Vibrational spectroscopy and crystal structure analysis of two polymorphs of the di-amino acid peptide cyclo(L-Glu-L-Glu)

Cyclo(L-Glu-L-Glu) has been crystallised in two different polymorphic forms. Both polymorphs are monoclinic, but form 1 is in space group P21 and form 2 is in space group C2. Raman scattering and FT-IR spectroscopic studies have been conducted for the N,O-protonated and deuterated derivatives. Raman spectra of orientated single crystals, solid-state and aqueous solution samples have also been recorded. The different hydrogen-bonding patterns for the two polymorphs have the greatest effect on vibrational modes with N&bond;H and C&dbond;O stretching character. DFT (B3-LYP/cc-pVDZ) calculations of the isolated cyclo(L-Glu-L-Glu) molecule predict that the minimum energy structure, assuming C2 symmetry, has a boat conformation for the diketopiperazine ring with the two L-Glu side chains being folded above the ring. The calculated geometry is in good agreement with the X-ray crystallographic structures for both polymorphs. Normal coordinate analysis has facilitated the band assignments for the experimental vibrational spectra. Copyright © 2009 John Wiley & Sons, Ltd.

A vibrational spectroscopic investigation of rhodanine and its derivatives in the solid state

Raman and infrared spectra are reported for rhodanine, 3-aminorhodanine and 3-methylrhodanine in the solid state. Comparisons of the spectra of non-deuterated/deuterated species facilitate discrimination of the bands associated with N-H, NH2, CH2 and CH3 vibrations. DFT calculations of structures and vibrational spectra of isolated gas-phase molecules, at the B3-LYP/cc-pVTZ and B3-PW91/cc-pVTZ level, enable normal coordinate analyses in terms of potential energy distributions for each vibrational normal mode. The cis amide I mode of rhodanine is associated with bands at ~ 1713 and 1779 cm-1, whereas a Raman and IR band at ~ 1457 cm-1 is assigned to the amide II mode. The thioamide II and III modes of rhodanine, 3-aminorhodanine and 3-methylrhodanine are observed at 1176 and 1066/1078; 1158 and 1044; 1107 and 984 cm-1 in the Raman and at 1187 and 1083; 1179 and 1074; 1116 and 983 cm-1 in the IR spectra, respectively.

Vibrational spectroscopy and DFT calculations of the di-amino acid peptide L-aspartyl-L-glutamic acid in the zwitterionic state

Solid state IR and Raman as well as aqueous solution state Raman spectra are reported for the linear di-amino acid peptide L-aspartyl-L-glutamic acid (L-Asp-L-Glu); the solution state Raman spectrum has also been obtained for the N,O-deuterated derivative. SCF-DFT calculations at the B3-LYP/cc-pVDZ level established that the structure and vibrational spectra of L-Asp-L-Glu can be interpreted using a model of the peptide with ten hydrogen-bonded water molecules, in conjunction with the conductor-like polarizable continuum solvation method. The DFT calculations resulted in the computation of a stable zwitterionic structure, which displays trans-amide conformation. The vibrational spectra were computed at the optimised molecular geometry, enabling normal coordinate analysis, which yielded satisfactory agreement with the experimental IR and Raman data. Computed potential energy distributions of the normal modes provided detailed vibrational assignments.

DFT calculations of the structures and vibrational spectra of the [Fe(bpy)(3)](2+) and [Ru(bpy)(3)](2+) complexes

Structures of the [M(bpy)(3)](2+) complexes (M = Fe and Ru) have been calculated at the B3-LYP/DZVP level. IR and Raman spectra were calculated using the optimised geometries, employing a scaled quantum chemical force field, and compared with an earlier normal coordinate analysis of [Ru(bpy)(3) ](2+) which was based upon experimental data alone, and the use of a simplified model. The results of the calculations provide a highly satisfactory fit to the experimental data and the normal coordinate analyses, in terms of potential energy distributions, allow a detailed understanding of the vibrational spectra of both complexes. Evidence is presented for Jahn-Teller distortion in the E-1 MLCT excited state. (C) 2008 Elsevier B.V. All rights reserved.

Network analysis of 2-mode data

Network analysis is distinguished from traditional social science by the dyadic nature of the standard data set. Whereas in traditional social science we study monadic attributes of individuals, in network analysis we study dyadic attributes of pairs of individuals. These dyadic attributes (e.g. social relations) may be represented in matrix form by a square 1-mode matrix. In contrast, the data in traditional social science are represented as 2-mode matrices. However, network analysis is not completely divorced from traditional social science, and often has occasion to collect and analyze 2-mode matrices. Furthermore, some of the methods developed in network analysis have uses in analysing non-network data. This paper presents and discusses ways of applying and interpreting traditional network analytic techniques to 2-mode data, as well as developing new techniques. Three areas are covered in detail: displaying 2-mode data as networks, detecting clusters and measuring centrality.

Experimental study and theoretical analysis of signage legibility distances as a function of observation angle

Signage systems are widely used in buildings to provide information for wayfinding, thereby assisting in navigation during normal circulation of pedestrians and, more importantly, exiting information during emergencies. An important consideration in determining the effectiveness of signs is establishing the region from which the sign is visible to occupants, the so-called Visibility Catchment Area (VCA). This paper attempts to factor into the determination of the VCA of signs, the observation angle of the observer using both experimental and theoretical analysis.

An analysis of a microfabricated solenoid inductor

A microscale solenoid inductor is manufactured using electrodeposition method. The inductor is designed for switching mode DC-DC converters operating at switching frequencies in the mega-Hertz range. Two magnetic core materials, electroformed permalloy Ni80 Fe20 film and Vitrovac 6025 which is a commercial magnetic film, have been analyzed using experimental and computer modeling techniques

Recommendations on the nature of the passenger response time distribution to be used in the MSC 1033 assembly time analysis based on data derived from sea trials

The passenger response time distributions adopted by the International Maritime Organisation (IMO)in their assessment of the assembly time for passanger ships involves two key assumptions. The first is that the response time distribution assumes the form of a uniform random distribution and the second concerns the actual response times. These two assumptions are core to the validity of the IMO analysis but are not based on real data, being the recommendations of an IMO committee. In this paper, response time data collected from assembly trials conducted at sea on a real passanger vessel using actual passangers are presented and discussed. Unlike the IMO specified response time distributions, the data collected from these trials displays a log-normal distribution, similar to that found in land based environments. Based on this data, response time distributions for use in the IMO assesmbly for the day and night scenarios are suggested

Computer modelling analysis of the globtop's effects on aluminium wirebond reliability

In power electronics modules, heavy aluminium wires, i.e. wire diameters greater than 100 microns, are bonded to the active semiconductor devices and conductor metallization to form electric circuits of the power electronic module. Due to the high currents that may flow through these wires, a single connection usually contains several wires and thus, a large number of wires are used in a power electronics module. Under normal operation or test condition, a significant amount of stresses and strains induced in the wire and bonding interfaces, resulting in failure over time. In this paper, computer modelling techniques are used to analyse the effect of globtop design on the reliability of aluminium wirebonds under cyclic thermal-mechanical loading conditions. The results will show the sensitivity of the reliability of the wirebonds to the changes in the geometry and the material properties of the wirebond globtop.

Assessing the suitability of ship design for human factors issues associated with evacuation and normal operations

Evaluating ship layout for human factors (HF) issues using simulation software such as maritimeEXODUS can be a long and complex process. The analysis requires the identification of relevant evaluation scenarios; encompassing evacuation and normal operations; the development of appropriate measures which can be used to gauge the performance of crew and vessel and finally; the interpretation of considerable simulation data. In this paper we present a systematic and transparent methodology for assessing the HF performance of ship design which is both discriminating and diagnostic. The methodology is demonstrated using two variants of a hypothetical naval ship.

Kinematics and EMG analysis of expert pole vaulter's lower limb during take off phase (P218)

Introduction: The critical phase, in jumping events in track and field, appears to be between touchdown and take-off. Since obvious similarities exist between the take off phase in both long jump and pole vault, numerous 3D kinematics and electromyographic studies have only looked at long jump. Currently there are few detailed kinematics electromyographic data on the pole vault take-off phase. The aim of this study was therefore to characterise kinematics and electromyographic variables during the take-off phase to provide a better understanding of this phase in pole vaulting and its role in performance outcome. Material and methods: Six pole-vaulters took part in the study. Kinematics data were captured with retro reflective markers fixed on the body. Hip, knee and ankle angle were calculated. Differential bipolar surface electrodes were placed on the following muscles of the take-off leg: tibialis anterior, lateral gastrocnemius, vastus lateralis, rectus femoris, bicep femoris and gluteus maximus. EMG activity was synchronously acquired with the kinematic data. EMG data were rectified and smoothed using a second order low pass Butterworth Bidirectional filter (resulting in a 4th order filter) with a cut-off frequency of 14 Hz. Results: Evolution of hip, knee and ankle angle show no significant differences during the last step before touchdown, the take-off phase and the beginning of fly phase. Meanwhile, strong differences in EMG signal are noted inter and intra pole vaulter. However for a same subject the EMG activities seem to converge to some phase locked point. Discussion: All pole vaulters have approximately the same visible coordination This coordination reflects a different muscular control among pole vaulters but also for a considered pole vaulter. These phase locked point could be considered as invariant of motor control i.e. a prerequisite for a normal sequence of the movement and performance realization.