Probing the dependence of long-range, four-atom interactions on intermolecular orientation. 1. Molecular hydrogen and iodine monochloride

The dependence of the long-range interactions between molecular hydrogen and iodine monochloride on the geometry between the molecules is investigated. Laser-induced fluorescence and action spectroscopy experiments have identified multiple conformers of the o,p-H2...I35,37Cl(X,v' '=0) van der Waals complexes. A conformer with the hydrogen molecule localized at the iodine end of the dihalogen, most likely with C2v symmetry, is significantly more stable than an asymmetric conformer with the hydrogen localized in the well oriented orthogonally to the I-Cl bond axis, D0' ' = 186.4(3) cm-1 versus 82.8(3) 相似文献   

Using auditory-visual speech to probe the basis of noise-impaired consonant-vowel perception in dyslexia and auditory neuropathy

Both dyslexics and auditory neuropathy (AN) subjects show inferior consonant-vowel (CV) perception in noise, relative to controls. To better understand these impairments, natural acoustic speech stimuli that were masked in speech-shaped noise at various intensities were presented to dyslexic, AN, and control subjects either in isolation or accompanied by visual articulatory cues. AN subjects were expected to benefit from the pairing of visual articulatory cues and auditory CV stimuli, provided that their speech perception impairment reflects a relatively peripheral auditory disorder. Assuming that dyslexia reflects a general impairment of speech processing rather than a disorder of audition, dyslexics were not expected to similarly benefit from an introduction of visual articulatory cues. The results revealed an increased effect of noise masking on the perception of isolated acoustic stimuli by both dyslexic and AN subjects. More importantly, dyslexics showed less effective use of visual articulatory cues in identifying masked speech stimuli and lower visual baseline performance relative to AN subjects and controls. Last, a significant positive correlation was found between reading ability and the ameliorating effect of visual articulatory cues on speech perception in noise. These results suggest that some reading impairments may stem from a central deficit of speech processing.     

An autocorrelation model with place dependence to account for the effect of harmonic number on fundamental frequency discrimination

Fundamental frequency (f0) difference limens (DLs) were measured as a function of f0 for sine- and random-phase harmonic complexes, bandpass filtered with 3-dB cutoff frequencies of 2.5 and 3.5 kHz (low region) or 5 and 7 kHz (high region), and presented at an average 15 dB sensation level (approximately 48 dB SPL) per component in a wideband background noise. Fundamental frequencies ranged from 50 to 300 Hz and 100 to 600 Hz in the low and high spectral regions, respectively. In each spectral region, f0 DLs improved dramatically with increasing f0 as approximately the tenth harmonic appeared in the passband. Generally, f0 DLs for complexes with similar harmonic numbers were similar in the two spectral regions. The dependence of f0 discrimination on harmonic number presents a significant challenge to autocorrelation (AC) models of pitch, in which predictions generally depend more on spectral region than harmonic number. A modification involving a "lag window"is proposed and tested, restricting the AC representation to a limited range of lags relative to each channel's characteristic frequency. This modified unitary pitch model was able to account for the dependence of f0 DLs on harmonic number, although this correct behavior was not based on peripheral harmonic resolvability.     

Compression and free expansion of single DNA molecules in nanochannels

We investigated compression and ensuing expansion of long DNA molecules confined in nanochannels. Transverse confinement of DNA molecules in the nanofluidic channels leads to elongation of their unconstrained equilibrium configuration. The extended molecules were compressed by electrophoretically driving them into porelike constrictions inside the nanochannels. When the electric field was turned off, the DNA strands expanded. This expansion, the dynamics of which has not previously been observable in artificial systems, is explained by a model that is a variation of de Gennes's polymer model.     

Synthesis and Biological Evaluation of the Antimicrobial Natural Product Lipoxazolidinone A

Natural products have historically been a major source of antibiotics and therefore novel scaffolds are constantly of interest. The lipoxazolidinone family of marine natural products, with an unusual 4‐oxazolidinone heterocycle at their core, represents a new scaffold for antimicrobial discovery; however, questions regarding their mechanism of action and high lipophilicity have likely slowed follow‐up studies. Herein, we report the first synthesis of lipoxazolidinone A, 15 structural analogues to explore its active pharmacophore, and initial resistance and mechanism of action studies. These results suggest that 4‐oxazolidinones are valuable scaffolds for antimicrobial development and reveal simplified lead compounds for further optimization.     

A Metal–Organic Framework with Exceptional Activity for C−H Bond Amination

The development of catalysts capable of fast, robust C?H bond amination under mild conditions is an unrealized goal despite substantial progress in the field of C?H activation in recent years. A Mn‐based metal–organic framework (CPF‐5) is described that promotes the direct amination of C?H bonds with exceptional activity. CPF‐5 is capable of functionalizing C?H bonds in an intermolecular fashion with unrivaled catalytic stability producing >10⁵ turnovers.     

Synthesis of heteroarylated ketones via bismuth(III) triflate-promoted regioselective 1,4- and 1,6-additions of electron-rich heteroarenes to cyclic enones and dienones

The development and optimization of bismuth(III) triflate-promoted regioselective 1,4- and 1,6-additions of electron-rich heteroarenes to cyclic, β,β-disubstituted enones and dienones is described. Additions of a range of heteroarenes, including furan, thiophene, pyrrole, and indole nucleophiles, to cyclic, β,β-disubstituted enones occur to form all-carbon quaternary centers in up to 88% yield. In addition, regioselective 1,6-additions of electron-rich heteroarenes to 3-vinyl-2-cyclohexenone occur to produce a variety of δ-heteroarylated, β,β-disubstituted enones in up to 93% yield. The high 1,6-selectivity for these reactions is attributed to the increased steric bulk at the β-position relative to the δ-position, and no competing 1,4-conjugate addition is observed.