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61.
A. Gareth Brenton A. Ruth Godfrey 《Journal of the American Society for Mass Spectrometry》2010,21(11):1821-1835
High-resolution mass spectrometry has become ever more accessible with improvements in instrumentation, such as modern FT-ICR
and Orbitrap mass spectrometers. This has resulted in an increase in the number of articles submitted for publication quoting
accurate mass data. There is a plethora of terms related to accurate mass analysis that are in current usage, many employed
incorrectly or inconsistently. This article is based on a set of notes prepared by the authors for research students and staff
in our laboratories as a guide to the correct terminology and basic statistical procedures to apply in relation to mass measurement,
particularly for accurate mass measurement. It elaborates on the editorial by Gross in 1994 regarding the use of accurate
masses for structure confirmation [1]. We have presented and defined the main terms in use with reference to the International
Union of Pure and Applied Chemistry (IUPAC) recommendations for nomenclature and symbolism for mass spectrometry. The correct
use of statistics and treatment of data is illustrated as a guide to new and existing mass spectrometry users with a series
of examples as well as statistical methods to compare different experimental methods and datasets. 相似文献
62.
Andrzej Rajca Prof. Velavan Kathirvelu Dr. Sandip K. Roy Dr. Maren Pink Dr. Suchada Rajca Dr. Santanu Sarkar Sandra S. Eaton Prof. Gareth R. Eaton Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(19):5778-5782
Site‐directed spin labeling and EPR spectroscopy offer accurate, sensitive tools for the characterization of structure and function of macromolecules and their assemblies. A new rigid spin label, spirocyclohexyl nitroxide α‐amino acid and its N‐(9‐fluorenylmethoxycarbonyl) derivative, have been synthesized, which exhibit slow enough spin‐echo dephasing to permit accurate distance measurements by pulsed EPR spectroscopy at temperatures up to 125 K in 1:1 water/glycerol and at higher temperatures in matrices with higher glass transition temperatures. Distance measurements in the liquid nitrogen temperature range are less expensive than those that require liquid helium, which will greatly facilitate applications of pulsed EPR spectroscopy to the study of structure and conformation of peptides and proteins. 相似文献
63.
Flávio B. Gonçalves Gareth O. Roberts 《Methodology and Computing in Applied Probability》2014,16(4):907-930
Exact simulation of SDEs is a very important and challenging problem. In this paper we discuss exact simulation problems for jump-diffusion processes. Motivated by statistical applications, our main contribution is to propose an algorithm that performs exact simulation of a class of jump-diffusion bridges. We also present and discuss the existing methods for forward simulation and propose an extension of one of them to account for unbounded jump rate. Finally, the exact algorithms are compared to competing non-exact ones in some simulated examples. 相似文献
64.
65.
Sebastien Graule Mark Rudolph Wenting Shen J. A. Gareth Williams Dr. Christophe Lescop Dr. Jochen Autschbach Prof. Jeanne Crassous Dr. Régis Réau Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(20):5976-6005
Aza[n]helicene phosphole derivatives have been prepared from aza[n]helicene diynes by the Fagan–Nugent route. Their photophysical properties (UV/Vis absorption and emission behavior) have been evaluated. Their behavior as P,N chelates towards coordination to PdII and CuI has been investigated: metal–bis(aza[n]helicene phosphole) assemblies are formed by a highly stereoselective coordination process, as demonstrated by X‐ray crystallography. An aza[6]helicene phosphole bearing an enantiopure helicene part has been obtained, which allows the preparation of enantiopure PdII and CuI complexes with original topologies and high molar rotation (MR) and circular dichroism (CD). The structure–property relationship established from the experimental data has been studied in detail by theoretical studies (TDDFT calculations of UV/Vis, CD, and MR). Aza[n]helicene phosphole derivatives show π conjugation extended over the entire molecule, and its influence on the MR of aza[6]helicene phosphole 5 c has been demonstrated. Finally, it has been shown that the nature of the metal (coordination geometry and electronic interaction) can have a great impact on the amplitude of the chiroptical properties in metal–bis(aza[n]helicene phosphole) assemblies. 相似文献
66.
67.
I. Yilgor E. Yilgor S. Das G. L. Wilkes 《Journal of Polymer Science.Polymer Physics》2009,47(5):471-483
Time‐dependent morphology development in segmented polyureas obtained by the stoichiometric reactions between amine terminated poly(tetramethylene oxide) (PTMO) and aromatic diisocyanates were investigated. Polyureas were prepared by reacting aminopropyl terminated PTMO oligomer (Mn = 1100 g/mol) and various aromatic diisocyanates, such as 1,4‐phenylene diisocyanate (PPDI), 1,3‐phenylene diisocyanate (MPDI), diphenylmethane diisocyanate (MDI), and tolylene diisocyanate (TDI). Time‐dependent FTIR studies were conducted on thin films cast onto KBr discs, which were annealed at 200 °C for 10 min in an air oven. After removing from the oven, samples were placed into the FTIR spectrometer at room temperature, where time‐dependent spectra were recorded until equilibrium was reached. Time‐dependent peak reorganization in 3500–3100 cm?1 (N? H region), 1750–1450 cm?1 (C?O region or amide I and amide II regions), and 1180–1020 cm?1 (C? O? C) were monitored. Depending on the chemical structure and the symmetry of the diisocyanate, major differences were observed in the time needed to reach an equilibrium morphology in these homologous poly(ether urea) copolymers. Symmetric PPDI‐based polyurea reached equilibrium in about 1 h compared with its asymmetric MPDI‐based counterpart, which needed about 150 h. Microphase development of the MPDI urea was also characterized by AFM, which gave similar results. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 471–483, 2009 相似文献
68.
69.
Ultraviolet Absorption Induces Hydrogen‐Atom Transfer in G⋅C Watson–Crick DNA Base Pairs in Solution
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Dr. Katharina Röttger Hugo J. B. Marroux Dr. Michael P. Grubb Philip M. Coulter Hendrik Böhnke Dr. Alexander S. Henderson Dr. M. Carmen Galan Prof. Friedrich Temps Prof. Andrew J. Orr‐Ewing Dr. Gareth M. Roberts 《Angewandte Chemie (International ed. in English)》2015,54(49):14719-14722
Ultrafast deactivation pathways bestow photostability on nucleobases and hence preserve the structural integrity of DNA following absorption of ultraviolet (UV) radiation. One controversial recovery mechanism proposed to account for this photostability involves electron‐driven proton transfer (EDPT) in Watson–Crick base pairs. The first direct observation is reported of the EDPT process after UV excitation of individual guanine–cytosine (G?C) Watson–Crick base pairs by ultrafast time‐resolved UV/visible and mid‐infrared spectroscopy. The formation of an intermediate biradical species (G[?H]?C[+H]) with a lifetime of 2.9 ps was tracked. The majority of these biradicals return to the original G?C Watson–Crick pairs, but up to 10 % of the initially excited molecules instead form a stable photoproduct G*?C* that has undergone double hydrogen‐atom transfer. The observation of these sequential EDPT mechanisms across intermolecular hydrogen bonds confirms an important and long debated pathway for the deactivation of photoexcited base pairs, with possible implications for the UV photochemistry of DNA. 相似文献