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91.
Kadish KM Wang LL Thuriere A Giribabu L Garcia R Van Caemelbecke E Bear JL 《Inorganic chemistry》2003,42(25):8309-8319
Three Ru2(5+) diruthenium complexes, (4,0) Ru2(2-CH3ap)4Cl, (3,1) Ru2(2-Fap)4Cl, and (3,1) Ru2(2,4,6-F3ap)4Cl where ap is the 2-anilinopyridinate anion, were examined as to their electrochemical and spectroelectrochemical properties in five different nonaqueous solvents (CH2Cl2, THF, PhCN, DMF, and DMSO). Each compound undergoes a single one-electron metal-centered oxidation in THF, DMF, and DMSO and two one-electron metal-centered oxidations in CH2Cl2 and PhCN. The three diruthenium complexes also undergo two reductions in each solvent except for CH2Cl2, and these electrode processes are assigned as Ru2(5+/4+) and Ru2(4+/3+). Each neutral, singly reduced, and singly oxidized species was characterized by UV-vis thin-layer spectroelectrochemistry, and the data are discussed in terms of the most probable electronic configuration of the compound in solution. The three neutral complexes contain three unpaired electrons as indicated by magnetic susceptibility measurements using the Evans method (3.91-3.95 muB), and the electronic configuration is assigned as sigma2pi4delta2pi(*2)delta, independent of the solvent. The three singly oxidized compounds have two unpaired electrons in CD2Cl2, DMSO-d6, or CD3CN (2.65-3.03 muB), and the electronic configuration is here assigned as sigma2pi4delta2pi(*2). The singly reduced compound also has two unpaired electrons (2.70-2.80 muB) in all three solvents, consistent with the electronic configuration sigma2pi4delta2pi(*2)delta(*2) or sigma2pi4delta2pi(*3)delta*. Finally, the overall effect of solvent on the number of observed redox processes is discussed in terms of solvent binding, and several formation constants were calculated. 相似文献
92.
Thermolysis of a 2'-[(16)O]-O-benzoyl-[(17)O]-5'-O-(tert-butyldimethylsilyl)-O(2),3'-cyclouridine derivative gave the more stable 3'-[(17)O]-O-benzoyl-[(16)O]- 5'-O-(tert-butyldimethylsilyl)-O(2),2'-cyclouridine isomer, which was converted into 3'-[(17)O]-2'-azido-2'-deoxyuridine by deprotection and nucleophilic ring opening at C2' with lithium azide. The 5'-diphosphate was prepared by nucleophilic displacement of the 5'-O-tosyl group with tris(tetrabutylammonium) hydrogen pyrophosphate. Model reactions gave (16)O and (18)O isotopomers, and base-promoted hydrolysis of an O(2),2'-cyclonucleoside gave stereodefined access to 3'-[(18)O]-1-(beta-D-arabinofuranosyl)uracil. Inactivation of ribonucleoside diphosphate reductase with 2'-azido-2'-deoxynucleotides results in appearance of EPR signals for a nitrogen-centered radical derived from azide, and 3'-[(17)O]-2'-azido-2'-deoxyuridine 5'-diphosphate provides an isotopomer to perturb EPR spectra in a predictable manner. 相似文献
93.
[reaction: see text]. The first total syntheses of four stereoisomers of 4alpha-hydroxy-1beta,7beta-peroxy-10betaH-guaia-5-ene are reported starting from the readily available (+)-dihydrocarvone. These compounds have been synthesized from dienes (-)-isoguaiene and (-)-10-epi-isoguaiene by tandem ene hydroperoxylation-[4 + 2] cycloaddition with O(2) followed by selective reduction. The structure of the natural 4alpha-hydroxy-1beta,7beta-peroxy-10betaH-guaia-5-ene isolated from Liabum floribundum has been confirmed. 相似文献
94.
A. B. Garcia E. R. Galán J. A. S. Blázquez C. V. Calahorro 《Journal of Thermal Analysis and Calorimetry》1986,31(2):247-251
The thermal behaviour of some 2-benzylamino-2-deoxyheptonic acids obtained from 2-benzylamino-2-deoxy-D-glycero-L-gluco, 2-benzylamino-2-deoxy-D-glycero-D-ido and 2-benzylamino-2-deoxy-D-glycero-D-taloheptononitriles (reported) previously has been studied in air (static atmosphere) and N2 (dynamic atmosphere, flow rate 200 ml/min).
Zusammenfassung Das thermische Verhalten einiger aus 2-Benzylamino-2-desoxy-D-glycero-L-gluco-, 2-Benzylamino-2-desoxy-D-glycero-D-ido und 2-Benzylamino-2-desoxy-D-glycero-D-talo-heplononitril (kürzlich beschrieben) erhaltenen 2-Benzylamino-2-desoxy-heptonsäuren wurde ín Luft (statische Atmosphäre) und N2 (dynamische Atmosphäre, Strömungsgeschwindigkeit 200 ml/min) untersucht.
( 200 /) 2--2- , 2--2---uepo-L, 2-2- ---- 2-2--- -- 2--2----ma .相似文献
95.
Mina AbdolahZadeh A. Catarina C. Esteves Sybrand van der Zwaag Santiago J. Garcia 《Journal of polymer science. Part A, Polymer chemistry》2014,52(14):1953-1961
In this article, the first generation of healable sol–gel based polymers is reported. A dual organic–inorganic crosslinked network is developed containing non‐reversible crosslinks and reversible (tetrasulfide) groups. The designed polymer architecture allows thermally induced mesoscale flow leading to damage closure followed by interfacial strength restoration due to reformation of the reversible groups. While the reversible bonds are responsible for the flow and the interface restoration, the irreversible crosslinks control the required mechanical integrity during the healing process. The temperature dependent gap closure kinetics is strongly affected by the crosslinking density and tetrasulfide content. Raman spectroscopy is used to explain the gap closure kinetics in air and dry nitrogen. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1953–1961 相似文献
96.
C. Cruces Blanco F. Garcia Sanchez 《International journal of environmental analytical chemistry》2013,93(4):513-523
Abstract A simple kinetic-spectrophotometric method for the analysis of the organophosphate insecticide methyl parathien is presented. The method is based on the alkaline hydrolysis of the insecticide into its main metabolite p-nitrophenol. The influence of reaction variables (pH and temperature), and the effect of other pesticides, are discussed. The calibration graphs (initial rate, fixed time, fixed absorbance) were linear from 2 to 30μg/ml. The precision was calculated for the different methods applied, the relative standard deviation being 6.25% for 4μg/ml. The proposed kinetic method can be applied directly to synthetic mixtures, commercial formulations and different aqueous environment, with recoveries close to 100%. 相似文献
97.
E. E. Garcia 《合成通讯》2013,43(6):397-400
Pyrido[2,3-d]pyrimidine derivatives are of chemotherapeutic interest since they have been shown1 to act as inhibitors of dihydrofolate reductase and also because of their reported2 anti-tumor activity. In view of the important biological implications of this ring system, we have investigated a new route to these substances. This paper details a simple and efficient route to the previously unknown 7-amino-1,3-dimethylpyrido[2,3-d]pyrimidine-2,4-dione (I). 相似文献
98.
The effect of molecular chirality in thermotropic mesomorphic H-bonded polymeric systems has not really been investigated so far. Therefore, five new chiral mesogenic diamides have been prepared and described. Besides more ordered mesophases, the enantiomers exhibit a chiral nematic polymorphism detected by microcalorimetry and probably corresponding to different modes of chiral coiling to give these singular twisted nematic phases. 相似文献
99.
Bis‐clickable Mesoporous Silica Nanoparticles: Straightforward Preparation of Light‐Actuated Nanomachines for Controlled Drug Delivery with Active Targeting 下载免费PDF全文
Dr. Achraf Noureddine Dr. Magali Gary‐Bobo Dr. Laure Lichon Dr. Marcel Garcia Prof. Jeffrey I. Zink Dr. Michel Wong Chi Man Dr. Xavier Cattoën 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(28):9624-9630
Bis(clickable) mesoporous silica nanospheres (ca. 100 nm) were obtained by the co‐condensation of TEOS with variable amounts (2–5 % each) of two clickable organosilanes in the presence of CTAB. Such nanoparticles could be easily functionalized with two independent functions using the copper‐catalyzed alkyne‐azide cycloaddition (CuAAC) reaction to transform them into nanomachines bearing cancer cell targeting ligands with the ability to deliver drugs on‐demand. The active targeting was made possible after anchoring folic acid by CuAAC click reaction, whereas the controlled delivery was performed by clicked azobenzene fragments. Indeed, the azobenzene groups are able to obstruct the pores of the nanoparticles in the dark whereas upon irradiation in the UV or in the blue range, their trans‐to‐cis photoisomerization provokes disorder in the pores, enabling the delivery of the cargo molecules. The on‐command delivery was proven in solution by dye release experiments, and in vitro by doxorubicin delivery. The added value of the folic acid ligand was clearly evidenced by the difference of cell killing induced by doxorubicin‐loaded nanoparticles under blue irradiation, depending on whether the particles featured the clicked folic acid ligand or not. 相似文献
100.