13C NMR investigations of molecular order of rod-like,bent-core,and thiophene mesogens

In this review, methods to obtain the orientational order of topologically variant molecular mesogens using by one- and two-dimensional (2D) solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy are described. Besides ¹³C chemical shifts, the ¹³C─¹H dipolar couplings measured from 2D-separated local field (SLF) technique are used for computing the order parameters of a variety of mesogens. The investigated molecules are composed of a variable number of rings in the core, that is, core ranging from simply one ring to five rings. Among the mesogens investigated, a special focus has been placed on mesogens with thiophene rings, which are gaining popularity as liquid crystalline organic semiconductors. The replacement of a phenyl ring by thiophene in the core has a dramatic influence on molecular topology, as observed from the measured order parameters. The review highlights the advantages of the 2D SLF method for understanding the local dynamics and for mapping the topology of mesogens through the measured order parameters. SLF NMR studies of as many as 24 molecular mesogens that vary in terms of the molecular structure as well as topology are covered in the review. Order parameters of the rings have been estimated from the ¹³C─¹H dipolar couplings in the nematic, smectic A, smectic C, and tilted hexatic phases as well as in B₁ and B₂ mesophases of various mesogens. It is anticipated that, in the years to come, the 2D SLF method would provide advanced molecular information on structurally complex mesogens that are emerging in liquid crystal science through the incessant efforts of synthetic chemists. The mini review covers the orientational order of topologically variant molecular mesogens determined by 1D and 2D solid-state ¹³C NMR spectroscopy. Accordingly, rod-like, bent-core, and thiophene mesogens were subjected to 2D SLF measurements to get the order parameters from which the topology was established. The replacement of phenyl ring by thiophene and its influence on order parameters as well as on molecular topology is also discussed.     

Face verification across age progression.

Human faces undergo considerable amounts of varialions with aging. While face recognition systems have been proven to be sensitive to factors such as illumination and pose, their sensitivity to facial aging effects is yet to be studied. How does age progression affect the similarity between a pair of face images of an individual? What is the confidence associated with establishing the identity between a pair of age separated face images? In this paper, we develop a Bayesian age difference classifier that classifies face images of individuals based on age differences and performs face verification across age progression. Further, we study the similarity of faces across age progression. Since age separated face images invariably differ in illumination and pose, we propose preprocessing methods for minimizing such variations. Experimental results using a database comprising of pairs of face images that were retrieved from the passports of 465 individuals are presented. The verification system for faces separated by as many as nine years, attains an equal error rate of 8.5%.     

Graphitic nanofillers in PMMA nanocomposites—An investigation of particle size and dispersion and their influence on nanocomposite properties

Mechanical, thermal, and electrical properties of graphite/PMMA composites have been evaluated as functions of particle size and dispersion of the graphitic nanofiller components via the use of three different graphitic nanofillers: “as received graphite” (ARG), “expanded graphite,” (EG) and “graphite nanoplatelets” (GNPs) EG, a graphitic materials with much lower density than ARG, was prepared from ARG flakes via an acid intercalation and thermal expansion. Subsequent sonication of EG in a liquid yielded GNPs as thin stacks of graphitic platelets with thicknesses of ～10 nm. Solution‐based processing was used to prepare PMMA composites with these three fillers. Dynamic mechanical analysis, thermal analysis, and electrical impedance measurements were carried out on the resulting composites, demonstrating that reduced particle size, high surface area, and increased surface roughness can significantly alter the graphite/polymer interface and enhance the mechanical, thermal, and electrical properties of the polymer matrix. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2097–2112, 2007     

Multicast tree generation in networks with asymmetric links

We formulate the problem of multicast tree generation as one of computing a directed Steiner tree of minimal cost. In this context, we present a polynomial-time algorithm that provides for trade-off selection, using a single parameter κ, between the tree-cost (Steiner cost) and the run time efficiency. Further, the same algorithm may be used for delay optimization or tree-cost minimization simply by configuring the value of κ appropriately. We present theoretical and experimental analysis characterizing the problem and the performance of our algorithm. Theoretically, we show that it is highly unlikely that there exists a polynomial-time algorithm with a performance guarantee of constant times optimum cost, introduce metrics for measuring the asymmetry of graphs, and show that the worst-case cost of the tree produced by our algorithm is, at most, twice the optimum cost times the asymmetry, for two of these asymmetry metrics. For graphs with bounded asymmetry, this gives constant times optimum performance guarantee. We also show that three well-known algorithms for (undirected) Steiner trees are but particular cases of our algorithm. Our experimental study shows that operating at a low κ gives nearly best possible expected tree cost while maintaining acceptable run-time efficiency     

Coulometric determination of NAD+ and NADH in normal and cancer cells using LDH, RVC and a polymer mediator

An electrochemical method for the measurement of NAD(+) and NADH in normal and cancer tissues using flow injection analysis (FIA) is reported. Reticulated vitreous carbon (RVC) electrodes with entrapped l-lactate dehydrogenase (LDH) and a new redox polymer containing covalently bound toluidine blue O (TBO) were employed for this purpose. Both NAD(+) and NADH were estimated coulometrically based on their reaction with LDH. The latter was immobilized on controlled pore glass (CPG) by cross-linking with glutaraldehyde and packed within the RVC. The concentrations of NAD(+) and NADH in the tissues, estimated using different electron mediators such as ferricyanide (FCN), meldola blue (MB) and TBO have also been compared. The effects of flow rate, pH, applied potential (versus Ag/AgCl reference) and adsorption of the mediators have also been investigated. Based on the measurements of NAD(+) and NADH in normal and cancer tissues it has been concluded that the NADH concentration is lower, while the NAD(+) concentration is higher in cancer tissues. Amongst the electron mediators TBO was found to be a more stable mediator for such measurements.     

Thermal decomposition kinetics of vanillidene anthranilic acid complexes of cobalt(II), nickel(II), copper(II) and zinc(II)

The thermal decomposition of cobalt(II), nickel(II), copper(II) and zinc(II) complexes of the Schiff base vanillidene anthranilic acid was studied by TG. The chelates show somewhat similar TG plots when heated in an atmosphere of air. Thermoanalytical data (TG and DTG) of these chelates are presented in this communication. Interpretation and mathematical analysis of these data and evaluation of order of reaction, the energy and entropy of activation based on the differential method employing the Freeman-Carroll equation, the integral method using Coats-Redfern equation and the approximation method using the Horowitz-Metzger equation are also given. On the basis of experimental findings in the present course of studies, it is concluded that the relative thermal stability of vanillidene anthranilic acid chelates can be aligned as Co(II)Ni(II)>Zn(II)>Cu(II).

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Zusammenfassung Die thermische Zersetzung von Cobalt(II)-, Nickel(II)-, Kupfer(II)- und Zink(II)-Komplexen der Schiffschen Base Vanillidenanthranilsäure wurde thermogravimetrisch untersucht. Die Chelate zeigen in einer Luftatmosphäre ähnliche TG-Kurven. Thermoanalytische Daten (TG and DTG) dieser Chelate werden mitgeteilt, interpretiert und mathematisch analysiert. Ebenfalls werden die Reaktionsordnung und die Energie und Entropie der Aktivierung nach der von Freeman-Carroll angewandten differentiellen Methode, nach der auf der Coats-Redfern-Gleichung basierenden integralen Methode und nach der die Horowitz-Metzger Gleichung benutzenden Näherungsmethode bestimmt. Aus den Befunden wird geschlossen, dass die thermische Stabilität von Vanillidenanthranilsäure-Chelaten in der Reihenfolge Co(II)Ni(II)>Zn(II)> >Cu(II) abnimmt.

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, , . - . . , , - , , - . , Ni>Zn>u.

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We thank Dr. C. P. Savariar, Professor of Chemistry, University of Calicut for encouragement. We are also grateful to the University Grants Commission for the award of a Senior Research Fellowship to one of us (J. C).     

Reduction of 1,4-dichlorobut-2-yne by titanocene to a 1,2,3-butatriene. Formation of a 1-titanacyclopent-3-yne and a 2,5-dititanabicyclo[2.2.0]hex-1(4)-ene

The 2,5-dititanabicyclo[2.2.0]hex-1(4)-ene (bis-titanocene-mu-(Z)-1,2,3-butatriene complex)3 is formed starting from [Cp2Ti(eta2-Me3SiC2SiMe3)] by in situ generated titanocene and 1,4-dichlorobut-2-yne via the 1-titanacyclobut-3-yne (2).     

Role of hadronic dynamics in proton decay

Aspects of hadronic dynamics which play a crucial role in proton decay (exclusive and inclusive) are examined in the context of a comprehensive Bethe-Salpeter (BS) formalism forq \(\bar q\) andqqq systems, under harmonic confinement. The BS model which is characterized by two basic parameters—the universal spring constant \(\tilde \omega \) GeV and the quark massm _q =0.28 GeV, has already provided an impressive set of agreements in respect of a large number and variety of hadronic observables (mass spectra, and an extensive list of e.m. and pionic couplings of both mesons and baryons). TheSU(5) GUT parameters, on the other hand, are kept fixed at the ‘standard’ values, (see e.g. Langacker's review). The absolute normalization of the baryon, which is rather crucial in this case, is fixed with reference to the (topologically equivalent) process of its ‘dissociation’ into three quarks by a hard photon, which makes use of the structure function sum rule \(\int\limits_0^1 {dxF_2^p (x)/x = \sum {Q_i^2 } } \) , instead of the usual BS normalization (which amounts to the conservation of charge). Thee ⁺ inclusive rate, which is about three times that of thee ⁺π⁰ mode, works out at0.54×10 ^?33 yr ^?1 which is smaller than most contemporary calculations by two orders of magnitude. Other exclusive modes are also consistent with the above estimate. The theoretical implications of these results vis a vis contemporary calculations as well as current experimental searches are discussed.     

Determination of some pesticides and intermediates by ion chromatography

The present paper deals with a method of solid-phase extraction of tocopherol acetate (TA, 49.6 microg/g) from emulsified nutritional supplements, which contains 50 kinds of compounds, followed by high-performance liquid chromatography (HPLC) with fluorescence detection The TA concentration is 5 to approximately 100,000 times lower than that of other compounds in the samples. Measuring the loading capacity of the larger amounts of vegetable oil onto the Bond Elut C18 cartridge was examined for the complete retention of smaller level of TA. A sample solution was applied to a solid-phase extraction cartridge and then TA was eluted by acetonitrile followed by HPLC. This method was suitable for the determination of TA in emulsified nutritional supplements. The proposed method was simple, rapid (analysis time: ca. 15 min), sensitive [detection limit: ca. 0.1 ng per injection (100 microl) at a signal-to-noise ratio of 3:1], and reproducible (relative standard deviation: ca. 2.5% (n=5)). The calibration graph of TA was linear in the range of 0.1 to 100 ng per injection (100 microl). Recovery of TA was over 90% by the standard addition method.