Engagement of CF3 Group in N-H center dot center dot center dot F-C Hydrogen Bond in the Solution State: NMR Spectroscopy and MD Simulation Studies

Unambiguous evidence for the engagement of CF3 group in N-H center dot center dot center dot F-C hydrogen bond in a low polarity solvent, the first observation of its kind, is reported. The presence of such weak molecular interactions in the solution state is convincingly established by one and two-dimensional H-1, F-19, and natural abundant N-15 NMR spectroscopic studies. The strong and direct evidence is derived by the observation of through-space couplings, such as, (1h)J(FH), (1h)J(FN), and (2h)J(FF), where the spin polarization is transmitted through hydrogen bond. In an interesting example of a molecule containing two CF3 groups getting simultaneously involved in hydrogen bond, where hydrogen bond mediated couplings are not reflected in the NMR spectrum, F-19-F-19 NOESY experiment yielded confirmatory evidence. Significant deviations in the strengths of (1)J(NH), variable temperature, and the solvent induced perturbations yielded additional support. The NMR results are corroborated by both DFT calculations and MD simulations, where the quantitative information on different ways of involvement of fluorine in two and three centered hydrogen bonds, their percentage of occurrences, and geometries have been obtained. The hydrogen bond interaction energies have also been calculated.

Selective excitation and detection of maximum quantum coherence of a group of scalar coupled protons in chiral molecules: an NMR experiment for enantiodiscrimination

The H-1 NMR spectroscopic discrimination of enantiomers in the solution state and the measurement of enantiomeric composition is most often hindered due to either very small chemical shift differences between the discriminated peaks or severe overlap of transitions from other chemically non-equivalent protons. In addition the use of chiral auxiliaries such as, crown ether and chiral lanthanide shift reagent may often cause enormous line broadening or give little degree of discrimination beyond the crown ether substrate ratio, hampering the discrimination. In circumventing such problems we are proposing the utilization of the difference in the additive values of all the chemical shifts of a scalar coupled spin system. The excitation and detection of appropriate highest quantum coherence yields the measurable difference in the frequencies between two transitions, one pertaining to each enantiomer in the maximum quantum dimension permitting their discrimination and the F-2 cross section at each of these frequencies yields an enantiopure spectrum. The advantage of the utility of the proposed method is demonstrated on several chiral compounds where the conventional one dimensional H-1 NMR spectra fail to differentiate the enantiomers.

Spectral-envelope and group-delay models for transient signals—applications to castanets and stop consonants

We present a novel approach to represent transients using spectral-domain amplitude-modulated/frequency -modulated (AM-FM) functions. The model is applied to the real and imaginary parts of the Fourier transform (FT) of the transient. The suitability of the model lies in the observation that since transients are well-localized in time, the real and imaginary parts of the Fourier spectrum have a modulation structure. The spectral AM is the envelope and the spectral FM is the group delay function. The group delay is estimated using spectral zero-crossings and the spectral envelope is estimated using a coherent demodulator. We show that the proposed technique is robust to additive noise. We present applications of the proposed technique to castanets and stop-consonants in speech.

Spectral-envelope-group-delay models for transients

Transient signals such as plosives in speech or Castanets in audio do not have a specific modulation or periodic structure in time domain. However, in the spectral domain they exhibit a prominent modulation structure, which is a direct consequence of their narrow time localization. Based on this observation, a spectral-domain AM-FM model for transients is proposed. The spectral AM-FM model is built starting from real spectral zero-crossings. The AM and FM correspond to the spectral envelope (SE) and group delay (GD), respectively. Taking into account the modulation structure and spectral continuity, a local polynomial regression technique is proposed to estimate the GD function from the real spectral zeros. The SE is estimated based on the phase function computed from the estimated GD. Since the GD estimation is parametric, the degree of smoothness can be controlled directly. Simulation results based on synthetic transient signals generated using a beta density function are presented to analyze the noise-robustness of the SEGD model. Three specific applications are considered: (1) SEGD based modeling of Castanet sounds; (2) appropriateness of the model for transient compression; and (3) determining glottal closure instants in speech using a short-time SEGD model of the linear prediction residue.

Fourteen gene GBM prognostic signature identifies association of immune response pathway and mesenchymal subtype with high risk group

Background: Recent research on glioblastoma (GBM) has focused on deducing gene signatures predicting prognosis. The present study evaluated the mRNA expression of selected genes and correlated with outcome to arrive at a prognostic gene signature. Methods: Patients with GBM (n = 123) were prospectively recruited, treated with a uniform protocol and followed up. Expression of 175 genes in GBM tissue was determined using qRT-PCR. A supervised principal component analysis followed by derivation of gene signature was performed. Independent validation of the signature was done using TCGA data. Gene Ontology and KEGG pathway analysis was carried out among patients from TCGA cohort. Results: A 14 gene signature was identified that predicted outcome in GBM. A weighted gene (WG) score was found to be an independent predictor of survival in multivariate analysis in the present cohort (HR = 2.507; B = 0.919; p < 0.001) and in TCGA cohort. Risk stratification by standardized WG score classified patients into low and high risk predicting survival both in our cohort (p = <0.001) and TCGA cohort (p = 0.001). Pathway analysis using the most differentially regulated genes (n = 76) between the low and high risk groups revealed association of activated inflammatory/immune response pathways and mesenchymal subtype in the high risk group. Conclusion: We have identified a 14 gene expression signature that can predict survival in GBM patients. A network analysis revealed activation of inflammatory response pathway specifically in high risk group. These findings may have implications in understanding of gliomagenesis, development of targeted therapies and selection of high risk cancer patients for alternate adjuvant therapies.

Highly regioselective C2-alkenylation of indoles using the N-benzoyl directing group: an efficient Ru-catalyzed coupling reaction

A highly regioselective alkenylation of indole at the C2-position has been achieved using the Ru(II) catalyst by employing a directing group strategy. This strategy offers rare selectivity for the alkenylation N-benzoylindole at the C-2 position in the presence of the more active C3- and C7-position of indole and the ortho-positions of the benzoyl protecting group. A simple deprotection of the benzoyl group has also been exemplified, and the resulting product serves as a useful synthon for natural product syntheses.

Reduced-complexity partial-interference-cancellation group decoder for STBCs

In this letter, we propose a reduced-complexity implementation of partial interference cancellation group decoder with successive interference cancellation (PIC-GD-SIC) by employing the theory of displacement structures. The proposed algorithm exploits the block-Toeplitz structure of the effective matrix and chooses an ordering of the groups such that the zero-forcing matrices associated with the various groups are obtained through Schur recursions without any approximations. We show using an example that the proposed implementation offers a significantly reduced computational complexity compared to the direct approach without any loss in performance.

DETERMINATION OF THE STRONG COUPLING FROM HADRONIC TAU DECAYS USING RENORMALIZATION GROUP SUMMED PERTURBATION THEORY

Be the strong coupling constant alpha(s) from the tau hadronn width using a renormalization group summed (RGS) expansion of the QCD Adler lunction. The main theoretical uncertainty in the extraction of as is due to the manner in which renormalization group invariance is implemented, and the as yet uncalculated higher order terms in the QCD perturbative series. We show that new expansion exhibits good renormalization group improvement and the behavior of the series is similar to that of the standard RGS expansion. The value of the strong coupling in (MS) over bar scheme obtained with the RCS expansion is alpha(s) (M-tau(2)) = 0.338 +/- 0.010. The convergence properties of the new expansion can be improved by Bond transformation and analytic continuation in t he Bond plane. This is discussed elsewhere in these issues.

Horizontal pullout capacity of a group of two vertical plate anchors in clay

The horizontal pullout capacity of a group of two vertical strip plate anchors, placed along the same vertical plane, in a fully cohesive soil has been computed by using the lower bound finite element limit analysis. The effect of spacing between the plate anchors on the magnitude of total group failure load (P-uT) has been evaluated. An increase of soil cohesion with depth has also been incorporated in the analysis. For a weightless medium, the total pullout resistance of the group becomes maximum corresponding to a certain optimum spacing between the anchor plates which has been found to vary generally between 0.5B and B; where B is the width of the anchor plate. As compared to a single plate anchor, the increase in the pullout resistance for a group of two anchors becomes greater at a higher embedment ratio. The effect of soil unit weight has also been analyzed. It is noted that the interference effect on the pullout resistance increases further with an increase in the unit weight of soil mass.

Domains in complex surfaces with a noncompact automorphism group - II

Let X be an arbitrary complex surface and D subset of X a domain that has a noncompact group of holomorphic automorphisms. A characterization of those domains D that admit a smooth real analytic, finite type, boundary orbit accumulation point and whose closures are contained in a complete hyperbolic domain D' subset of X is obtained.

Group testing based spectrum hole search using a simple sub-nyquist sampling scheme

In this paper, we consider the problem of finding a spectrum hole of a specified bandwidth in a given wide band of interest. We propose a new, simple and easily implementable sub-Nyquist sampling scheme for signal acquisition and a spectrum hole search algorithm that exploits sparsity in the primary spectral occupancy in the frequency domain by testing a group of adjacent subbands in a single test. The sampling scheme deliberately introduces aliasing during signal acquisition, resulting in a signal that is the sum of signals from adjacent sub-bands. Energy-based hypothesis tests are used to provide an occupancy decision over the group of subbands, and this forms the basis of the proposed algorithm to find contiguous spectrum holes. We extend this framework to a multi-stage sensing algorithm that can be employed in a variety of spectrum sensing scenarios, including non-contiguous spectrum hole search. Further, we provide the analytical means to optimize the hypothesis tests with respect to the detection thresholds, number of samples and group size to minimize the detection delay under a given error rate constraint. Depending on the sparsity and SNR, the proposed algorithms can lead to significantly lower detection delays compared to a conventional bin-by-bin energy detection scheme; the latter is in fact a special case of the group test when the group size is set to 1. We validate our analytical results via Monte Carlo simulations.

Horizontal pullout resistance of a group of two vertical anchors in sand

The horizontal pullout capacity of a group of two vertical strip anchors placed along the same vertical plane in sand has been determined by using the upper bound finite elements limit analysis. The variation of the efficiency factor (xi (gamma) ) with changes in clear spacing (S) between the anchors has been established to evaluate the total group failure load for different values of (i) embedment ratio (H/B), (ii) soil internal friction angle (phi), and (iii) anchor-soil interface friction angle (delta). The total group failure load, for a given H/B, becomes always maximum corresponding to a certain optimal spacing (S-opt). The value of S-opt/B was found to lie in a range of 0.5-1.4. The maximum magnitude of xi (gamma) increases generally with increases in H/B, phi and delta.

Realistic coherent phantom track generation by a group of electronic combat aerial vehicles

We consider the problem of generating a realistic coherent phantom track by a group of ECAVs (Electronic Combat Aerial Vehicles) to deceive a radar network. The phantom track considered is the trajectory of a missile guided by proportional navigation. Sufficient conditions for the existence of feasible ECAV trajectories to generate the phantom track is presented. The line-of-sight guidance law is used to control the ECAVs for practical implementation. A performance index is developed to assess the performance of the ECAVS. Simulation results for single and multiple ECAVs generating the coherent phantom track are presented.

On the images of Sobolev spaces under the heat kernel transform on the Heisenberg group

The aim of this paper is to obtain certain characterizations for the image of a Sobolev space on the Heisenberg group under the heat kernel transform. We give three types of characterizations for the image of a Sobolev space of positive order H-m (H-n), m is an element of N-n, under the heat kernel transform on H-n, using direct sum and direct integral of Bergmann spaces and certain unitary representations of H-n which can be realized on the Hilbert space of Hilbert-Schmidt operators on L-2 (R-n). We also show that the image of Sobolev space of negative order H-s (H-n), s(> 0) is an element of R is a direct sum of two weighted Bergman spaces. Finally, we try to obtain some pointwise estimates for the functions in the image of Schwartz class on H-n under the heat kernel transform. (C) 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Regioselective Synthesis of 4-Substituted Indoles via C-H Activation: A Ruthenium Catalyzed Novel Directing Group Strategy

A highly regioselective functionalization of indole at the C-4 position by employing an aldehyde functional group as a directing group, and Ru as a catalyst, under mild reaction conditions (open flask) has been uncovered. This strategy to synthesize 4-substituted indoles is important, as this class of privileged molecules serves as a precursor for ergot alkaloids and related heterocyclic compounds.