排序方式: 共有88条查询结果,搜索用时 31 毫秒
41.
Rappich J Merson A Roodenko K Dittrich T Gensch M Hinrichs K Shapira Y 《The journal of physical chemistry. B》2006,110(3):1332-1337
The electrochemical grafting process of 4-nitrobenzene and 4-methoxybenzene (anisole) from diazonium salt solutions has been investigated in situ by monitoring the current density, the band bending, and the nonradiative surface recombination during grafting at different potentials and different concentrations of the diazonium salt in the solution. Ex situ infrared spectroscopic ellipsometry has been used to inspect the Si surface species before and after the grafting process. The band bending decreases with either increasing concentration of diazonium salt or when the redox potential of the diazonium compound (anisole) is nearer to the competing H+/H2 couple. The surface recombination increases at more cathodic potentials if an electron donor group is present at the phenyl ring (nitrobenzene) and vice versa for the electron acceptor group (anisole). The influence of side reactions can be reduced by use of moderate concentration and moderate or strong cathodic potential, depending on the redox potential of the diazonium compound. 相似文献
42.
Abbott AP Capper G McKenzie KJ Glidle A Ryder KS 《Physical chemistry chemical physics : PCCP》2006,8(36):4214-4221
We have studied the anodic dissolution (electropolishing) of various stainless steel alloys in an ionic liquid comprising a 2 : 1 stoichiometric mix of ethylene glycol (EG) and choline chloride. We have used a combination of electrochemical and spectroscopic methods together with in situ liquid probe microscopy. We discuss the role and influence of the surface oxide passivation layer, characterized here by X-ray photoelectron spectroscopy (XPS) and linear sweep voltammetry, on the polishing process. We address the question of dealloying during the polish in order to contribute to our understanding of the viability of the ionic liquid as a replacement industrial electropolishing medium; the current commercial process uses a corrosive mixture of phosphoric and sulfuric acids. Also, we present data from ex situ and in situ liquid AFM studies giving both a qualitative and quantitative insight into the nature and scale of morphological changes at the steel surface during the polishing process. 相似文献
43.
M. A. Jeannot J. Zheng L. Li 《Journal of the American Society for Mass Spectrometry》1999,10(8):784-784
44.
This article introduces a suite of approaches and measures to study the impact of co‐authorship teams based on the number of publications and their citations on a local and global scale. In particular, we present a novel weighted graph representation that encodes coupled author‐paper networks as a weighted co‐authorship graph. This weighted graph representation is applied to a dataset that captures the emergence of a new field of science and comprises 614 articles published by 1036 unique authors between 1974 and 2004. To characterize the properties and evolution of this field, we first use four different measures of centrality to identify the impact of authors. A global statistical analysis is performed to characterize the distribution of paper production and paper citations and its correlation with the co‐authorship team size. The size of co‐authorship clusters over time is examined. Finally, a novel local, author‐centered measure based on entropy is applied to determine the global evolution of the field and the identification of the contribution of a single author's impact across all of its co‐authorship relations. A visualization of the growth of the weighted co‐author network, and the results obtained from the statistical analysis indicate a drift toward a more cooperative, global collaboration process as the main drive in the production of scientific knowledge. © 2005 Wiley Periodicals, Inc. Complexity 10: 57–67, 2005 相似文献
45.
Grace E. Florence Katy A. Bruce Dr. Helena J. Shepherd Dr. William J. Gee 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(41):9597-9601
A metastable form of 9-fluorenone (MS9F) has been characterized using Raman spectroscopy, fluorimetry, and X-ray diffraction techniques. MS9F emits blue fluorescence (λmax=495 nm) upon 365 nm irradiation and undergoes a single-crystal-to-single-crystal (SCSC) transformation to reach the ground state form (GS9F) over approximately 30 minutes, whereupon it emits the expected green fluorescence. A structure–property relationship for this fluorescent behavior has been posited. MS9F and GS9F were applied as a means of visualizing latent fingermarks on a nonporous surface. This approach identified three different modes of fluorescent fingermark visualization using 9-fluorenone. 相似文献
46.
Sarah Hostachy Tillmann Utesch Katy Franke Gillian Leigh Dornan David Furkert Berke Türkaydin Volker Haucke Han Sun Dorothea Fiedler 《Chemical science》2021,12(32):10696
Inositol poly- and pyrophosphates (InsPs and PP-InsPs) are densely phosphorylated eukaryotic messengers, which are involved in numerous cellular processes. To elucidate their signaling functions at the molecular level, non-hydrolyzable bisphosphonate analogs of inositol pyrophosphates, PCP-InsPs, have been instrumental. Here, an efficient synthetic strategy to obtain these analogs in unprecedented quantities is described – relying on the use of combined phosphate ester-phosphoramidite reagents. The PCP-analogs, alongside their natural counterparts, were applied to investigate their regulatory effect on insulin-degrading enzyme (IDE), using a range of biochemical, biophysical and computational methods. A unique interplay between IDE, its substrates and the PP-InsPs was uncovered, in which the PP-InsPs differentially modulated the activity of the enzyme towards short peptide substrates. Aided by molecular docking and molecular dynamics simulations, a flexible binding mode for the InsPs/PP-InsPs was identified at the anion binding site of IDE. Targeting IDE for therapeutic purposes should thus take regulation by endogenous PP-InsP metabolites into account.An efficient synthesis of non-hydrolyzable inositol pyrophosphate analogs was developed to subsequently investigate the regulation of insulin-degrading enzyme by these hyperphosphorylated signaling molecules. 相似文献
47.
The TCP window size process appears in the modeling of the famous transmission control protocol used for data transmission over the Internet. This continuous time Markov process takes its values in [0,∞), and is ergodic and irreversible. It belongs to the additive increase–multiplicative decrease class of processes. The sample paths are piecewise linear deterministic and the whole randomness of the dynamics comes from the jump mechanism. Several aspects of this process have already been investigated in the literature. In the present paper, we mainly get quantitative estimates for the convergence to equilibrium, in terms of the W1 Wasserstein coupling distance, for the process and also for its embedded chain. 相似文献
48.
Drewette KJ Henderson KW Kennedy AR Mulvey RE O'Hara CT Rowlings RB 《Chemical communications (Cambridge, England)》2002,(11):1176-1177
A series of composite lithium- or sodium-magnesium-alkoxide-diisopropylamides of general formula [(MMg[N(Pri)2]2OR)2] (where M = Li, R = Octn; M = Na, R = Bun or Octn), has been synthesised rationally by treating synergic amide mixtures with the appropriate alcohol. 相似文献
49.
Ehly M Gemperline PJ Nordon A Littlejohn D Basford JK De Cecco M 《Analytica chimica acta》2007,595(1-2):80-88
The scale-up of batch kinetic models was studied by examining the kinetic fitting results of batch esterification reactions completed in 75 mL and 5 L reactors. Different temperatures, amounts of catalysts, and amounts of initial starting reagents were used to completely characterize the reaction. A custom written Matlab toolbox called GUIPRO was used to fit first-principles kinetic models directly to in-line NIR and Raman spectroscopic data. Second-order kinetic models provided calibration-free estimates of kinetic and thermodynamic reaction parameters, time dependent concentration profiles, and pure component spectra of reagents and product. The estimated kinetic and thermodynamic parameters showed good agreement between small-scale and large-scale reactions. The accuracy of pure component spectra estimates was validated by comparison to collected NIR and Raman pure component spectra. The model estimated product concentrations were also validated by comparison to concentrations measured by off-line GC analysis. Based on the good agreement between kinetic and thermodynamic parameters and comparison between actual and estimated concentration and spectral profiles, it was concluded that the scale-up of batch kinetic models was successful. 相似文献
50.