Assignment of fundamental vibrations of. ,N'-dimethylthiourea,

The infrared spectra of symmetric N,N′-dimethylthiourea (s-DMTU) and its N-deuterated (s-DMTU-d2) species have been measured. The fundamental frequencies have been assigned by comparison with the assignments in structurally related molecules and the infrared band shifts on N-deuteration, S-methylation, available Raman data and with the aid of theoretical band assignments from normal coordinate treatments for s-DMTU-d0 and -d2. A force field is derived for s-DMTU by transferring the force constants chiefly from N-methylthiourea and the subsequent refinement of the force constants by a least squares procedure.

Bottleneck assignment problems under categorization

This paper considers two special cases of bottleneck grouped assignment problems when n jobs belong to m distinct categories (m < n). Solving these special problems through the available branch and bound algorithms will result in a heavy computational burden. Sequentially identifying nonopitmal variables, this paper provides more efficient methods for those cases. Propositions leading to the algorithms have been established. Numerical examples illustrate the respective algorithms.

Infrared spectra of 1.3-dithiole-2-thione and its selenium analogues ând frequency assignment and molecular force constants

Infrared spectra of 1,3-dithiole-2-thione (DTT) and its four selenium analogues have been studied in the region 4000 to 20 cm�1. Assignment of all the fundamental frequencies was made by noting the band shifts on progressive selenation. Normal coordinate analysis procedures have been applied for both in-plane and out-of-plane vibrations to help the assignments. The Urey�Bradley force function supplemented with valence force constants for the out-of-plane vibrations was employed for coordinate calculations. A correlation of the infrared assignments of DTT with its different selenium analogues is accomplished. Further, the infrared assignments are compared with those of trithiocarbonate ion and its selenium analogues and other structurally related heterocyclic molecules.

CSSI-PRO: a method for secondary structure type editing, assignment and estimation in proteins using linear combination of backbone chemical shifts

Estimation of secondary structure in polypeptides is important for studying their structure, folding and dynamics. In NMR spectroscopy, such information is generally obtained after sequence specific resonance assignments are completed. We present here a new methodology for assignment of secondary structure type to spin systems in proteins directly from NMR spectra, without prior knowledge of resonance assignments. The methodology, named Combination of Shifts for Secondary Structure Identification in Proteins (CSSI-PRO), involves detection of specific linear combination of backbone H-1(alpha) and C-13' chemical shifts in a two-dimensional (2D) NMR experiment based on G-matrix Fourier transform (GFT) NMR spectroscopy. Such linear combinations of shifts facilitate editing of residues belonging to alpha-helical/beta-strand regions into distinct spectral regions nearly independent of the amino acid type, thereby allowing the estimation of overall secondary structure content of the protein. Comparison of the predicted secondary structure content with those estimated based on their respective 3D structures and/or the method of Chemical Shift Index for 237 proteins gives a correlation of more than 90% and an overall rmsd of 7.0%, which is comparable to other biophysical techniques used for structural characterization of proteins. Taken together, this methodology has a wide range of applications in NMR spectroscopy such as rapid protein structure determination, monitoring conformational changes in protein-folding/ligand-binding studies and automated resonance assignment.

A chitotetrose specific lectin from Luffa acutangula :Physico-chemical properties and the assignment of orientation of sugars in the lectin binding site

A chitooligosaccharide specific lectin (Luffa acutangula agglutinin) has been purified from the exudate of ridge gourd fruits by affinity chromatography on soybean agglutininglycopeptides coupled to Sepharose-6B. The affinity purified lectin was found homogeneous by polyacrylamide gel electrophoresis, in sodium dodecyl sulphate-polyacrylamide gels, by gel filtration on Sephadex G-100 and by sedimentation velocity experiments. The relative molecular weight of this lectin is determined to be 48,000 ± 1,000 by gel chromatography and sedimentation equilibrium experiments. The sedimentation coefficient (S20, w) was obtained to be 4·06 S. The Stokes’ radius of the protein was found to be 2·9 nm by gel filtration. In sodium dodecyl sulphate-polyacrylamide gel electrophoresis the lectin gave a molecular weight of 24,000 in the presence as well as absence of 2-mercaptoethanol. The subunits in this dimeric lectin are therefore held by non-covalent interactions alone. The lectin is not a glycoprotein and circular dichroism spectral studies indicate that this lectin has 31% α-helix and no ß-sheet. The lectin is found to bind specifically to chitooligosaccharides and the affinity of the lectin increases with increasing oligosaccharide chain length as monitored by near ultra-violetcircular dichroism and intrinsic fluorescence titration. The values of ΔG, ΔΗ and ΔS for the binding process showed a pronounced dependence on the size of the oligosaccharide. The values for both ΔΗ and ΔS show a significant increase with increase in the oligosaccharide chain length showing that the binding of higher oligomers is progressively more favoured thermodynamically than chitobiose itself. The thermodynamic data is consistent with an extended binding site in the lectin which accommodates a tetrasaccharide. Based on the thermodynamic data, blue shifts and fluorescence enhancement, spatial orientation of chitooligosaccharides in the combining site of the lectin is assigned.

Proton NMR and infrared investigations of secondary dithiocarbamate ester: molecular conformation and vibrational assignment of S-methyl N-methyl dithiocarbamate

Rotational isomerism of S-methyl N-methyl dithiocarbamate (MMDTC) has been investigated by means of variable temperature proton NMR and i.r. spectroscopy. The i.r. spectra of MMDTC as neat, solution and at sub-ambient temperatures have been examined. Normal vibrational analysis of all the fundamentals of MMDTC has been carried out, the vibrational assignment has been compared with those of related secondary thioamides to note the consistency in the assignments and to obtain the pattern characteristic of the secondary thioamide vibrations.

Some Generalisations of the Time Minimising Assignment Problem

The time minimising assignment problem is the problem of finding an assignment of n jobs to n facilities, one to each, which minimises the total time for completing all the jobs. The usual assumption made in these problems is that all the jobs are commenced simultaneously. In this paper two generalisations of this assumption are considered, and algorithms are presented to solve these general problems. Numerical examples are worked out illustrating the algorithms.

Structural assignment of monothiocarbonohydrazones by 1H NMR spectroscopy

Analysis of the 1H NMR spectra of several monothiocarbonohydrazones, some of them synthesized for the first time, shows that they exist as two structural isomers. Whereas, in general, the derivatives of aromatic aldehydes conform to a linear structure, the aliphatic carbonyl derivatives conform to heterocyclic or linear structures, depending on the size of the substituent groups. This dual behaviour is explained in terms of extended conjugation and steric hindrance.

Genetic algorithm for satellite customer assignment

The problem of assigning customers to satellite channels is considered. Finding an optimal allocation of customers to satellite channels is a difficult combinatorial optimization problem and is shown to be NP-complete in an earlier study. We propose a genetic algorithm (GA) approach to search for the best/optimal assignment of customers to satellite channels. Various issues related to genetic algorithms such as solution representation, selection methods, genetic operators and repair of invalid solutions are presented. A comparison of this approach with the standard optimization method is presented to show the advantages of this approach in terms of computation time

Task assignment in a multiprocessor system

One of the key problems in the design of any incompletely connected multiprocessor system is to appropriately assign the set of tasks in a program to the Processing Elements (PEs) in the system. The task assignment problem has proven difficult both in theory and in practice. This paper presents a simple and efficient heuristic algorithm for assigning program tasks with precedence and communication constraints to the PEs in a Message-based Multiple-bus Multiprocessor System, M3, so that the total execution time for the program is minimized. The algorithm uses a cost function: “Minimum Distance and Parallel Transfer” to minimize the completion time. The effectiveness of the algorithm has been demonstrated by comparing the results with (i) the lower bound on the execution time of a program (task) graph and (ii) a random assignment.

cis-trans Enantiomerism in the Diels-Alder cycloadducts of 6-arylfulvenes with maleic anhydride: resolution of the exo adducts via the N-((1S)-1-(naphth-1-yl)ethyl)imide derivatives: assignment of the absolute configurations based on the crystal structure of an imide diastereomer

A new case of the uncommon cis-trans enantiomerism is presented. The titled anhydride adducts were prepared in good yields by the known reaction of three 6-arylfulvenes with maleic anhydride (aryl = phenyl, p-tolyl and p-anisyl). The exo adducts were converted to the corresponding imides by reaction with (1S)-1-(naphth-1-yl)ethylamine in similar to 80% yields, and the resulting diastereomeric imides separated by silica gel column chromatography. They were hydrolysed and recyclised to the chiral anhydrides, in `one-pot' with 10% NaOH-EtOH, followed by treatment with 2 M HCl, in similar to 40% yields. The titled anhydrides were thus obtained in homochiral form, in enantiomeric purities (generally) of similar to 90% as indicated by chiral HPLC. The chiral anhydrides were also converted to the corresponding imides (presumably stereospecifically), by treatment with ammonia solution in excellent yields. The crystal structure of one of the above diastereomeric imides (derived from 6-phenylfulvene) was determined, and based on the known (S)-configuration of the naphthylethylamine moiety, the `configurations' of the original anhydride adducts were assigned. (c) 2005 Elsevier Ltd. All rights reserved.

Assignment of Fundamental Vibrations of Hydrazo Derivatives. Carbohydrazide and Diprotonated Carbohydrazide

The Infrared spectra of carbohydrazide, diprotonated carbohydrazide and their deuterated compounds have been measured in the solid state. From the results on thio- and selenocarbohydrazides and other related molecules and normal coordinate analyses using a Urey-Bradley force field assignments of the fundamental vibrational frequencies and a description of the normal modes of carbohydrazide, diprotonated carbohydrazide and their deuterated species are given.