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11.
[reaction: see text] We report here the enantioselective synthesis of Boc-alpha-methyl-d-cysteine(PMB)-OH and lanthionine building blocks through the regioselective ring opening of key intermediate Boc-alpha-methyl-d-serine-beta-lactone. 相似文献
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The thermodynamics and dynamics of a model S(N)1 reaction: t-BuCl --> t-Bu+ + Cl- is studied at the water liquid/vapor interface using molecular-dynamics computer simulations. The empirical valence bond approach is used to couple two diabatic states, covalent and ionic, in the electronically adiabatic limit. Umbrella sampling calculations are used to calculate the potential of mean force along the reaction coordinate (defined as the t-Bu to Cl distance) in bulk water and in several locations at the interface. We find a significant increase of the dissociation barrier height and of the reaction free energy at the interface relative to the bulk. This is shown to be due to the reduced polarity of the interface. Reactive flux correlation function calculations show significant deviation of the rate constant from the transition-state theory: The transmission coefficients range from 0.49 in the bulk to 0.05 above the Gibbs surface. The low transmission coefficient at the interface despite the lower friction is shown to be due to slow vibrational relaxation. 相似文献
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How Modifying Third‐Party Information Affects Interpersonal Impressions and the Evaluation of Collaborative Online Media 下载免费PDF全文
David C. DeAndrea Brandon Van Der Heide Nicole Easley 《The Journal of communication》2015,65(1):62-78
Previous research has drawn upon warranting theory to help explain how viewers evaluate people and entities online. Extending previous research, this study assesses how the ability of a target to modify third‐party information affects perceptions of warranting value, and in turn, interpersonal impressions and the perceived legitimacy of online media that host evaluations. Additionally, this work explores how the perceived objectivity of a third‐party evaluator affects impressions in online settings. The results provide support for warranting theory and help clarify how impressions are formed in online environments when people have the ability to generate and modify content collectively. The theoretical implications this study has for warranting theory and future research directions are discussed. 相似文献
16.
Christopher M. MacNeill Robert C. Coffin David L. Carroll Nicole H. Levi‐Polyachenko 《Macromolecular bioscience》2013,13(1):28-34
Low band gap D‐A conjugated PNs consisting of 2‐ethylhexyl cyclopentadithiophene co‐polymerized with 2,1,3‐benzothiadiazole (for nano‐PCPDTBT) or 2,1,3‐benzoselenadiazole (for nano‐PCPDTBSe) have been developed. The PNs are stable in aqueous media and showed no significant toxicity up to 1 mg · mL?1. Upon exposure to 808 nm light, the PNs generated temperatures above 50 °C. Photothermal ablation studies of the PNs with RKO and HCT116 colorectal cancer cells were performed. At concentrations above 100 µg · mL?1 for nano‐PCPDTBSe, cell viability was less than 20%, while at concentrations above 62 µg · mL?1 for nano‐PCPDTBT, cell viability was less than 10%. The results of this work demonstrate that low band gap D‐A conjugated polymers 1) can be formed into nanoparticles that are stable in aqueous media; 2) are non‐toxic until stimulated by IR light and 3) have a high photothermal efficiency.
17.
We consider dark matter annihilation into standard model particles and show that the least detectable final states, namely, neutrinos, define an upper bound on the total cross section. Calculating the cosmic diffuse neutrino signal, and comparing it to the measured terrestrial atmospheric neutrino background, we derive a strong and general bound. This can be evaded if the annihilation products are dominantly new and truly invisible particles. Our bound is much stronger than the unitarity bound at the most interesting masses, shows that dark matter halos cannot be significantly modified by annihilations, and can be improved by a factor of 10-100 with existing neutrino experiments. 相似文献
18.
Molecular beacons with oxidized bases report on substrate specificity of DNA oxoguanine glycosylases
DNA glycosylase enzymes recognize and remove structurally distinct modified forms of DNA bases, thereby repairing genomic DNA from chemically induced damage or erasing epigenetic marks. However, these enzymes are often promiscuous, and advanced tools are needed to evaluate and engineer their substrate specificity. Thus, in the present study, we developed a new strategy to rapidly profile the substrate specificity of 8-oxoguanine glycosylases, which cleave biologically relevant oxidized forms of guanine. We monitored the enzymatic excision of fluorophore-labeled oligonucleotides containing synthetic modifications 8-oxoG and FapyG, or G. Using this molecular beacon approach, we identified several hOGG1 mutants with higher specificity for FapyG than 8-oxoG. This approach and the newly synthesized probes will be useful for the characterization of glycosylase substrate specificity and damage excision mechanisms, as well as for evaluating engineered enzymes with altered reactivities.A three-color fluorescent molecular beacon assay for rapid profiling of substrate specificity of hOGG1 variants, and for engineering proteins to map genomic modifications. 相似文献
19.
Peter Sörös Jonathan Marmurek Fred Tam Nicole Baker W Richard Staines Simon J Graham 《BMC neuroscience》2007,8(1):48
Background
Focal lesions of the frontal, parietal and temporal lobe may interfere with tactile working memory and attention. To characterise the neural correlates of intact vibrotactile working memory and attention, functional MRI was conducted in 12 healthy young adults. Participants performed a forced-choice vibrotactile frequency discrimination task, comparing a cue stimulus of fixed frequency to their right thumb with a probe stimulus of identical or higher frequency. To investigate working memory, the time interval between the 2 stimuli was pseudo-randomized (either 2 or 8 s). To investigate selective attention, a distractor stimulus was occasionally presented contralaterally, simultaneous to the probe. 相似文献20.
First-principles calculations are presented for the layered perovskite Ca3Mn2O7. The results reveal a rich set of coupled structural, magnetic, and polar domains in which oxygen octahedron rotations induce ferroelectricity, magnetoelectricity, and weak ferromagnetism. The key point is that the rotation distortion is a combination of two nonpolar modes with different symmetries. We use the term "hybrid" improper ferroelectricity to describe this phenomenon and discuss how control over magnetism is achieved through these functional antiferrodistortive octahedron rotations. 相似文献