Hexa-arm star shaped hydrazone derivatives from hexakis(4-formylphenoxy)-cyclotriphosphazene core

A series of novel hexasubstituted cyclophosphazene hydrazones [N(3)P(3)(-OC(6)H(4)-p-CH=N-NH-C(O)-C(6)H(4)-p-X)(6)] (X = H, Br, Cl, F, OH, OCH(3), CH(3), NO(2), NH(2)) were prepared by a sixfold condensation reaction of [N(3)P(3)(-OC(6)H(4)-p-CHO)(6)] with para-substituted benzoic hydrazides [NH(2)-NH-C(O)-C(6)H(4)-p-X] with excellent yields (91-98%). The structures of the compounds were confirmed by elemental analysis, FT-IR, (1)H, (13)C, (31)P, 2D-HSQC NMR and mass spectrometry (MALDI-TOF). All the synthesized cyclophosphazene hydrazones exhibit high thermal stability. The crystal structure of a homogeneously substituted hexakis(4-formylphenoxy)-cyclotriphosphazene was determined by X-ray diffraction analysis. The compound crystallizes in the monoclinic system, space group P2(1)/n with a = 16.558(3) angstrom, b = 10.250(2) angstrom, c = 23.429(5) angstrom, alpha = gamma = 90.00 degrees, beta = 90.461(4)degrees, V = 3976.5(14) angstrom(3) and Z = 4. The R value is 0.0823 for 4290 observed reflections. The conformations of the 4-formylphenoxy-groups are different at the three phosphorus atoms. (C) 2011 Elsevier B.V. All rights reserved.

Phase Characterization and Study of Molecular Order of a Three-Ring Mesogen by (13)C NMR in Smectic C and Nematic Phases

Molecules exhibiting a thermotropic liquid-crystalline property have acquired significant importance due to their sensitivity to external stimuli such as temperature, mechanical forces, and electric and magnetic fields. As a result, several novel mesogens have been synthesized by the introduction of various functional groups in the vicinity of the aromatic core as well as in the side chains and their properties have been studied. In the present study, we report three-ring mesogens with hydroxyl groups at one terminal. These mesogens were synthesized by a multistep route, and structural characterization was accomplished by spectral techniques. The mesophase properties were studied by hot-stage optical polarizing microscopy, differential scanning calorimetry, and small-angle X-ray scattering. An enantiotropic nematic phase was noticed for lower homologues, while an additional smectic C phase was found for higher homologues. Solid-state high-resolution natural abundance (13)C NMR studies of a typical mesogen in the solid phase and in the mesophases have been carried out. The (13)C NMR spectrum of the mesogen in the smectic C and nematic phases indicated spontaneous alignment of the molecule in the magnetic field. By utilizing the two-dimensional separated local field (SLF) NMR experiment known as SAMPI4, (13)C-(1)H dipolar couplings have been obtained, which were utilized to determine the orientational order parameters of the mesogen.

Sol-Gel Transition in Dispersions of Layered Double-Hydroxide Nanosheets

Surfactant-intercalated layered double-hydroxide solid Mg-Al LDH-dodecyl sulfate (DDS) undergoes rapid and facile delamination to its ultimate constituent, single sheets of nanometer thickness and micrometer size, in a nonpolar solvent such as toluene to form stable dispersions. The delaminated nanosheets are electrically neutral because the surfactant chains remain tethered to the inorganic layer even on exfoliation. With increasing volume fraction of the solid, the dispersion transforms from a free-flowing sol to a solidlike gel. Here we have investigated the sol-gel transition in dispersions of the hydrophobically modified Mg-Al LDH-DDS in toluene by rheology, SAXS, and (1)H NMR measurements. The rheo-SAXS measurements show that the sharp rise in the viscosity of the dispersion during gel formation is a consequence of a tactoidal microstructure formed by the stacking of the nanosheets with an intersheet separation of 3.92 nm. The origin and nature of the attractive forces that lead to the formation of the tactoidal structure were obtained from 1D and 2D (1)H NMR measurements that provided direct evidence of the association of the toluene solvent molecules with the terminal methyl of the tethered DDS surfactant chains. Gel formation is a consequence of the attractive dispersive interactions of toluene molecules with the tails of DDS chains anchored to opposing Mg-Al LDH sheets. The toluene solvent molecules function as molecular ``glue'' holding the nanosheets within the tactoidal microstructure together. Our study shows how rheology, SAXS, and NMR measurements complement each other to provide a molecular-level description of the sol-gel transition in dispersions of a hydrophobically modified layered double hydroxide.

Scalable processes for fabricating non-volatile memory devices using self-assembled 2D arrays of gold nanoparticles as charge storage nodes

We propose robust and scalable processes for the fabrication of floating gate devices using ordered arrays of 7 nm size gold nanoparticles as charge storage nodes. The proposed strategy can be readily adapted for fabricating next generation (sub-20 nm node) non-volatile memory devices.

Evaluation of 2D image reconstruction using fan-beam FBP algorithm with no backprojection weight from WLP completed truncated projection data

This paper presents the image reconstruction using the fan-beam filtered backprojection (FBP) algorithm with no backprojection weight from windowed linear prediction (WLP) completed truncated projection data. The image reconstruction from truncated projections aims to reconstruct the object accurately from the available limited projection data. Due to the incomplete projection data, the reconstructed image contains truncation artifacts which extends into the region of interest (ROI) making the reconstructed image unsuitable for further use. Data completion techniques have been shown to be effective in such situations. We use windowed linear prediction technique for projection completion and then use the fan-beam FBP algorithm with no backprojection weight for the 2-D image reconstruction. We evaluate the quality of the reconstructed image using fan-beam FBP algorithm with no backprojection weight after WLP completion.

Parallel Computation of 2D Morse-Smale Complexes

The Morse-Smale complex is a useful topological data structure for the analysis and visualization of scalar data. This paper describes an algorithm that processes all mesh elements of the domain in parallel to compute the Morse-Smale complex of large two-dimensional data sets at interactive speeds. We employ a reformulation of the Morse-Smale complex using Forman's Discrete Morse Theory and achieve scalability by computing the discrete gradient using local accesses only. We also introduce a novel approach to merge gradient paths that ensures accurate geometry of the computed complex. We demonstrate that our algorithm performs well on both multicore environments and on massively parallel architectures such as the GPU.

NMR methods for fast data acquisition

NMR spectroscopy has witnessed tremendous advancements in recent years with the development of new methodologies for structure determination and availability of high-field strength spectrometers equipped with cryogenic probes. Supported by these advancements, a new dimension in NMR research has emerged which aims to increase the speed with data is collected and analyzed. Several novel methodologies have been proposed in this direction. This review focuses on the principles on which these different approaches are based with an emphasis on G-matrix Fourier transform NMR spectroscopy.

Study of liquid crystalline order by NMR

The liquid crystalline phase represents a unique state of matter where partial order exists on molecular and supra-molecular levels and is responsible for several interesting properties observed in this phase. Hence a detailed study of ordering in liquid crystals is of significant scientific and technological interest. NMR provides several parameters that can be used to obtain information about the liquid crystalline phase. Of these, the measurement of dipolar couplings between nuclei has proved to be a convenient way of obtaining liquid crystalline ordering since the coupling is dependent on the average orientation of the dipolar vector in the magnetic field which also aligns the liquid crystal.However, measurement of the dipolar coupling between a pair of selected nuclei is beset with problems that require special solutions. In this article the use of cross polarization for measuring dipolar couplings in liquid crystals is illustrated. Transient oscillations observed during cross polarization provide the dipolar couplings between essentially isolated nearest neighbor spins which can be extracted for several sites simultaneously by employing two-dimensional NMR techniques. The use of the method for obtaining heteronuclear dipolar couplings and hence the order parameters of liquid crystals is presented. Several modifications to the basic experiment are considered and their utility illustrated. A method for obtaining proton–proton dipolar couplings, by utilizing cross polarization from the dipolar reservoir, is presented. Some applications are also highlighted.

Three-Component Chiral Derivatizing Protocols for NMR Spectroscopic Enantiodiscrimination of Hydroxy Acids and Primary Amines

The novel three-component chiral derivatization protocols have been derived for (1)H and (19)F NMR spectroscopic discrimination of a series of chiral hydroxy acids by their coordination and self-assembly with optically active a-methylbenzylamine and 2-formylphenylboronic acid. In addition, the optically pure (S)-mandelic acid in combination with 2-formylphenylboronic acid permits visualization of enantiomers of primary amines. These protocols have been demonstrated on enantiodiscrimination of chiral amines and hydroxy acids.

NMR Structure Implications of Enhanced Efficacy of Obestatin Fragment Analogs

Obestatin is a more recently discovered hormone that is encoded by the ghrelin gene and produced in the stomach and gut. We report NMR analysis on synthetic Obestatin (OB23), a 23 residue peptide, along with three overlapping fragments of the same in methanol solvent as a first step towards structure activity relationship. Selective substitutions on the promising N-terminal and middle fragments of obestatin have been carried out in order to improve the efficacy and potency. In the N-terminal fragment two peptides were obtained by the replacement of Gly (8) with a-aminoisobutyric acid (Aib, U) and Phe (F5) with Cyclohexylalanine (Cha). In case of the middle fragment both Gly (3) and Gly (8) were replaced with Aib residues. The rationale being, these unusual amino acids could provide protection from immediate degradation and aid structure stabilization. Our previous studies showed that the N-terminal and the middle fragment were unstructured and hence this substitution would directly evaluate the effect of structure on the activity of these fragment analogs. Detailed NMR analysis clearly demonstrates formation of helical secondary structure in all the peptide analogues and provides justification for relative activities reported by our group previously (Nagaraj et al. 2009).

Selective double quantum resolved correlation experiment for the complete separation of entire proton NMR spectra of enantiomers

The present study reports a two dimensional NMR experiment which separates single quantum spectra of enantiomers from that of a racemic mixture. This is a blend of selective double quantum refocusing, for resolving couplings and chemical shift interactions along two dimensions followed by correlation of the selectively excited protons to the entire coupled spin network. The concept is solely based on the presence of distinct intra methyl dipolar couplings of different enantiomers when dissolved in chiral orienting media. The analysis of single enantiomer spectrum obtained from respective F-2 cross sections yield all the spectral information. (C) 2011 Elsevier Inc. All rights reserved.

Spontaneous self-assembly of designed cyclic dipeptide (Phg-Phg) into two-dimensional nano- and mesosheets

In this study, we present the spontaneous self-assembly of designed simplest aromatic cyclic dipeptides of (L-Phg-L-Phg) and (D-Phg-L-Phg) to form highly stable two-dimensional (2D) nano- and mesosheets with large lateral surface area. Various microscopy data revealed that the morphology of 2D mesosheets resembles the hierarchical natural materials with layered structure. Solution and solid-state NMR studies on cyclo(L-Phg-L-Phg) revealed the presence of strong (N-H-O) hydrogen-bonded molecular chains supported by aromatic pi-pi interactions to form 2D mesosheets. Interestingly, cyclo(D-Phg-L-Phg) self-assembles to form single-crystalline as well as non-crystalline 2D rhomboid sheets with large lateral dimension. X-ray diffraction analysis revealed the stacking of (N-H-O) hydrogen-bonded molecular layers along c-axis supported by aromatic pi-pi interactions. The thermogravimetric analysis shows two transitions with overall high thermal stability attributed to layered hierarchy found in 2D mesosheets.

Algorithmic approach to simulate Hamiltonian dynamics and an NMR simulation of quantum state transfer

We propose an iterative algorithm to simulate the dynamics generated by any n-qubit Hamiltonian. The simulation entails decomposing the unitary time evolution operator U (unitary) into a product of different time-step unitaries. The algorithm product-decomposes U in a chosen operator basis by identifying a certain symmetry of U that is intimately related to the number of gates in the decomposition. We illustrate the algorithm by first obtaining a polynomial decomposition in the Pauli basis of the n-qubit quantum state transfer unitary by Di Franco et al. [Phys. Rev. Lett. 101, 230502 (2008)] that transports quantum information from one end of a spin chain to the other, and then implement it in nuclear magnetic resonance to demonstrate that the decomposition is experimentally viable. We further experimentally test the resilience of the state transfer to static errors in the coupling parameters of the simulated Hamiltonian. This is done by decomposing and simulating the corresponding imperfect unitaries.