Synthetic and conformational studies on dehydroalanine-containing model peptides

Three model dipeptides containing a dehydroalanine residue (Ala) at the C-terminal, Boc-X-Ala-NHCH3 [X = Ala, Val, and Phe,] have been synthesized and their solution conformations investigated by 1H-NMR, IR, and CD spectroscopy. NMR studies on these peptides in CDCl3 clearly indicate that the NH group of dehydroalanine is involved in an intramolecular hydrogen bond. This conclusion is supported by IR studies also. Nuclear Overhauser effect (NOE) studies are also accommodative of an inverse -turn-type of conformation that is characterised by conformational angles of -70° and +70° around the X residue, and a C[stack i+1 ]H-Ni+2H interproton distance of 2.5 Å. It appears that unlike dehydrophenylalanine or dehydroleucine, which tend to stabilize -turn type of structures occupying the i + 2 position of the turn, dehydroalanine favors the formation of an inverse -turn, centered at the proceeding L-residue in such solvents as CDCl3 and (CD3)2SO. A comparison of solution conformation of Boc Val-Ala-NHCH3 with the corresponding saturated analogue, Boc-Val-Ala-NHCH3, is also presented and shows that dehydroalanine is responsible for inducing the turn structure. It may be possible to design peptides with different preferred conformations using the suitable dehydroamino acid.

Suitability of a point-contact SAW-based stiffness transducer for biomedical applications

Methods of diagnosis in Biomedical applications can be broadly divided into contact and non-contact based methods. So far, ultrasound based methods have been found to be most favorable for non-contact, non-invasive diagnosis, especially in the case of tissue stiffness analysis. We report here, the fabrication and characterization details of a new contact based transducer system for qualitative determination of the stiffnesses of non-piezoelectric substrates using the phenomenon of Surface Acoustic Waves (SAW). Preliminary trials to study the functionality of this system were carried out on various metallic and non-metallic substrates, and the results were found to be satisfactory. To confirm the suitability of this system for biomedical applications, similar trials have been conducted on tissue mimicking phantoms with varying degrees of stiffness.

A combined extended and helical backbone for Boc-(Ala-Leu-Ac(7)c-)(2)-OMe

The structure of the peptide Boc-Ala-Leu-Ac(7)c-Ala-Leu-Ac(7)c-OMe (Ac(7)c,1-aminocycloheptane-1-carboxylic acid) is described in crystals. The presence of two Ac(7)c residues was expected to stabilize a 3(10)-helical fold. Contrary to expectation the structural analysis revealed an unfolded amino terminus, with Ala(1) adopting an extended beta-conformation (phi = -93degrees,psi = 112degrees). Residues 2-5 form a 3(10)-helix, stabilized by three successive intramolecular hydrogen bonds. Notably, two NH groups Ala(1) and Ac(7)c(3) do not form any hydrogen bonds in the crystal. Peptide assembly appears to be dominated by packing of the cycloheptane rings that stack against one another within the molecule and also throughout the crystal in columns.

Singularity and controllability analysis of parallel manipulators and closed-loop mechanisms

This paper presents a study of kinematic and force singularities in parallel manipulators and closed-loop mechanisms and their relationship to accessibility and controllability of such manipulators and closed-loop mechanisms, Parallel manipulators and closed-loop mechanisms are classified according to their degrees of freedom, number of output Cartesian variables used to describe their motion and the number of actuated joint inputs. The singularities in the workspace are obtained by considering the force transformation matrix which maps the forces and torques in joint space to output forces and torques ill Cartesian space. The regions in the workspace which violate the small time local controllability (STLC) and small time local accessibility (STLA) condition are obtained by deriving the equations of motion in terms of Cartesian variables and by using techniques from Lie algebra.We show that for fully actuated manipulators when the number ofactuated joint inputs is equal to the number of output Cartesian variables, and the force transformation matrix loses rank, the parallel manipulator does not meet the STLC requirement. For the case where the number of joint inputs is less than the number of output Cartesian variables, if the constraint forces and torques (represented by the Lagrange multipliers) become infinite, the force transformation matrix loses rank. Finally, we show that the singular and non-STLC regions in the workspace of a parallel manipulator and closed-loop mechanism can be reduced by adding redundant joint actuators and links. The results are illustrated with the help of numerical examples where we plot the singular and non-STLC/non-STLA regions of parallel manipulators and closed-loop mechanisms belonging to the above mentioned classes. (C) 2000 Elsevier Science Ltd. All rights reserved.

InMnO3: A biferroic

InMnO3 which has a hexagonal structure similar to that of YMnO3 is found to show a canted antiferromagnetic behavior below 50 K (T-N) and a ferroelectric (FE) transition at 500 K accompanied by hystersis. We have determined the structure, polarization, and energetics of the FE and paraelectric (PE) phases of InMnO3 using first-principles density functional theory calculations based on pseudopotentials and a plane-wave basis, and find the polarization of the PE phase to be a half-integer quantum. The difference in polarization of the FE and PE phases calculated along a simple path is different from the absolute value of polarization of the FE phase. A weak piezoelectric response is exhibited by InMnO3 to uniaxial strain.

Nonlinear Sliding Mode Control Design for an Air-breathing Engine with State Estimation

A modern system theory based nonlinear control design is discussed in this paper for successful operation of an air-breathing engine operating at supersonic speed. The primary objective of the control design of such an air-breathing engine is to ensure that the engine dynamically produces the thrust that tracks a commanded value of thrust as closely as possible by regulating the fuel flow to the combustion system. However, since the engine operates in the supersonic range, an important secondary objective is to manage the shock wave configuration in the intake section of the engine which is manipulated by varying the throat area of the nozzle. A nonlinear sliding mode control technique has been successfully used to achieve both of the above objectives. In this problem, since the process is faster than the actuators, independent control designs are also carried out for the actuators as well to assure the satisfactory performance of the system. Moreover, to filter out the sensor and process noises and to estimate the states for making the control design operate based on output feedback, an Extended Kalman Filter based state estimation design is also carried out. The promising simulation results suggest that the proposed control design approach is quite successful in obtaining robust performance of the air-breathing engine.

Effects of electron correlations in conjugated organic molecules and solids

The discrepancies between the non-interacting models and experimental results for conjugated systems is highlighted in this brief review. The interacting model hamiltonians correctly give the forbidden singlet state below the optical gap in polyenes and also explain both the nonvanishing optical gap in polyacetylenes and the vanishing optical gap in symmetric cyanine dyes. The negative spin densities in polyene radicals is also understood in terms of a correlated picture. The role of electron-electron interactions in other strongly correlated systems, such as polydiacetylene and mixed and segregated stack charge transfer solids, are also briefly discussed.

Topological analysis off charge density distribution in concomitant polymorphs of 3-acetylcoumarin, a case off packing polymorphism

Detailed investigation of the charge density distribution in concomitant polymorphs of 3-acetylcoumarin in terms of experimental and theoretical densities shows significant differences in the intermolecular features when analyzed based on the topological properties via the quantum theory of atoms in molecules. The two forms, triclinic and monoclinic (Form A and Form B), pack in the crystal lattice via weak C-H---O and C-H---pi interactions. Form A results in a head-to-head molecular stack, while Form B generates a head-to-tail stack. Form A crystallizes in PI (Z' = 2) and Form B crystallizes in P2(1)/n (Z = 1). The electron density maps of the polymorphs demonstrate the differences in the nature of the charge density distribution in general. The charges derived from experimental and theoretical analysis show significant differences with respect to the polymorphic forms. The molecular dipole moments differ significantly for the two forms. The lattice energies evaluated at the HF and DFT (B3LYP) methods with 6-31G** basis set for the two forms clearly suggest that Form A is the thermodynamically stable form as compared to Form B. Mapping of electrostatic potential over the molecular surface shows dominant variations in the electronegative region, which bring out the differences between the two forms.

Development of a low-cost portable colorimeter for the estimation of fluoride in drinking water

People in many countries are affected by fluorosis owing to the high levels of fluoride in drinking water. An inexpensive method for estimating the concentration of the fluoride ion in drinking water would be helpful in identifying safe sources of water and also in monitoring the performance of defluoridation techniques. For this purpose, a simple, inexpensive, and portable colorimeter has been developed in the present work. It is used in conjunction with the SPADNS method, which shows a color change in the visible region on addition of water containing fluoride to a reagent solution. Groundwater samples were collected from different parts of the state of Karnataka, India and analysed for fluoride. The results obtained using the colorimeter and the double beam spectrophotometer agreed fairly well. The costs of the colorimeter and of the chemicals required per test were about Rs. 250 (US$ 5) and Rs. 2.5 (US$ 0.05), respectively. In addition, the cost of the chemicals required for constructing the calibration curve was about Rs. 15 (US$ 0.3). (C) 2010 Elsevier B.V. All rights reserved.

An SOx (x = 2, 3) sensor using ?-alumina/Na2SO4 couple

A solid-state sensor for SOx (x = 2, 3) species has been designed using ?-alumina as the solid electrolyte and Na2SO4 as the auxiliary electrode. The measured e.m.f. of the cell Pt, O?2 + SO?2 + SO?3|Na2SO4short parallel?-aluminashort parallelNa2SO4|SO?3 + SO?2 + O?2, PT in the temperature range 700 K to 1150 K agrees well with values calculated using the Nernst equation. The sodium sulphate acts both as a protective covering, preventing direct access of the gaseous SOx species to the ?-alumina electrolyte, and as an auxiliary electrode, converting chemical potentials of SOx species and O2 into an equivalent sodium potential. The open-circuit e.m.f. varies non-linearly with temperature for fixed composition of inlet gas mixtures containing SO2, O2 and Ar. The response time (t0.99) of the cell varies between 1.9 ks at 750 K and 0.06 ks at 1100 K. The e.m.f. response is faster when the partial pressure of SOx at the electrode is increased than when it is decreased.

A Hub System for Cloud-Computing Based Business-Collaboration: Automating Ontology-Enabled Electronic Business-Service Discovery

The management and coordination of business-process collaboration experiences changes because of globalization, specialization, and innovation. Service-oriented computing (SOC) is a means towards businessprocess automation and recently, many industry standards emerged to become part of the service-oriented architecture (SOA) stack. In a globalized world, organizations face new challenges for setting up and carrying out collaborations in semi-automating ecosystems for business services. For being efficient and effective, many companies express their services electronically in what we term business-process as a service (BPaaS). Companies then source BPaaS on the fly from third parties if they are not able to create all service-value inhouse because of reasons such as lack of reasoures, lack of know-how, cost- and time-reduction needs. Thus, a need emerges for BPaaS-HUBs that not only store service offers and requests together with information about their issuing organizations and assigned owners, but that also allow an evaluation of trust and reputation in an anonymized electronic service marketplace. In this paper, we analyze the requirements, design architecture and system behavior of such a BPaaS-HUB to enable a fast setup and enactment of business-process collaboration. Moving into a cloud-computing setting, the results of this paper allow system designers to quickly evaluate which services they need for instantiationg the BPaaS-HUB architecture. Furthermore, the results also show what the protocol of a backbone service bus is that allows a communication between services that implement the BPaaS-HUB. Finally, the paper analyzes where an instantiation must assign additional computing resources vor the avoidance of performance bottlenecks.

Redundancy resolution using tractrix -- Simulations and Experiments

Hyper-redundant robots are characterized by the presence of a large number of actuated joints, many more than the number required to perform a given task. These robots have been proposed and used for many applications involving avoiding obstacles or, in general, to provide enhanced dexterity in performing tasks. Making effective use of the extra degrees of freedom or resolution of redundancy has been an extensive topic of research and several methods have been proposed in literature. In this paper, we compare three known methods and show that an algorithm based on a classical curve called the tractrix leads to a more 'natural' motion of the hyper-redundant robot, with the displacements diminishing from the end-effector to the fixed base. In addition, since the actuators nearer the base 'see' a greater inertia due to the links farther away, smaller motion of the actuators nearer the base results in better motion of the end-effector as compared to other two approaches. We present simulation and experimental results performed on a prototype eight link planar hyper-redundant manipulator.

X-ray studies on crystalline complexes involving amino acids and peptides. XXV. Structures of DL-proline hemisuccinic acid and glycyl-L-histidinium semisuccinate monohydrate and a comparative study of amino-acid and peptide complexes of succinic acid

DL-Proline hemisuccinic acid, C5H9NO2.1/2C4H6O4, M(r) = 174.2, P2(1/c) a = 5.254 (1), b = 17.480 (1), c = 10.230 (i) angstrom, beta = 119.60 (6)-degrees Z = 4, D(m) = 1.41 (4), D(x) = 1.42 g cm-3, R = 0.045 for 973 observed reflections. Glycyl-L-histidinium semisuccinate monohydrate, C8H13N4O3+.C4H5O4-.H2O, M(r) = 348.4, P2(1), a = 4.864 (1), b = 17.071 (2), c = 9.397 (1) angstrom, beta = 90.58-degrees, Z = 2, D(m) = 1.45 (1), D(x) = 1.48 g cm-3, R = 0.027 for 1610 observed reflections. Normal amino-acid and dipeptide aggregation patterns are preserved in the structures in spite of the presence of succinic acid/semisuccinate ions. In both the structures, the amino-acid/dipeptide layers stack in such a way that the succinic acid molecules/semisuccinate ions are enclosed in voids created during stacking. Substantial variability in the ionization state and the stoichiometry is observed in amino-acid and peptide complexes of succinic acid. Succinic acid molecules and succinate ions appear to prefer a planar centro-symmetric conformation with the two carboxyl (carboxylate) groups trans with respect to the central C=C bond. Considerable variation is seen in the departure from and modification of normal amino-acid aggregation patterns produced by the presence of succinic acid. Some of the complexes can be described as inclusion compounds with the amino acid/dipeptide as the 'host' and succinic acid/semisuccinate/succinate as the 'guest'. The effects of change in chirality, though very substantial, are not the same in different pairs of complexes involving DL and L isomers of the same amino acid.

Ultracapacitor Based Ride Through System for Control Power Supplies in High Power Converters

High power converters are used in variable speed induction motor drive applications. Riding through a short term power supply glitch is becoming an important requirement in these power converters. The power converter uses a large number of control circuit boards for its operation. The control power supply need to ensure that any glitch in the grid side does not affect any of these control circuit boards. A power supply failure of these control cards results in shut down of the entire system. The paper discusses the ride through system developed to overcome voltage sags and short duration outages at the power supply terminals of the control cards in these converters. A 240VA non-isolated, bi-directional buck-boost converter has been designed to be used along with a stack of ultracapacitors to achieve the same. A micro-controller based digital control platform made use of to achieve the control objective. The design of the ultracapacitor stack and the bidirectional converter is described the performance of the experimental set-up is evaluated.

Phenomenological Ginzburg-Landau-like theory for superconductivity in the cuprates

We propose and develop here a phenomenological Ginzburg-Landau-like theory of cuprate high-temperature superconductivity. The free energy of a cuprate superconductor is expressed as a functional F of the complex spin-singlet pair amplitude psi(ij) equivalent to psi(m) = Delta(m) exp(i phi(m)), where i and j are nearest-neighbor sites of the square planar Cu lattice in which the superconductivity is believed to primarily reside, and m labels the site located at the center of the bond between i and j. The system is modeled as a weakly coupled stack of such planes. We hypothesize a simple form FDelta, phi] = Sigma(m)A Delta(2)(m) + (B/2)Delta(4)(m)] + C Sigma(< mn >) Delta(m) Delta(n) cos(phi(m) - phi(n)) for the functional, where m and n are nearest-neighbor sites on the bond-center lattice. This form is analogous to the original continuum Ginzburg-Landau free-energy functional; the coefficients A, B, and C are determined from comparison with experiments. A combination of analytic approximations, numerical minimization, and Monte Carlo simulations is used to work out a number of consequences of the proposed functional for specific choices of A, B, and C as functions of hole density x and temperature T. There can be a rapid crossover of from small to large values as A changes sign from positive to negative on lowering T; this crossover temperature T-ms(x) is identified with the observed pseudogap temperature T*(x). The thermodynamic superconducting phase-coherence transition occurs at a lower temperature T-c(x), and describes superconductivity with d-wave symmetry for positive C. The calculated T-c(x) curve has the observed parabolic shape. The results for the superfluid density rho(s)(x, T), the local gap magnitude , the specific heat C-v(x, T) (with and without a magnetic field), as well as vortex properties, all obtained using the proposed functional, are compared successfully with experiments. We also obtain the electron spectral density as influenced by the coupling between the electrons and the correlation function of the pair amplitude calculated from the functional, and compare the results successfully with the electronic spectrum measured through angle resolved photoemission spectroscopy (ARPES). For the specific heat, vortex structure, and electron spectral density, only some of the final results are reported here; the details are presented in subsequent papers.