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841.
Boudreault PL Wakim S Blouin N Simard M Tessier C Tao Y Leclerc M 《Journal of the American Chemical Society》2007,129(29):9125-9136
The synthesis, characterization, and field-effect transistor (FET) properties of new indolo[3,2-b]carbazoles are described. In particular, an extensive characterization of their crystal structures has revealed the importance of the nature of the side chains (alkyl, phenyl, thienyl substituents) on their solid-state organization. These organic materials have exhibited p-type FET behavior with hole mobilities as high as 0.2 cm2 V(-1) s(-1) with an on/off current ratio higher than 10(6). Best results were obtained with phenyl-substituted indolo[3,2-b]carbazoles since the presence of phenyl substituents seems to allow efficient overlap between the oligomeric molecules. More importantly, FET properties were kept constant during several months in air. 相似文献
842.
Bastida A Hidalgo A Chiara JL Torrado M Corzana F Pérez-Cañadillas JM Groves P Garcia-Junceda E Gonzalez C Jimenez-Barbero J Asensio JL 《Journal of the American Chemical Society》2006,128(1):100-116
The emergence of bacterial resistance to the major classes of antibiotics has become a serious problem over recent years. For aminoglycosides, the major biochemical mechanism for bacterial resistance is the enzymatic modification of the drug. Interestingly, in several cases, the oligosaccharide conformation recognized by the ribosomic RNA and the enzymes responsible for the antibiotic inactivation is remarkably different. This observation suggests a possible structure-based chemical strategy to overcome bacterial resistance; in principle, it should be possible to design a conformationally locked oligosaccharide that still retains antibiotic activity but that is not susceptible to enzymatic inactivation. To explore the scope and limitations of this strategy, we have synthesized several aminoglycoside derivatives locked in the ribosome-bound "bioactive" conformation. The effect of the structural preorganization on RNA binding, together with its influence on the aminoglycoside inactivation by several enzymes involved in bacterial resistance, has been studied. Our results indicate that the conformational constraint has a modest effect on their interaction with ribosomal RNA. In contrast, it may display a large impact on their enzymatic inactivation. Thus, the work presented herein provides a key example of how the conformational differences exhibited by these ligands within the binding pockets of the ribosome and of those enzymes involved in bacterial resistance can, in favorable cases, be exploited for designing new antibiotic derivatives with improved activity in resistant strains. 相似文献
843.
Del Pópolo MG Kohanoff J Lynden-Bell RM 《The journal of physical chemistry. B》2006,110(17):8798-8803
Ab initio simulations of a single molecule of HCl in liquid dimethyl imidazolium chloride [dmim][Cl] show that the acidic proton exists as a symmetric, linear ClHCl(-) species. Details of the solvation structure around this molecule are given. The proton-transfer process was investigated by applying a force along the antisymmetric stretch coordinate until the molecule broke. Changes in the free energy and local solvation structure during this process were investigated. In the reaction mechanism identified, a free chloride approaches the proton from the side. As the original ClHCl(-) distorts and the incoming chloride forms a new bond to the proton, one of the original chlorine atoms is expelled and a new linear molecule is formed. 相似文献
844.
Euro Solari Stefania De Angelis Mario Latronico Carlo Floriani Angiola Chiesi-Villa Corrado Rizzoli 《Journal of Cluster Science》1996,7(4):553-566
The function of the solvent in the self-assembling mode of [CuCl] with tetrahydrothiophene is reported. Copper(l) chloride has been used in the form of [CuCOCl]
n
, which is slightly soluble in the most common solvents, and to allow an homogeneous phase reaction. The reaction of [CuCOCl]
n
with THT gave [(CuCl)2(THT)3]
x
,1, in CH3OH, [(CuCl)(THT)2]
x
,2 in THF [(CuCl)(THT)]
x
,3, in CH2Cl2, and [(CuCl)3(THT)2]
x
,4, in DME. Compound1 consists of polymeric chains of centrosymmetric Cu2Cl2 dinuclear units bridged by THIT molecules running parallel to the [101] axis. In the structure of2 we found polymeric layers generated from the [(CuCl)(THT)] asymmetric unit by the center of symmetry and by the twofold axis. In compound3 the structure consists of layers generated through the center of symmetry by the [(Cu2Cl2)(THT)2] asymmetric unit, while4 consists of layers generated through the center of symmetry by the [(Cu3Cl3)(THT)2] asymmetric unit. Crystallographic details are as [ollows:2 is monoclinic, space group P21/c.a=9.657(3) A,b=6.441(2) A,c=11.459(3) A,\=111.96(2)°,V=661.0(4) A3. andR=0.075;3 is monoclinic, space group P21/n,a=19.327(7) A,b=6.703(2) A,c=10.116(3) A,ß=103.04(3)°,V=1276.7(7) A3 andR=0.043:4 is triclinic, space group Pl,a=12.513(2) A,b=6.698(1) A,c=9.651(1) A,=91.98(1)°,\=107.86(1)°,=74.59(1)°,V=741.2(2) A3, andR=0.044. 相似文献
845.
X-ray crystallographic study of K[OsO2(O2CMe)3]· 2MeCO2H shows that the anion has cis dioxo, one chelate and two trans monodentate acetato groups. 相似文献
846.
847.
Licarion Pinto César Horacio Díaz Nieto María Alicia Zón Héctor Fernández Mario Cesar Ugulino de Araujo 《Analytica chimica acta》2016
Biogenic amines (BAs) are used for identifying spoilage in food. The most common are tryptamine (TRY), 2-phenylethylamine (PHE), putrescine (PUT), cadaverine (CAD) and histamine (HIS). Due to lack of chromophores, chemical derivatization with dansyl was employed to analyze these BAs using high performance liquid chromatography with a diode array detector (HPLC-DAD). However, the derivatization reaction occurs with any primary or secondary amine, leading to co-elution of analytes and interferents with identical spectral profiles, and thus causing rank deficiency. When the spectral profile is the same and peak misalignment is present on the chromatographic runs, it is not possible to handle the data only with Multivariate Curve Resolution and Alternative Least Square (MCR-ALS), by augmenting the time, or the spectral mode. A way to circumvent this drawback is to receive information from another detector that leads to a selective profile for the analyte. To overcome both problems, (tri-linearity break in time, and spectral mode), this paper proposes a new analytical methodology for fast quantitation of these BAs in fish with HPLC-DAD by using the icoshift algorithm for temporal misalignment correction before MCR-ALS spectral mode augmented treatment. Limits of detection, relative errors of prediction (REP) and average recoveries, ranging from 0.14 to 0.50 µg mL−1, 3.5–8.8% and 88.08%–99.68%, respectively. These are outstanding results obtained, reaching quantification limits for the five BAs much lower than those established by the Food and Agriculture Organization of the United Nations and World Health Organization (FAO/WHO), and the European Food Safety Authority (EFSA), all without any pre-concentration steps. The concentrations of BAs in fish samples ranged from 7.82 to 29.41 µg g−1, 8.68–25.95 µg g−1, 4.76–28.54 µg g−1, 5.18–39.95 µg g−1 and 1.45–52.62 µg g−1 for TRY, PHE, PUT, CAD, and HIS, respectively. In addition, the proposed method spends less than 4 min in an isocratic run, consuming less solvent in accordance with the principles of green analytical chemistry. 相似文献
848.
849.
850.
Laura Asturias‐Arribas Mario Raúl Delfino M. Asunción Alonso‐Lomillo Olga Domínguez‐Renedo M. Julia Arcos‐Martínez 《Electroanalysis》2016,28(9):2081-2086
This paper describes the voltammetric study of the electrochemical oxidation of the antiretroviral drug Nelfinavir using a screen‐printed sensor modified with carbon nanotubes. The performance of the sensor in the determination of the drug was characterized in terms of precision (RSD 5.05 %, n=5) and capability of detection (10.99±0.87 μM for α=β=0.05, n=5) under optimized voltammetric conditions of pH, accumulation time and potential, in the calibration range from 10 to 150 μM of NFV. In order to check the viability of the device, the determination of the analyte in pharmaceutical and biological samples was carried out and its performance was also validated comparing it with HPLC. 相似文献