Effect of H-bonding on the ambivalence of SCN- towards copper(II)

Condensations of 2-(2-aminoethyl)pyridine with 4-methylimidazole-5-carboxaldehyde and 1-methyl-2-imidazolecarboxaldehyde generate the tridentate N donor ligands L and L' respectively. Reactions of Cu(NCS)(2) with L and L' yield respectively CuL(SCN)(NCS) (1) containing a CuN4S core and CuL'(NCS)(2) (2) having a CuN5 core. Both the cores are square pyramidal with SCN bound in 1 at the axial position through the S end. This differential behaviour of SCN in the two complexes despite the ligands being very similar, is investigated by DFT calculations at the B3LYP/TZV level. It is found that DFT calculations predict isolation of the Cu(ligand)(NCS)(2) species for both the ligands L and L'. Presence of an offsetting intermolecular H-bonding between the N atom of the thiocyanate and the N-H proton of the ligand L of an adjacent molecule makes the binding of SCN via the S end feasible in 1 resulting in the H-bonded-dimer Cu2L2(SCN)(2)(NCS)(2). The strength of the H-bond is estimated as 27.1 kJ mol (1) from the DFT calculations. The question of such H-bonding does not arise with L' as it lacks in a similar H atom. Dimeric 1 represents a case of two non-interacting spins. (C) 2008 Elsevier B. V. All rights reserved.

Synthesis, crystal structure, magnetic behavior and thermal property of three polynuclear complexes: [M(dca)(2)(H2O)2](n)center dot(hmt)(n) [M = Mn(II), Co(II)] and [Co(dca)(2)(bpds)](n) [dca, dicyanamide; hint, hexamethylenetetramine; bpds, 4,4 '-bipyridyl disulfide]

Three mu(1.5)-dicyanamide bridged Mn(II) and Co(II) complexes having molecular formula [Mn(dca)(2)(H2O)(2)](n)center dot(hmt)(n) (1), [Co(dca)(2) (H2O)(2)](n)center dot(hmt)(n) (2) and [Co(dca)(2)(bpds)](n) (3) [dca = dicyanamide; hmt = hexamethylenetetramine; bpds = 4,4'-bipyridyl disulfide] have been synthesized and characterized by single crystal X-ray diffraction study, low temperature (300-2 K) magnetic measurement and thermal behavior. The X-ray diffraction analysis of 1 and 2 reveals that they are isostructural, comprising of 1D coordination polymers [M(dca)(2)(H2O)(2)](n) [M = Mn(II), Co(II) for 1 and 2. respectively] with uncoordinated hmt molecules located among the chains. The [M(dca)(2)(H2O)(2)](n) chains and the lattice hint molecules are connected through H-bonds resulting in a 3D supramolecular architecture. The octahedral N4O2 chromophore surrounding the metal ion forms via two trans located water oxygens and four nitrogens from four nitrile dca. Complex 3 is a 1D chain formed by two mu(1.5)-dca and one bridging bpds. The octahedral N-6 coordination sphere surrounding the cobalt ions comprises four nitrogens from dca and two from bpds. Low temperature magnetic study indicates small antiferromagnetic coupling for all the complexes. Best fit parameters for 1: J = -0.17 cm(-1), g = -2.03 with R = 6.1 x 10(-4), for 2, J = -0.50 cm(-1), and for 3, J = -0.95 cm(-1). (c) 2005 Elsevier B.V. All rights reserved.

Tuning of intramolecular electron transfer between Ru(II) and the disulfide bond

Reaction of 2,2'-dithiodipyridine (DTDP) with cis-Ru(bpy)(2)Cl-2 (bpy = 2,2'-bipyridine) and cis-Ru(phen)(2)Cl-2 (phen = 1,10-phenanthroline) respectively yields the dicationic species [Ru(bpy) (2)(DTDP)](2+) and [Ru(phen)(2) (DTDP)](2+) in which the S-S bond of DTDP remains intact. The S-S bond undergoes a reductive cleavage when DTDP is reacted with cis-Ru(bisox)(2)Cl-2 (bisox = 4,4,4',4'-tetramethyl-2,2'-bisoxazoline) under identical conditions to generate the monocationic species [Ru(bisox)(2)(2-thiolatopyridine)]. The intramolecular electron transfer between the metal and the S-S bond is found to be subtly controlled by the crystal field strength of the ancillary bidentate N-donor ligands.

C-H...O hydrogen bonding in 4-phenyl-benzaldehyde: a comprehensive crystallographic, spectroscopic and computational study

The crystal structure of 4-phenyl-benzaldehyde reveals the presence of a dimer linked by the C=O and C( 9)-H groups of adjacent molecules. In the liquid phase, the presence of C-(HO)-O-... bonded forms is revealed by both vibrational and NMR spectroscopy. A Delta H value of - 8.2 +/- 0.5 kJ mol(-1) for the dimerisation equilibrium is established from the temperature-dependent intensities of the bands assigned to the carbonyl-stretching modes. The NMR data suggest the preferential engagement of the C(2,6)-H and C(10/12)/C(11)-H groups as hydrogen bond donors, instead of the C(9)-H group. While ab initio calculations for the isolated dimers are unable to corroborate these NMR results, the radial distribution functions obtained from molecular dynamics simulations show a preference for C(2,6)-H and C(10/12)/C(11)-(HO)-O-... contacts relative to the C(9)-(HO)-O-... ones.

Thermally responsive elastomeric supramolecular polymers featuring flexible aliphatic hydrogen-bonding end-groups

The present paper details the synthesis, characterization, and preliminary physical analyses of a series of polyisobutylene derivatives featuring urethane and urea end-groups that enable supramolecular network formation to occur via hydrogen bonding. These polymers are readily accessible from relatively inexpensive and commercially available starting materials using a simple two-step synthetic approach. In the bulk, these supramolecular networks were found to possess thermoreversible and elastomeric characteristics as determined by temperature-dependent rheological analysis. These thermoreversible and elastomeric properties make these supramolecular materials potentially very useful in applications such as adhesives and healable surface coatings.

Analysis of chain and blood group type and branching pattern of sialylated oligosaccharides by negative ion electrospray tandem mass spectrometry

We previously reported sequence determination of neutral oligosaccharides by negative ion electrospray tandem mass spectrometry on a quadrupole-orthogonal time-of-flight instrument with high sensitivity and without the need of derivatization. In the present report, we extend our strategies to sialylated oligosaccharides for analysis of chain and blood group types together with branching patterns. A main feature in the negative ion mass spectrometry approach is the unique double glycosidic cleavage induced by 3-glycosidic substitution, producing characteristic D-type fragments which can be used to distinguish the type 1 and type 2 chains, the blood group related Lewis determinants, 3,6-disubstituted core branching patterns, and to assign the structural details of each of the branches. Twenty mono- and disialylated linear and branched oligosaccharides were used for the investigation, and the sensitivity achieved is in the femtomole range. To demonstrate the efficacy of the strategy, we have determined a novel complex disialylated and monofucosylated tridecasaccharide that is based on the lacto-N-decaose core. The structure and sequence assignment was corroborated by :methylation analysis and H-1 NMR spectroscopy.

Towards a unifying framework for pattern transformation in swarm systems

This paper identifies the major challenges in the area of pattern formation. The work is also motivated by the need for development of a single framework to surmount these challenges. A framework based on the control of macroscopic parameters is proposed. The issue of transformation of patterns is specifically considered. A definition for transformation and four special cases, namely elementary and geometrical transformations by repositioning all or some robots in the pattern are provided. Two feasible tools for pattern transformation namely, a macroscopic parameter method and a mathematical tool - Moebius transformation also known as the linear fractional transformation are introduced. The realization of the unifying framework considering planning and communication is reported.

Modeling and simulating a mathematical tool for multi-robot pattern transformation

The work reported in this paper is motivated by the need to investigate general methods for pattern transformation. A formal definition for pattern transformation is provided and four special cases namely, elementary and geometric transformation based on repositioning all and some agents in the pattern are introduced. The need for a mathematical tool and simulations for visualizing the behavior of a transformation method is highlighted. A mathematical method based on the Moebius transformation is proposed. The transformation method involves discretization of events for planning paths of individual robots in a pattern. Simulations on a particle physics simulator are used to validate the feasibility of the proposed method.

Swarm pattern transformation methodologies

The work reported in this paper is motivated by the need for developing swarm pattern transformation methodologies. Two methods, namely a macroscopic method and a mathematical method are investigated for pattern transformation. The first method is based on macroscopic parameters while the second method is based on both microscopic and macroscopic parameters. A formal definition to pattern transformation considering four special cases of transformation is presented. Simulations on a physics simulation engine are used to confirm the feasibility of the proposed transformation methods. A brief comparison between the two methods is also presented.

A swarm pattern transformation method based on macroscopic parameter operations

The work reported in this paper is motivated by biomimetic inspiration - the transformation of patterns. The major issue addressed is the development of feasible methods for transformation based on a macroscopic tool. The general requirement for the feasibility of the transformation method is determined by classifying pattern formation approaches an their characteristics. A formal definition for pattern transformation is provided and four special cases namely, elementary and geometric transformation based on repositioning all and some robotic agents are introduced. A feasible method for transforming patterns geometrically, based on the macroscopic parameter operation of a swarm is considered. The transformation method is applied to a swarm model which lends itself to the transformation technique. Simulation studies are developed to validate the feasibility of the approach, and do indeed confirm the approach.

Efficient FPGA-based regular expression pattern matching

An approach to the automatic generation of efficient Field Programmable Gate Arrays (FPGAs) circuits for the Regular Expression-based (RegEx) Pattern Matching problems is presented. Using a novel design strategy, as proposed, circuits that are highly area-and-time-efficient can be automatically generated for arbitrary sets of regular expressions. This makes the technique suitable for applications that must handle very large sets of patterns at high speed, such as in the network security and intrusion detection application domains. We have combined several existing techniques to optimise our solution for such domains and proposed the way the whole process of dynamic generation of FPGAs for RegEX pattern matching could be automated efficiently.

Evolving features-algorithms knowledge map to support NIDS data intelligence and learning loop architecting – a generalised approach to NIDS pattern feature space knowledge processing

This paper describes a proposed new approach to the Computer Network Security Intrusion Detection Systems (NIDS) application domain knowledge processing focused on a topic map technology-enabled representation of features of the threat pattern space as well as the knowledge of situated efficacy of alternative candidate algorithms for pattern recognition within the NIDS domain. Thus an integrative knowledge representation framework for virtualisation, data intelligence and learning loop architecting in the NIDS domain is described together with specific aspects of its deployment.

Investigating feasible tools for swarm pattern transformation

Abstract-The work reported in this paper is motivated by the need for developing swarm pattern transformation methodologies. Two methods, namely a macroscopic method and a mathematical method are investigated for pattern transformation. The first method is based on macroscopic parameters while the second method is based on both microscopic and macroscopic parameters. A formal definition to pattern transformation considering four special cases of transformation is presented. Simulations on a physics simulation engine are used to confirm the feasibility of the proposed transformation methods. A brief comparison between the two methods is also presented.