near‐visible light leads overwhelmingly to ultrafast population of their triplet states on the femtosecond time scale. The results presented in this work lend strong support to the proposal that photoexcitation of these unnatural nucleosides can accelerate oxidatively generated damage to DNA and other biomolecules within the cellular environment. 相似文献
10.
César Adolfo Melo Hernández Edgar Yesid Lancheros Mayorga 《Mathematische Nachrichten》2020,293(4):721-734
In this paper, information about the instability of equilibrium solutions of a nonlinear family of localized reaction-diffusion equations in dimension one is provided. More precisely, explicit formulas to the equilibrium solutions are computed and, via analytic perturbation theory, the exact number of positive eigenvalues of the linear operator associated to the stability problem is analyzed. In addition, sufficient conditions for blow up of the solutions of the equation are also discussed. 相似文献