Experimental and Theoretical Studies of Unusual Four-Membered Metallacycles from Reactions of Group 4 Metallocene Bis(trimethylsilyl)-acetylene Complexes with the Sulfurdiimide Me3SiN=S=NSiMe3

The use of the sulfurdiimide RN=S=NR' (R = R' = SiMe3, 3) in reactions with group 4 metallocene bis(trimethylsilyl)-acetylene complexes of the type [Cp2M(L (eta(2)-Me3Si-C2SiMe3)] (1: M = Ti, no L; 2: M = Zr, L = pyridine) has led to the formation of four-membered metallacycles 4M containing the group 4 metal, nitrogen and sulfur. DFT calculations performed on compound 4Ti indicate that this complex is best described as a sigma-complex with cyclic delocalisation of the ring electrons. Moreover, pseudo-Jahn-Teller distortion plays a significant role in stabilising this complex.

Synthesis and Molecular Structures of Carboxylic Acid Group Bearing Two Ketoimines that Exist in Enaminone Form

Condensation reaction involving substituted aminobenzoic acids (2-aminobenzoic acid and 4-aminobenzoic acid) and acetylacetone results in the formation of ketoimines [CH3C(= O)CH2C(CH3)(= NAr)] (Ar = C6H4COOH-4; 1 and C6H4COOH-2 2). Compounds 1 and 2 have been characterized by spectroscopic techniques and by single crystal X-ray diffraction studies. The absorption, emission and lifetime measurement studies have also been performed for the new compounds. While compound 1 forms a linear chain type of aggregation though intermolecular hydrogen bonding, compound 2 forms a discrete dimer in the solid state.

Density matrix renormalization group algorithm for Bethe lattices of spin-1/2 or spin-1 sites with Heisenberg antiferromagnetic exchange

A density matrix renormalization group (DMRG) algorithm is presented for the Bethe lattice with connectivity Z = 3 and antiferromagnetic exchange between nearest-neighbor spins s = 1/2 or 1 sites in successive generations g. The algorithm is accurate for s = 1 sites. The ground states are magnetic with spin S(g) = 2(g)s, staggered magnetization that persists for large g > 20, and short-range spin correlation functions that decrease exponentially. A finite energy gap to S > S(g) leads to a magnetization plateau in the extended lattice. Closely similar DMRG results for s = 1/2 and 1 are interpreted in terms of an analytical three-site model.

Vertical Uplift Resistance of a Group of Two Coaxial Anchors in Clay

The vertical uplift resistance for a group of two horizontal coaxial rigid strip anchors embedded in clay under undrained condition has been determined by using the upper bound theorem of limit analysis in combination with finite elements. An increase of undrained shear strength of soil mass with depth has been incorporated. The uplift factor F-c gamma has been computed. As compared to a single isolated anchor, a group of two anchors provides greater magnitude of the uplift resistance. For a given embedment ratio, the group of two anchors generates almost the maximum uplift resistance when the upper anchor is located midway between ground surface and the lower anchor. For a given embedment ratio, F-c gamma increases linearly with an increase in the normalized unit weight of soil mass up to a certain value before attaining a certain maximum magnitude; the maximum value of F-c gamma increases with an increase in embedment ratio. DOI: 10.1061/(ASCE)GT.19435606.0000599. (C) 2012 American Society of Civil Engineers.

Combining adiabatic and Hartmann-Hahn cross-polarization for sensitivity enhancement in solid state separated local field 2D-NMR experiments of partially ordered systems

In this Letter, we examine magnetization in double- and zero-quantum reservoirs of an ensemble of spin-1/2 nuclei and describe their role in determining the sensitivity of a class of separated local field NMR experiments based on Hartmann-Hahn cross-polarization. We observe that for the liquid crystal system studied, a large dilute spin-polarization, obtained initially by the use of adiabatic cross-polarization, can enhance the sensitivity of the above experiment. The signal enhancement factors, however, are found to vary and depend on the local dynamics. The experimental results have been utilized to obtain the local order-parameters of the system. (C) 2012 Elsevier B. V. All rights reserved.

Crystal Engineering in the Desiraju Research Group in Bangalore

Over the years, crystal engineering has transformed into a mature and multidisciplinary subject. New understanding, challenges, and opportunities have emerged in the design of complex structures and structure-property evaluation. Revolutionary pathways adopted by many leaders have shaped and directed this subject. In this short essay to celebrate the 60th birthday of Prof. Gautam R. Desiraju, we, his current research group members, contemplate the development of some of the topics explored by our group in the context of the overall subject. These topics, though not entirely new, are of significant interest to the crystal engineering community.

Analyticity of the Schrodinger propagator on the Heisenberg group

We discuss the analytic extension property of the Schrodinger propagator for the Heisenberg sublaplacian and some related operators. The result for the sublaplacian is proved by interpreting the sublaplacian as a direct integral of an one parameter family of dilated special Hermite operators.

Generalized top-spin analysis and new physics in e(+)e(-) collisions with beam polarization

A generalized top-spin analysis proposed some time ago in the context of the standard model and subsequently studied in varying contexts is now applied primarily to the case of e(+)e(-) -> t (tww) over bar with transversely polarized beams. This extends our recent work with new physics couplings of scalar (S) and tensor (T) types. We carry out a comprehensive analysis assuming only the electron beam to be transversely polarized, which is sufficient to probe these interactions, and also eliminates any azimuthal angular dependence due to the standard model or new physics of the vector (V) and axial-vector (A) type interactions. We then consider new physics of the general four-Fermi type of V and A type with both beams transversely polarized and discuss implications with longitudinal polarization as well. The generalized spin bases are all investigated in the presence of either longitudinal or transverse beam polarization to look for appreciable deviation from the SM prediction in case of the new physics. 90% confidence level limits are obtained on the interactions for the generalized spin bases with realistic integrated luminosity. In order to achieve this we present a general discussion based on helicity amplitudes and derive a general transformation matrix that enables us to treat the spin basis. We find that beamline basis combined with transverse polarization provides an excellent window of opportunity both for S, T and V, A new physics, followed by the off-diagonal basis. The helicity basis is shown to be the best in case of longitudinal polarization to look for new physics effects due to V and A. DOI: 10.1103/PhysRevD.86.114019

Top-spin analysis of new scalar and tensor interactions in e(+) e (-) collisions with transverse beam polarization

The top polarization at the International Linear Collider (ILC) with transverse beam polarization is utilized in the process to probe interactions of the scalar and tensor type beyond the Standard Model and to disentangle their individual contributions. Confidence level limits of 90% are presented on the interactions with realistic integrated luminosity and are found to improve by an order of magnitude compared to the case when the spin of the top quark is not measured. Sensitivities of the order of a few times 10 (-aEuro parts per thousand 3) TeV (-aEuro parts per thousand 2) for real and imaginary parts of both scalar and tensor couplings at and 800 GeV with an integrated luminosity of 500 fb (-aEuro parts per thousand 1) and completely polarized beams are shown to be possible.

Perturbative expansion of the QCD Adler function improved by renormalization-group summation and analytic continuation in the Borel plane

We examine the large-order behavior of a recently proposed renormalization-group-improved expansion of the Adler function in perturbative QCD, which sums in an analytically closed form the leading logarithms accessible from renormalization-group invariance. The expansion is first written as an effective series in powers of the one-loop coupling, and its leading singularities in the Borel plane are shown to be identical to those of the standard ``contour-improved'' expansion. Applying the technique of conformal mappings for the analytic continuation in the Borel plane, we define a class of improved expansions, which implement both the renormalization-group invariance and the knowledge about the large-order behavior of the series. Detailed numerical studies of specific models for the Adler function indicate that the new expansions have remarkable convergence properties up to high orders. Using these expansions for the determination of the strong coupling from the hadronic width of the tau lepton we obtain, with a conservative estimate of the uncertainty due to the nonperturbative corrections, alpha(s)(M-tau(2)) = 0.3189(-0.0151)(+0.0173), which translates to alpha(s)(M-Z(2)) = 0.1184(-0.0018)(+0.0021). DOI: 10.1103/PhysRevD.87.014008

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.

Fabrication and characterization of micro-arc oxidized fluoride containing titania films on Cp Ti

The present study is focussed at establishing an appropriate electrolyte system for developing electrochemically stable and fluorine (F) containing titania (F-TiO2) films on Cp Ti by micro-arc oxidation (MAO) technique. To fabricate the F-TiO2 films on Cp Ti, different electrolyte solutions of chosen concentrations of tri-sodium orthophosphate (TSOP, Na3PO4 center dot I2H2O), potassium hydroxide (KOH) and various F-containing compounds such as ammonium fluoride (NH4F), potassium fluoride (KF), sodium fluoride (NaF) and potassium fluorotitanate (K2TiF6) are employed. The structural and morphological characteristics, thickness and elemental composition of the developed films have been assessed by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) techniques. The in-vitro electrochemical corrosion behavior of the films was studied under Kokubo simulated body fluid (SBF) environment by potentiodynamic polarization, long term potential measurement and electrochemical impedance spectroscopy (EIS) methods. The XRD and SEM-EDS results show that the rutile content in the films vary in the range of 15-37 wt% and the F and P contents in the films is found to be in the range of 2-3 at% and 2.9-4.7 at% respectively, suggesting that the anatase to rutile phase transformation and the incorporation of F and P into the films are significantly controlled by the respective electrolyte solution. The SEM elemental mapping results show that the electrolyte borne F and P elements are incorporated and distributed uniformly in all the films. Among all the films under study, the film developed with 5 g TSOP+2 g KOH+3 g K2TiF6 electrolyte system exhibits considerably improved in-vitro corrosion resistance and therefore best suited for biomedical applications. (C) 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

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.