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101.
Yantasee W Charnhattakorn B Fryxell GE Lin Y Timchalk C Addleman RS 《Analytica chimica acta》2008,620(1-2):55-63
Electrochemical sensors have great potential for environmental monitoring of toxic metal ions in waters due to their portability, field-deployability and excellent detection limits. However, electrochemical sensors employing mercury-free approaches typically suffer from binding competition for metal ions and fouling by organic substances and surfactants in natural waters, making sample pretreatments such as wet ashing necessary. In this work, we have developed mercury-free sensors by coating a composite of thiol self-assembled monolayers on mesoporous supports (SH-SAMMS™) and Nafion on glassy-carbon electrodes. With the combined benefit of SH-SAMMS™ as an outstanding metal preconcentrator and Nafion as an antifouling binder, the sensors could detect 0.5 ppb of Pb and 2.5 ppb of Cd in river water, Hanford groundwater, and seawater with a minimal amount of preconcentration time (few minutes) and without any sample pretreatment. The sensor could also detect 2.5 ppb of Cd, Pb, and Cu simultaneously. The electrodes have long service times and excellent single and inter-electrode reproducibility (5% R.S.D. after 8 consecutive measurements). Unlike SAMMS™-carbon paste electrodes, the SAMMS™-Nafion electrodes were not fouled in samples containing albumin and successfully detected Cd in human urine. Other potentially confounding factors affecting metal detection at SAMMS™-Nafion electrodes were studied, including pH effect, transport resistance of metal ions, and detection interference. With the ability to reliably detect low metal concentration ranges without sample pretreatment and fouling, SAMMS™-Nafion composite sensors have the potential to become the next-generation metal analyzers for environmental and bio-monitoring of toxic metals. 相似文献
102.
SERS spectroscopy and SERS imaging of Shewanella oneidensis using silver nanoparticles and nanowires
Preciado-Flores S Wheeler DA Tran TM Tanaka Z Jiang C Barboza-Flores M Qian F Li Y Chen B Zhang JZ 《Chemical communications (Cambridge, England)》2011,47(14):4129-4131
Facile and reproducible SERS signals from Shewanella oneidensis were obtained utilizing silver nanoparticles (AgNPs) and silver nanowires (AgNWs). Additionally, SERS images identify the distribution of SERS hot-spots. One important observation is the synergistically enhanced SERS signal when AgNPs and AgNWs are used in conjunction, due to constructively enhanced electromagnetic field. 相似文献
103.
A new method, called chemical potential perturbation (CPP), has been developed to predict the chemical potential as a function of density in periodic molecular simulations. The CPP method applies a spatially varying external force field to the simulation, causing the density to depend upon position in the simulation cell. Following equilibration the homogeneous (uniform or bulk) chemical potential as a function of density can be determined relative to some reference state after correcting for the effects of the inhomogeneity of the system. We compare three different methods of approximating this correction. The first method uses the van der Waals density gradient theory to approximate the inhomogeneous Helmholtz free energy density. The second method uses the local pressure tensor to approximate the homogeneous pressure. The third method uses the Triezenberg-Zwanzig definition of surface tension to approximate the inhomogeneous free energy density. If desired, the homogeneous pressure and Helmholtz free energy can also be predicted by the new method, as well as binodal and spinodal densities of a two-phase fluid region. The CPP method is tested using a Lennard-Jones (LJ) fluid at vapor, liquid, two-phase, and supercritical conditions. Satisfactory agreement is found between the CPP method and an LJ equation of state. The efficiency of the CPP method is compared to that for Widom's method under the tested conditions. In particular, the new method works well for dense fluids where Widom's method starts to fail. 相似文献
104.
Neil J. Shirtcliffe Glen McHale Michael I. Newton 《Journal of Polymer Science.Polymer Physics》2011,49(17):1203-1217
Superhydrophobicity is the extreme water repellence of highly textured surfaces. The field of superhydrophobicity research has reached a stage where huge numbers of candidate treatments have been proposed and jumps have been made in theoretically describing them. There now seems to be a move to more practical concerns and to considering the demands of individual applications instead of more general cases. With these developments, polymeric surfaces with their huge variety of properties have come to the fore and are fast becoming the material of choice for designing, developing, and producing superhydrophobic surfaces. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1203–1217, 2011 相似文献
105.
Marshall M. Siegel Rushung Tsao William Bouley Theodore Kornas Glen Brubaker 《Journal of the American Society for Mass Spectrometry》1993,4(6):504-506
An inexpensive multisample fast-atom bombardment (FAB) probe assembly was designed for high-throughput analysis of samples on a VG ZAB-SE mass spectrometer. The system consists of a vacuum lock system and a FAB probe whose tip contains five or more sample wells. The probe enters the mass spectrometer source region perpendicular to the secondary ion beam axis, The probe is maintained at high voltage on contact with a spring clip attached to the screen plate of the source block. Sample throughput with the multisample probe is twice that of a coaxial probe, with about twice the sensitivity and no sample cross contamination. 相似文献
106.
Stereoelectronic Basis for the Kinetic Resolution of N‐Heterocycles with Chiral Acylating Reagents 下载免费PDF全文
Sheng‐Ying Hsieh Benedikt Wanner Dr. Philip Wheeler Prof. Dr. André M. Beauchemin Prof. Dr. Tomislav Rovis Prof. Dr. Jeffrey W. Bode 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7228-7231
The kinetic resolution of N‐heterocycles with chiral acylating agents reveals a previously unrecognized stereoelectronic effect in amine acylation. Combined with a new achiral hydroxamate, this effect makes possible the resolution of various N‐heterocycles by using easily prepared reagents. A transition‐state model to rationalize the stereochemical outcome of this kinetic resolution is also proposed. 相似文献
107.
Okram B Nagle A Adrián FJ Lee C Ren P Wang X Sim T Xie Y Wang X Xia G Spraggon G Warmuth M Liu Y Gray NS 《Chemistry & biology》2006,13(7):779-786
Kinase inhibitors that bind to the ATP cleft can be broadly classified into two groups: those that bind exclusively to the ATP site with the kinase assuming a conformation otherwise conducive to phosphotransfer (type I), and those that exploit a hydrophobic site immediately adjacent to the ATP pocket made accessible by a conformational rearrangement of the activation loop (type II). To date, all type II inhibitors were discovered by using structure-activity-guided optimization strategies. Here, we describe a general pharmacophore model of type II inhibition that enables a rational "hybrid-design" approach whereby a 3-trifluoromethylbenzamide functionality is appended to four distinct type I scaffolds in order to convert them into their corresponding type II counterparts. We demonstrate that the designed compounds function as type II inhibitors by using biochemical and cellular kinase assays and by cocrystallography with Abl. 相似文献
108.
Andrews PC Deacon GB Junk PC Kumar I Silberstein M 《Dalton transactions (Cambridge, England : 2003)》2006,(40):4852-4858
Two synthetic approaches to the formation of bismuth(III) carboxylates have been explored and compared. Ph(3)Bi was reacted with a series of carboxylic acids (RCO(2)H) of varying pK(a) and functionality (R = PhCH[double bond, length as m-dash]CH, o-MeOC(6)H(4), m-MeOC(6)H(4), o-H(2)NC(6)H, o-O(2)NC(6)H(4), p-O(2)NC(6)H(4), 2-(C(5)H(4)N)) under reflux conditions in toluene and solvent-free. The thermochemical profiles of the solvent-free reactions were also studied by DSC-TGA. All reactions produced the tri-substituted bismuth carboxylates in comparable yields and purity with the exceptions of picolinic acid and p-nitrobenzoic acid. 2-Picolinic acid exclusively formed the di-substituted complex, [PhBi(2-(C(5)H(4)N)CO(2))(2)](4), by both methods, while p-nitrobenzoic acid gave the tri-substituted complex through reflux and the di-substituted complex under solvent-free conditions. Two of the complexes were structurally authenticated by single crystal X-ray diffraction: [PhBi(2-(C(5)H(4)N)CO(2))(2)](4) is tetrameric formed through five membered chelate rings involving the pyridyl N and O(-C) rather than the less stable carboxylate (-CO(2)) chelates, while [Bi(o-MeOC(6)H(4)CO(2))(3)](infinity), is a polymer in which dimeric units, constructed around two chelating and one unsymmetrical bridging carboxylate on each Bi centre, are then joined together through longer intermolecular Bi-O bridging bonds. 相似文献
109.
A microfluidic SELEX prototype 总被引:5,自引:0,他引:5
Hybarger G Bynum J Williams RF Valdes JJ Chambers JP 《Analytical and bioanalytical chemistry》2006,384(1):191-198
Aptamers are nucleic acid binding species capable of recognizing a wide variety of targets ranging from small organic molecules
to supramolecular structures, including organisms. They are isolated from combinatorial libraries of synthetic nucleic acid
by an iterative process referred to as SELEX (Systematic Evolution of Ligands by Exponential Enrichment). Here we describe
an automated microfluidic, microline-based assembly that uses LabView-controlled actuatable valves and a PCR machine, and
which is capable of the selection and synthesis of an anti-lysozyme aptamer as verified by sequence analysis. The microfluidic
prototype described is 1) a simple apparatus that is relatively inexpensive to assemble, making automated aptamer selection
accessible to many investigators, and 2) useful for the continued “morphing” of macro→meso→microfabricated structures until
a convergence to a few functional systems evolves and emerges, partly or completely achieving simpler, smaller and more rapid
SELEX applications. 相似文献
110.
Kurdyumov AV Lin N Hsung RP Gullickson GC Cole KP Sydorenko N Swidorski JJ 《Organic letters》2006,8(2):191-193
[reaction: see text] A Lewis acid-catalyzed formal cycloaddition of alpha,beta-unsaturated aldehydes with 6-methyl-4-hydroxy-2-pyrone, 1,3-diketones, and vinylogous silyl esters is described here. 相似文献