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891.
Verbeck GF Ruotolo BT Gillig KJ Russell DH 《Journal of the American Society for Mass Spectrometry》2004,15(9):1320-1324
An extension of current mobility resolution equations as they apply to high-field ion mobility spectrometry is presented. The new resolution expression is applied to arrival time distributions for ions having a large range of ion mobilities and mass-to-charge ratios (m/z). The results indicate that the new equation can be utilized to predict the mobility resolution over a broader range of applied electric fields than previous ion mobility resolution expressions. 相似文献
892.
Oualid Talhi Guido R. Lopes Sérgio M. Santos Diana C. G. A. Pinto Artur M. S. Silva 《Journal of Physical Organic Chemistry》2014,27(9):756-763
The diastereoselective photodependent isomerization equilibrium of E/Z‐1,3‐ditolyl‐5‐[3‐oxobenzofuran‐2(3H)‐ylidene]imidazolidine‐2,4‐dione ( 5 ) is reported. Both diastereomers E-5 and Z-5 are stereochemically stable in solid state but show significant photosensibility in solutions of halogenated solvent. The photoisomerization equilibrium of E/Z‐ 5 is therefore deduced from the 1H NMR profile after visible‐light irradiation of both E-5 and Z-5 samples. The results of the kinetic study, monitored by UV‐HPLC, reveal that the E/Z equilibrium is diastereoselective and photodependent, being the transformation E ? Z proceeding faster than that of Z ? E, and the E/Z ratio at the equilibrium depends on the used solvent, light source, and temperature. Both diastereomers are visible‐light photosensitive tending to coexist together in equilibrium solutions at a determined ratio, which is always in favor of the Z‐product assuming a minimum thermodynamic energy and an increased entropy of the system. Time‐dependent density functional theory calculations suggest that the photoisomerization mechanism proceeds via a conical intersection involving the first‐excited state: Upon irradiation, the E-5 isomer is excited to the S1 potential energy surface, where it relaxes through rotation of the C=C bond and reaches a conical intersection with the ground‐state potential energy surface, thus yielding the Z-5 isomer. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
893.
The Multi-Handler Knapsack Problem under Uncertainty is a new stochastic knapsack problem where, given a set of items, characterized by volume and random profit, and a set of potential handlers, we want to find a subset of items which maximizes the expected total profit. The item profit is given by the sum of a deterministic profit plus a stochastic profit due to the random handling costs of the handlers. On the contrary of other stochastic problems in the literature, the probability distribution of the stochastic profit is unknown. By using the asymptotic theory of extreme values, a deterministic approximation for the stochastic problem is derived. The accuracy of such a deterministic approximation is tested against the two-stage with fixed recourse formulation of the problem. Very promising results are obtained on a large set of instances in negligible computing time. 相似文献
894.
Diazabicyclo[5.4.0]undecene (DBU) reacts with carbon dioxide and N-subsititued-2-chloroacetoamides in a very simple one-step procedure, to give the corresponding 3-substituted oxazolidin-2,4-diones in excellent yields. 相似文献
895.
The use of DNA as a molecular wire in nanoscale electronic architectures would greatly benefit from its capability of sequence-specific self-assembly. Although single electrons and positive charges have been shown to be transmitted by natural DNA over a distance of several base pairs, the high ohmic resistance of unmodified oligonucleotides imposes a serious obstacle. Exchanging some or all of the Watson–Crick base pairs in DNA by metal complexes may solve this problem and evolve DNA-like materials with superior conductivity for future nano-electronic applications. The so-called metal–base pairs are formed from suitable transition metal ions and ligand-like nucleosides which are introduced into both of the two pairing strands by automated DNA synthesis. This review illustrates the basic concepts of metal–base pairing and highlights recent developments in the field. 相似文献
896.
897.
Susanna Vogliardi Donata Favretto Giampietro Frison Sergio Maietti Guido Viel Roberta Seraglia Pietro Traldi Santo Davide Ferrara 《Analytical and bioanalytical chemistry》2010,396(7):2435-2440
The sensitivity and specificity of a novel method of screening for cocaine in hair, based on matrix-assisted laser desorption/ionisation
(MALDI) mass spectrometry (MS), have been evaluated. The method entails a rapid extraction procedure consisting of shaking
2.5 mg pulverised hair at high frequency in the presence of an acidic solution (160 μL of water, 20 μL of acetonitrile and
20 μL of 1 M trifluoroacetic acid) and a stainless-steel bullet. Following centrifugation, the supernatant is dried under
a nitrogen stream, and the residue is reconstituted in 10 μL of methanol/trifluoroacetic acid (7:3; v/v). One microlitre of the extract is deposed on a MALDI sample holder previously scrubbed with graphite; an α-cyano-4-hydroxycinnamic
acid (matrix) solution is electrosprayed over the dried sample surface to achieve a uniform distribution of matrix crystals.
The identification of cocaine is obtained by post-source decay experiments performed on its MH+ ion (m/z 304), with a limit of detection of 0.1 ng/mg of cocaine. A total of 304 hair samples were analysed in parallel by MALDI-MS
and a reference gas chromatography-MS method. The obtained results demonstrate specificity and sensitivity of 100% for MALDI-MS.
Evidence of cocaine presence was easily obtained even when hair samples exhibiting particularly low cocaine levels (<0.5 ng/mg)
were analysed. 相似文献
898.
Tangbunsuk S Whittell GR Ryadnov MG Vandermeulen GW Woolfson DN Manners I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(9):2524-2535
Conjugates of poly(ferrocenyldimethylsilane) (PFDMS) with Ac-(GA)(2)-OH, Ac-A(4)-OH, Ac-G(4)-OH and Ac-V(4)-OH have been prepared by reaction of the tetrapeptide units with the amino-terminated metallopolymer. The number average degree of polymerisation (DP(n)) of the PFDMS was approximately 20 and comparable materials with shorter (DP(n) ≈ 10) and/or amorphous chains have been prepared by the same procedure. Poly(ferrocenylethylmethylsilane) (PFEMS) was employed for the latter purpose. All conjugates were characterised by GPC, MALDI-TOF?MS, NMR and IR spectroscopy. With the exception of Ac-V(4)-PFDMS(20), all materials exhibited some anti-parallel β-sheet structure in the solid state. The self-assembly of the conjugates was studied in toluene by DLS. The vast majority of the materials, irrespective of peptide sequence or chain crystallinity, afforded fibres consisting of a peptidic core surrounded by a PFS corona. These fibres were found in the form of cross-linked networks by TEM and AFM. The accessibility of the chemically reducing PFS corona has been demonstrated by the localised formation of silver nanoparticles on the surface of the fibres. 相似文献
899.
Full-field magnetic transmission x-ray microscopy at high spatial resolution down to 20 nm is used to directly observe field-driven domain wall motion in notch-patterned permalloy nanowires. The depinning process of a domain wall around a notch exhibits a stochastic nature in most nanowires. The stochasticity of the domain wall depinning sensitively depends on the geometry of the nanowire such as the wire thickness, the wire width, and the notch depth. We propose an optimized design of the nanowire for deterministic domain wall depinning field at a notch. 相似文献
900.
Graphite was dispersed in immiscible polyvinylidene fluoride/maleated polypropylene (PVDF/PPgMA) blends to improve electrical and thermal conductive properties by building a double‐percolation structure. The morphology of PVDF/PPgMA blends was first investigated for several compositions by selective solvent extraction, scanning electron microscopy, and dynamic mechanical thermal analysis. Blends of PVDF and PPgMA were prepared in different relative fractions, and a PVDF/PPgMA ratio of 7/3 showed a well‐co‐continuous structure. From this blend, the morphology and properties of composites with different concentrations of graphite were investigated to prepare double‐percolated structures. Graphite was observed to selectively localize in the PPgMA phase. The electrical and thermal conductive properties of graphite‐containing blends were measured, showing enhanced conductivity for the double‐percolation structures compared with single‐polymer composites containing the same graphite loadings. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献