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11.
Most protocols used for open-path Fourier transform infrared spectrometry (OP/FT-IR) require that spectra be measured at a resolution of 1 cm(-1) and that the concentrations of the analytes be calculated by classical least squares regression (CLS). These specifications were largely developed for monitoring light molecules with easily resolvable rotational fine structure. For most volatile organic compounds in air, the rotational fine structure is not resolvable and better accuracy can be obtained when the spectrum is measured at lower resolution (typically 8 cm(-1)), provided that the algorithm used for quantification is partial least squares regression (PLS). By measuring the spectrum at low resolution, the need for a liquid-nitrogen-cooled mercury cadmium telluride detector is reduced and a pyroelectric detector operating at ambient temperature can be used instead. By using PLS rather than CLS, spectral features due to water vapor do not have to be compensated and a short-path background spectrum can be used, greatly simplifying field measurements. 相似文献
12.
Kritzer JA Tirado-Rives J Hart SA Lear JD Jorgensen WL Schepartz A 《Journal of the American Chemical Society》2005,127(1):167-178
Folded polymers are used in Nature for virtually every vital process. Nonnatural folded polymers, or foldamers, have the potential for similar versatility, and the design and refinement of such molecules is of considerable current interest. Here we report a complete and systematic analysis of the relationship between side chain structure and the 14-helicity of a well-studied class of foldamers, beta(3)-peptides, in water. Our experimental results (1) verify the importance of macrodipole stabilization for maintaining 14-helix structure, (2) provide comprehensive evidence that beta(3)-amino acids branched at the first side chain carbon are 14-helix-stabilizing, (3) suggest a novel role for side chain hydrogen bonding as an additional stabilizing force in beta(3)-peptides containing beta(3)-homoserine or beta(3)-homothreonine, and (4) demonstrate that diverse functionality can be incorporated into a stable 14-helix. Gas- and solution-phase calculations and Monte Carlo simulations recapitulate the experimental trends only in the context of oligomers, yielding insight into the mechanisms behind 14-helix folding. The 14-helix propensities of beta(3)-amino acids differ starkly from the alpha-helix propensities of analogous alpha-amino acids. This contrast informs current models for alpha-helix folding, and suggests that 14-helix folding is governed by different biophysical forces than is alpha-helix folding. The ability to modulate 14-helix structure through side chain choice will assist rational design of 14-helical beta-peptide ligands for macromolecular targets. 相似文献
13.
14.
The absorption spectra of a number of saturated hydrocarbons in the vacuum ultra-violet region have been examined and compared with their photoelectron and electron-loss spectra. Important conclusions about the quantum defect associated with the excited electrons and the nature of the excited states have been drawn from the relative positions of these spectra. The Rydberg bands of ethane, which were initially thought to originate in the C-C bond, have been shown to be associated with an electron largely localized in the CH3 group. 相似文献
15.
Chargaff’s second parity rule (CSPR) asserts that the frequencies of short polynucleotide chains are the same as those of
the complementary reversed chains. Up to now, this hypothesis has only been observed empirically and there is currently no
explanation for its presence in DNA strands. Here we argue that CSPR is a probabilistic consequence of the reverse complementarity
between paired strands, because the Gibbs distribution associated with the chemical energy between the bonds satisfies CSPR.
We develop a statistical test to study the validity of CSPR under the Gibbsian assumption and we apply it to a large set of
bacterial genomes taken from the GenBank repository. 相似文献
16.
Dr. Romaric Gérardy Dr. Anirudh M. K. Nambiar Travis Hart Prajwal T. Mahesh Prof. Dr. Klavs F. Jensen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(43):e202201385
The implementation of self-optimizing flow reactors has been mostly limited to model reactions or known synthesis routes. In this work, a self-optimizing flow photochemistry platform is used to develop an original synthesis of the bioactive fragment of Salbutamol and derivatives. The key photochemical steps for the construction of the aryl vicinyl amino alcohol moiety consist of a C−C bond forming reaction followed by an unprecedented, high yielding (>80 %), benzylic oxidative cyclization. 相似文献
17.
Aubert B Barate R Bona M Boutigny D Couderc F Karyotakis Y Lees JP Poireau V Tisserand V Zghiche A Grauges E Palano A Chen JC Qi ND Rong G Wang P Zhu YS Eigen G Ofte I Stugu B Abrams GS Battaglia M Brown DN Button-Shafer J Cahn RN Charles E Gill MS Groysman Y Jacobsen RG Kadyk JA Kerth LT Kolomensky YG Kukartsev G Lynch G Mir LM Orimoto TJ Pripstein M Roe NA Ronan MT Wenzel WA del Amo Sanchez P Barrett M Ford KE Harrison TJ Hart AJ Hawkes CM Morgan SE Watson AT Held T Koch H Lewandowski B 《Physical review letters》2007,98(5):051802
We present an observation of B-->eta'K*. The data sample corresponds to 232x10(6) BB[over ] pairs collected with the BABAR detector at the PEP-II asymmetric-energy B factory at the Stanford Linear Accelerator Center. We measure the branching fractions (in units of 10(-6)) B(B(0)-->eta'K*0)=3.8+/-1.1+/-0.5 and B(B+-->eta'K*+)=4.9(1.7)(+1.9)+/-0.8, where the first error is statistical and the second systematic. A simultaneous fit results in the observation of B-->eta'K* with B(B-->eta'K*)=4.1(-0.9)(+1.0)+/-0.5. We also search for B-->eta'rho and eta'f(0)(980)(f(0)-->pi+pi-) with results and 90% confidence level upper limits B(B+-->eta'rho+)=8.7(-2.8-1.3)(+3.1+2.3) (<14), B(B(0)-->eta'rho0)<3.7, and B(B(0)-->eta'f(0)(980)(f(0)-->pi+pi-))<1.5. Charge asymmetries in the channels with significant yields are consistent with zero. 相似文献
18.
CM Silva MF Duarte ML Mira MH Florêncio K Versluis AJ Heck 《Rapid communications in mass spectrometry : RCM》1999,13(12):1098-1103
Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
19.
Aubert B Bona M Boutigny D Couderc F Karyotakis Y Lees JP Poireau V Tisserand V Zghiche A Grauges E Palano A Chen JC Qi ND Rong G Wang P Zhu YS Eigen G Ofte I Stugu B Abrams GS Battaglia M Brown DN Button-Shafer J Cahn RN Charles E Gill MS Groysman Y Jacobsen RG Kadyk JA Kerth LT Kolomensky YG Kukartsev G Lynch G Mir LM Orimoto TJ Pripstein M Roe NA Ronan MT Wenzel WA del Amo Sanchez P Barrett M Ford KE Hart AJ Harrison TJ Hawkes CM Watson AT Held T Koch H Lewandowski B Pelizaeus M Peters K 《Physical review letters》2006,97(23):232001
We report the first observation of an excited singly charmed baryon Omega c* (css) in the radiative decay Omega c0gamma, where the Omega c0 baryon is reconstructed in the decays to the final states Omega(-)pi+, Omega(-)pi+pi0, Omega(-)pi+pi(-)pi+, and Xi(-)K(-)pi+pi+. This analysis is performed using a data set of 230.7 fb(-1) collected by the BABAR detector at the PEP-II asymmetric-energy B factory at the Stanford Linear Accelerator Center. The mass difference between the Omega c* and the Omega c0 baryons is measured to be 70.8+/-1.0(stat)+/-1.1(syst) MeV/c2. We also measure the ratio of inclusive production cross sections of Omega c* and Omega c0 in e+e(-) annihilation. 相似文献
20.
Markus Keel Hart F. Smith Christopher D. Sogge 《Journal of the American Mathematical Society》2004,17(1):109-153
We prove almost global existence for multiple speed quasilinear wave equations with quadratic nonlinearities in three spatial dimensions. We prove new results both for Minkowski space and also for nonlinear Dirichlet-wave equations outside of star shaped obstacles. The results for Minkowski space generalize a classical theorem of John and Klainerman. Our techniques only use the classical invariance of the wave operator under translations, spatial rotations, and scaling. We exploit the decay of solutions of the wave equation as much as the decay. Accordingly, a key step in our approach is to prove a pointwise estimate of solutions of the wave equation that gives decay of solutions of the inhomogeneous linear wave equation in terms of a -weighted norm on the forcing term. A weighted space-time estimate for inhomogeneous wave equations is also important in making the spatial decay useful for the long-term existence argument.