Cruciform pi-systems for molecular electronics applications

This study details a modular and general synthesis of a new class of molecules consisting of cruciform pi-systems. The key to synthesizing these molecules was an unprecedented double Staudinger cyclization. Once formed, these rigid compounds assemble into ordered monolayer films on metal and metal oxide surfaces to orient their conjugated, bis-phenyloxazole subunits upright. This surface orientation is enforced by the external phenyl substituents that are out of the ring plane, thus preventing the prone conformation.     

Meshfree Extrapolation with Application to Enhanced Near-Boundary Approximation with Local Lagrange Kernels

Foundations of Computational Mathematics - The paper deals with the problem of extrapolating data derived from sampling a $$C^m$$ function at scattered sites on a Lipschitz region $$\varOmega $$ in...     

Following photoinduced dynamics in bacteriorhodopsin with 7-fs impulsive vibrational spectroscopy

Sub-10-fs laser pulses are used to impulsively photoexcite bacteriorhodopsin (BR) suspensions and probe the evolution of the resulting vibrational wave packets. Fourier analysis of the spectral modulations induced by transform-limited as well as linearly chirped excitation pulses allows the delineation of excited- and ground-state contributions to the data. On the basis of amplitude and phase variations of the modulations as a function of the dispersed probe wavelength, periodic modulations in absorption above 540 nm are assigned to ground-state vibrational coherences induced by resonance impulsive Raman spectral activity (RISRS). Probing at wavelengths below 540 nm-the red edge of the intense excited-state absorption band-uncovers new vibrational features which are accordingly assigned to wave packet motions along bound coordinates on the short-lived reactive electronic surface. They consist of high- and low-frequency shoulders adjacent to the strong C=C stretching and methyl rock modes, respectively, which have ground-state frequencies of 1008 and 1530 cm-1. Brief activity centered at approximately 900 cm-1, which is characteristic of ground-state HOOP modes, and strong modulations in the torsional frequency range appear as well. Possible assignments of the bands and their implication to photoinduced reaction dynamics in BR are discussed. Reasons for the absence of similar signatures in the pump-probe spectral modulations at longer probing wavelengths are considered as well.     

Quantitative structure-activity relationship analysis of β-amyloid aggregation inhibitors

Inhibiting the aggregation process of the β-amyloid peptide is a promising strategy in treating Alzheimer’s disease. In this work, we have collected a dataset of 80 small molecules with known inhibition levels and utilized them to develop two comprehensive quantitative structure–activity relationship models: a Bayesian model and a decision tree model. These models have exhibited high predictive accuracy: 87% of the training and test sets using the Bayesian model and 89 and 93% of the training and test sets, respectively, by the decision tree model. Subsequently these models were used to predict the activities of several new potential β-amyloid aggregation inhibitors and these predictions were indeed validated by in vitro experiments. Key chemical features correlated with the inhibition ability were identified. These include the electro-topological state of carbonyl groups, AlogP and the number of hydrogen bond donor groups. The results demonstrate the feasibility of the developed models as tools for rapid screening, which could help in the design of novel potential drug candidates for Alzheimer’s disease.     

An achiral manganese salen catalyst encapsulated in a peptidic phosphonate homochiral solid for the enantioselective formation of diols by consecutive epoxidation and hydration reactions

An insoluble, porous, amorphous, homochiral material based on a polypeptide titanium-phosphonate scaffold with an encapsulated achiral Mn(III)-salen was prepared and characterized. Consecutive epoxidation and hydration of styrene and its derivatives by aqueous hypochlorite in THF showed the highly enantioselective (>99%) formation of styrene diol derivatives.     

Kinetic bromine isotope effect: example from the microbial debromination of brominated phenols

The increasing use of kinetic isotope effects for environmental studies has motivated the development of new compound-specific isotope analysis techniques for emerging pollutants. Recently, high-precision bromine isotope analysis in individual brominated organic compounds was proposed, by the coupling of gas chromatography to a multi-collector inductively coupled plasma mass spectrometer using strontium as an external spike for instrumental bias correction. The present study, for the first time, demonstrates an application of this technique for determining bromine kinetic isotope effects during biological reaction, focusing on the reductive debromination of brominated phenols under anaerobic conditions. Results show bromine isotope enrichment factors (ε) of ?0.76?±?0.08, ?0.46?±?0.19, and ?0.20?±?0.06?‰ for the debromination of 4-bromophenol, 2,4-dibromophenol, and 2,4,6-tribromophenol, respectively. These values are rather low, yet still high enough to be obtained with satisfying certainty. This further implies that the analytical method may be also appropriate for future environmental applications.     

The perceptual nature of vocal register change

This study focuses on the perceptual nature of chest and falsetto registers as a function of various production tokens and methods of perceptual evaluation. Fifteen target tones, ranging from G#3 to A#4, were sung by a male and a female subject in the context of ascending and descending sequences on the vowels /a/ and /i/. Register transitions were elicited by setting strict constraints on production. Segments of 1-s duration were extracted from the target notes, digitized, and acoustically analyzed. These excerpts were presented to ten trained listeners in four different perceptual tasks. Identification and discrimination tasks yielded nearly identical results, suggesting that the primary registers are perceived as distinct entities. The marked change from chest to falsetto as well as the locus of the transition between these registers did not vary systematically as a function of production token or perceptual task. Mean register shift-point frequencies of the male and female subjects were perceived at 320 Hz and 353 Hz, respectively. Multidimensional scaling and hierarchical clustering analyses were utilized to capture the dimensionality and the internal structure of perceptual data sets derived from the pair-wise similarity ratings. Optimal spatial representation of these data required no more than two orthogonal dimensions, with the quality attribute represented by the dominant dimension. The representation of pitch differences was reflected only in the internal ordering of the stimuli within registers, but did not affect the perceptual discontinuity between registers.     

A Push–Pull Network with Infinite Supply of Work

We consider a two-node multiclass queueing network with two types of jobs moving through two servers in opposite directions, and there is infinite supply of work of both types. We assume exponential processing times and preemptive resume service. We identify a family of policies which keep both servers busy at all times and keep the queues between the servers positive recurrent. We analyze two specific policies in detail, obtaining steady state distributions. We perform extensive calculations of expected queue lengths under these policies. We compare this network with the Kumar–Seidman–Rybko–Stolyar network, in which there are two random streams of arriving jobs rather than infinite supply of work.