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141.
142.
Roldán ML Sanchez-Cortes S García-Ramos JV Domingo C 《Physical chemistry chemical physics : PCCP》2012,14(14):4935-4941
In this work, we have studied the pH-dependence of the formation of DQCB[8] complexes by surface-enhanced Raman scattering (SERS) spectroscopy. The SERS spectra suggest that at acidic pH CB[8] can form a binary complex with the dication DQ(+2) while at higher pH ternary complexes with the radical cation dimer (DQ(+)˙)(2) and the radical cation-dication dimer (DQ(+)˙DQ(+2)) are formed. The pH-enhanced diquat (DQ) dimerization inside the cucurbit[8]uril cavity has not been reported until now. In addition, this study provides very valuable information regarding the use of CB[8] functionalized silver nanoparticles as SERS substrate for sensing applications. 相似文献
143.
Betancor L Berne C Luckarift HR Spain JC 《Chemical communications (Cambridge, England)》2006,(34):3640-3642
The coimmobilization of nitrobenzene nitroreductase and glucose-6-phosphate dehydrogenase in silica particles enables the continuous conversion of nitrobenzene to hydroxylaminobenzene with NADPH recycling. 相似文献
144.
Iriarte G Ferreirós N Ibarrondo I Alonso RM Maguregi MI Gonzalez L Jiménez RM 《Journal of separation science》2006,29(15):2265-2283
A chemometric approach was applied for the optimization of the extraction and separation of the antihypertensive drug valsartan and its metabolite valeryl-4-hydroxy-valsartan from human plasma samples. Due to the high number of experimental and response variables to be studied, fractional factorial design (FFD) and central composite design (CCD) were used to optimize the HPLC-UV-fluorescence method. First, the significant variables were chosen with the help of FFD; then, a CCD was run to obtain the optimal values for the significant variables. The measured responses were the corrected areas of the two analytes and the resolution between the chromatographic peaks. Separation of valsartan, its metabolite valeryl-4-hydroxy-valsartan and candesartan M1, used as internal standard, was made using an Atlantis dC18 100 mm x 3.9 mm id, 100 angstroms, 3 microm chromatographic column. The mobile phase was run in gradient elution mode and consisted of ACN with 0.025% TFA and a 5 mM phosphate buffer with 0.025% TFA at pH 2.5. The initial percentage of ACN was 32% with a stepness of 4.5%/min to reach the 50%. A flow rate of 1.30 mL/min was applied throughout the chromatographic run, and the column temperature was kept to 40+/-0.2 degrees C. In the SPE procedure, experimental design was also used in order at achieve a maximum recovery percentage and extracts free from plasma interferences. The extraction procedure for spiked human plasma samples was carried out using C8 cartridges, phosphate buffer (pH 2, 60 mM) as conditioning agent, a washing step with methanol-phosphate buffer (40:60 v/v), a drying step of 8 min, and diethyl ether as eluent. The SPE-HPLC-UV-fluorescence method developed allowed the separation and quantitation of valsartan and its metabolite from human plasma samples with an adequate resolution and a total analysis time of 1 h. 相似文献
145.
Samuel Goroshin Lorena Camargo John H.S. Lee 《Proceedings of the Combustion Institute》2005,30(2):2561-2568
Thermodynamic calculations show that some metals can react with sulfur without the formation of gaseous products at normal pressure and yet demonstrate sufficiently high flame temperatures to support the propagation of stable flames. For example, a stoichiometric ternary mixture of iron, manganese, and sulfur demonstrates gasless combustion at an equimolar concentration of iron and of manganese with an adiabatic flame temperature of about 2000 °C. Differential thermal analysis of the mixture shows no exothermic reactions below 280 °C. Therefore, sulfur in the mixture can be safely melted (m.p. 119 °C), converting a powder blend into a liquid suspension that is free from gas bubbles. Symmetrical cylindrical flames in shallow pools of suspensions of Fe and Mn powders in liquid sulfur and combustion of the same liquid mixtures in preheated narrow steel tubes have been studied to determine flame propagation speeds as a function of mixture composition. It was found that, contrary to the behavior of the calculated flame temperature, flame speed decreases with the increase of the manganese content in the mixture and is not affected by mixture dilution with the combustion product. Direct measurements of the flame temperatures by thermocouples indicated a weak dependence of the peak flame temperature on mixture composition and revealed a two-stage flame structure. The existence of the two distinct reaction zones in the mixture of two reactive metals with sulfur is in accordance with qualitative theoretical predictions by the theory of flame with parallel reactions existing in the literature. According to theory, the reaction with the higher flame speed in a corresponding binary single-metal–sulfur mixture will form the leading stage of the complex flame front and will govern the flame propagation speed in the ternary composition. The speed of flame propagation in pure Fe–S mixture is almost three times higher than the flame speed in Mn–S mixture. As a result, the iron–sulfur reaction dominates the flame propagation mechanism in Fe–Mn–S suspension. 相似文献
146.
Effect of Gold Nanoparticles on the Structure and Electron‐Transfer Characteristics of Glucose Oxidase Redox Polyelectrolyte‐Surfactant Complexes
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Dr. M. Lorena Cortez Dr. Waldemar Marmisollé Dr. Diego Pallarola Dr. Lía I. Pietrasanta Dr. Daniel H. Murgida Dr. Marcelo Ceolín Dr. Omar Azzaroni Dr. Fernando Battaglini 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13366-13374
Efficient electrical communication between redox proteins and electrodes is a critical issue in the operation and development of amperometric biosensors. The present study explores the advantages of a nanostructured redox‐active polyelectrolyte–surfactant complex containing [Os(bpy)2Clpy]2+ (bpy=2,2′‐bipyridine, py= pyridine) as the redox centers and gold nanoparticles (AuNPs) as nanodomains for boosting the electron‐transfer propagation throughout the assembled film in the presence of glucose oxidase (GOx). Film structure was characterized by grazing‐incidence small‐angle X‐ray scattering (GISAXS) and atomic force microscopy (AFM), GOx incorporation was followed by surface plasmon resonance (SPR) and quartz‐crystal microbalance with dissipation (QCM‐D), whereas Raman spectroelectrochemistry and electrochemical studies confirmed the ability of the entrapped gold nanoparticles to enhance the electron‐transfer processes between the enzyme and the electrode surface. Our results show that nanocomposite films exhibit five‐fold increase in current response to glucose compared with analogous supramolecular AuNP‐free films. The introduction of colloidal gold promotes drastic mesostructural changes in the film, which in turn leads to a rigid, amorphous interfacial architecture where nanoparticles, redox centers, and GOx remain in close proximity, thus improving the electron‐transfer process. 相似文献
147.
Biphenyl‐Derived Phosphepines as Chiral Nucleophilic Catalysts: Enantioselective [4+1] Annulations To Form Functionalized Cyclopentenes
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Daniel T. Ziegler Lorena Riesgo Takuya Ikeda Yuji Fujiwara Prof. Gregory C. Fu 《Angewandte Chemie (International ed. in English)》2014,53(48):13183-13187
Because of the frequent occurrence of cyclopentane subunits in bioactive compounds, the development of efficient catalytic asymmetric methods for their synthesis is an important objective. Introduced herein is a new family of chiral nucleophilic catalysts, biphenyl‐derived phosphepines, and we apply them to an enantioselective variant of a useful [4+1] annulation. A range of one‐carbon coupling partners can be employed, thereby generating cyclopentenes which bear a fully substituted stereocenter [either all‐carbon or heteroatom‐substituted (sulfur and phosphorus)]. Stereocenters at the other four positions of the cyclopentane ring can also be introduced with good stereoselectivity. An initial mechanistic study indicates that phosphine addition to the electrophilic four‐carbon coupling partner is not the turnover‐limiting step of the catalytic cycle. 相似文献
148.
Copper(I) bromide catalyzes the regioselective Michael addition reaction of 2-amino-1,4-naphthoquinone (5) with methyl vinyl ketone and 2-propenal to provide easy access to C-alkylated quinone derivatives, useful precursors of 1-azaanthraquinones. 相似文献
149.
Michael Hailmann Lorena Herkert Dr. Alexander Himmelspach Prof. Dr. Maik Finze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(46):15745-15758
Carba‐closo‐dodecaborate anions with two functional groups have been synthesized via a simple two‐step procedure starting from monoamino‐functionalized {closo‐1‐CB11} clusters. Iodination at the antipodal boron atom provided access to [1‐H2N‐12‐I‐closo‐1‐CB11H10]? ( 1 a ) and [2‐H2N‐12‐I‐closo‐1‐CB11H10]? ( 2 a ), which have been transformed into the anions [1‐H2N‐12‐RC?C‐closo‐1‐CB11H10]? (R=H ( 1 b ), Ph ( 1 c ), Et3Si ( 1 d )) and [2‐H2N‐12‐RC?C‐closo‐1‐CB11H10]? (R=H ( 2 b ), Ph ( 2 c ), Et3Si ( 2 d )) by microwave‐assisted Kumada‐type cross‐coupling reactions. The syntheses of the inner salts 1‐Me3N‐12‐RC?C‐closo‐1‐CB11H10 (R=H ( 1 e ), Et3Si ( 1 f )) and 2‐Me3N‐12‐RC?C‐closo‐1‐CB11H10 (R=H ( 2 e ), Et3Si ( 2 f )) are the first examples for a further derivatization of the new anions. All {closo‐1‐CB11} clusters have been characterized by multinuclear NMR and vibrational spectroscopy as well as by mass spectrometry. The crystal structures of Cs 1 a , [Et4N] 2 a , K 1 b , [Et4N] 1 c , [Et4N] 2 c , 1 e , and [Et4N][1‐H2N‐2‐F‐12‐I‐closo‐1‐CB11H9]?0.5 H2O ([Et4N ]4 a ?0.5 H2O) have been determined. Experimental spectroscopic data and especially spectroscopic data and bond properties derived from DFT calculations provide some information on the importance of inductive and resonance‐type effects for the transfer of electronic effects through the {closo‐1‐CB11} cage. 相似文献
150.
Paola Baile Juan Medina Lorena Vidal Antonio Canals 《Journal of separation science》2020,43(9-10):1808-1816
A novel approach is presented to determine four bisphenols in water and urine samples, employing magnetic dispersive solid‐phase extraction combined with liquid chromatography and diode array detection. A modified zeolite‐based magnetic composite was used as an efficient sorbent, combining the advantages of magnetic materials with the remarkable properties of zeolites. A multivariate optimization design was employed to optimize some experimental factors affecting magnetic dispersive solid‐phase extraction. The method was evaluated under optimized conditions (i.e., amount of sorbent, 50 mg; sample pH, unadjusted; NaCl concentration, 1.25%; extraction and elution time, 2 min; eluent solvent, ethanol; eluent solvent volume, 400 µL), obtaining good linearity with correlation coefficients ranging between 0.995 and 0.999 (N = 5) (from 2 to 250 µg/L for bisphenol A, bisphenol AP, and bisphenol P and from 5 to 250 µg/L for bisphenol AF). Method repeatability was assessed obtaining coefficients of variation between 3 and 11% (n = 6). Finally, the method was applied to spiked real samples, obtaining for water samples relative recoveries between 83 and 105%, and for urine samples between 81 and 108% for bisphenol A, bisphenol AP, and bisphenol AF, and between 47 and 59% for bisphenol P. 相似文献