The generalized anomeric effect in the 1,3-thiazolidines: Evidence forboth sulphur and nitrogen as electron donors. Crystal structures of various N-acylthiazolidines including mercury(II) complexes. Possible relevance to penicillin action

Evidence for the generalized anomeric effect (GAE) in the N-acyl-1,3-thiazolidines, an important structural motif in the penicillins, was sought in the crystal structures of N-(4-nitrobenzoyl)-1,3-thiazolidine and its (2:1) complex with mercuric chloride, N-acetyl-2-phenyl-1,3-thiazolidine, and the (2:1) complex of N-benzoyl-1,3-thiazolidine with mercuric bromide. An inverse relationship was generally observed between the. C-2-N and C-2-S bond lengths of the thiazolidine ring, supporting the existence of the GAE. (Maximal bond length changes were similar to 0.04 angstrom for C-2-N-3, S-1-C-2, and similar to 0.08 angstrom for N-3-C-6.) Comparison with N-acylpyrrolidines and tetrahydrothiophenes indicates that both the nitrogen-to-sulphur and sulphur-to-nitrogen GAE's operate simultaneously in the 1,3-thiazolidines, the former being dominant. (This is analogous to the normal and exo-anomeric effects in pyranoses, and also leads to an interesting application of Baldwin's rules.) The nitrogen-to-sulphur GAE is generally enhanced in the mercury(II) complexes (presumably via coordination at the sulphur); a 'competition' between the GAE and the amide resonance of the N-acyl moiety is apparent. There is evidence for a 'push-pull' charge transfer between the thiazolidine moieties in the mercury(II) complexes, and for a 'back-donation' of charge from the bromine atoms to the thiazolidine moieties in the HgBr2 complex. (The sulphur atom appears to be sp(2) hybridised in the mercury(II) complexes, possibly for stereoelectronic reasons.) These results are apparently relevant to the mode of action of the penicillins. (c) 2006 Elsevier B.V. All rights reserved.

Excitation energy transfer from a fluorophore to single-walled carbon nanotubes

We study the process of electronic excitation energy transfer from a fluorophore to the electronic energy levels of a single-walled carbon nanotube. The matrix element for the energy transfer involves the Coulombic interaction between the transition densities on the donor and the acceptor. In the Foumlrster approach, this is approximated as the interaction between the corresponding transition dipoles. For energy transfer from a dye to a nanotube, one can use the dipole approximation for the dye, but not for the nanotube. We have therefore calculated the rate using an approach that avoids the dipole approximation for the nanotube. We find that for the metallic nanotubes, the rate has an exponential dependence if the energy that is to be transferred, h is less than a threshold and a d(-5) dependence otherwise. The threshold is the minimum energy required for a transition other than the k(i,perpendicular to)=0 and l=0 transition. Our numerical evaluation of the rate of energy transfer from the dye pyrene to a (5,5) carbon nanotube, which is metallic leads to a distance of similar to 165 A degrees up to which energy transfer is appreciable. For the case of transfer to semiconducting carbon nanotubes, apart from the process of transfer to the electronic energy levels within the one electron picture, we also consider the possibility of energy transfer to the lowest possible excitonic state. Transfer to semiconducting carbon nanotubes is possible only if>=epsilon(g)-epsilon(b). The long range behavior of the rate of transfer has been found to have a d(-5) dependence if h >=epsilon(g). But, when the emission energy of the fluorophore is in the range epsilon(g)>h >=epsilon(g)-epsilon(b), the rate has an exponential dependence on the distance. For the case of transfer from pyrene to the semiconducting (6,4) carbon nanotube, energy transfer is found to be appreciable up to a distance of similar to 175 A degrees.

Analysis of Energy Quantization Effects on Single-Electron Transistor Circuits

In this paper, the effects of energy quantization on different single-electron transistor (SET) circuits (logic inverter, current-biased circuits, and hybrid MOS-SET circuits) are analyzed through analytical modeling and Monte Carlo simulations. It is shown that energy quantizationmainly increases the Coulomb blockade area and Coulomb blockade oscillation periodicity, and thus, affects the SET circuit performance. A new model for the noise margin of the SET inverter is proposed, which includes the energy quantization effects. Using the noise margin as a metric, the robustness of the SET inverter is studied against the effects of energy quantization. An analytical expression is developed, which explicitly defines the maximum energy quantization (termed as ``quantization threshold'') that an SET inverter can withstand before its noise margin falls below a specified tolerance level. The effects of energy quantization are further studiedfor the current-biased negative differential resistance (NDR) circuitand hybrid SETMOS circuit. A new model for the conductance of NDR characteristics is also formulated that explains the energy quantization effects.

In situ transmission electron microscope study of single asperity sliding contacts

Direct observation of events taking place at the contacting interfaces is important to understand many tribological phenomena. Transmission electron microscope (TEM) has the ability to look through materials at very high magnifications. Most of the TEM observations are done long after the deforming loads and stresses have been relaxed and the material state is further disturbed during the specimen preparation. We have developed a specimen holder in which two electron transparent surfaces can be brought in contact and moved relative to each other in JEOL 2000FX microscope. This holder enables visualization of not only the contacting surfaces at nanoscale but also the subsurface deformation resulting from the contact interaction. Sliding experimentS have been carried out mimicking a single asperity sliding contact. A sharp tungsten probe is moved laterally against a tip mounted on a cantilever. Magnitude of the contact instability, when the contact is broken is found to be dependent on the local geometry of the contact.(C) 2009 Elsevier Ltd. All rights reserved.

Synthesis and Characterization of a Class of Donor-Acceptor Conjugated Molecules: Experiments and Theoretical Calculations

A class of conjugated molecules containing donor (thiophene) and acceptor (malononitrile) is synthesized by Knoevenagel condensation reaction between 2-(2,6-dimethy1-4H-pyran-4-ylidene) malononitrile and thiophene carbaldehyde containing two and three thiophene units. The resulting molecules are characterized by H-1 and C-13 NMR. We have performed UV-vis absorption, fluorescence, and cyclic voltammetry measurements on these materials. The spectroscopic and electrochemical measurements proved beyond doubt that these materials possess lowexcitation gap and are suitable for being an active material in various electronic devices. We have also performed electronic structure calculations using density functional theory (DFT) and INDO/SCI methods to characterize the ground and excited states of this class of molecules. These donor-acceptor molecules show a strong charge transfercharacter that increases with the increase in the number of thiophene rings coupled to the malononitrile acceptor moiety. We have also calculated the pi-coherence length, Stoke's shift, and effect of solvents on excited states for this class of molecules, Our theoretical values agree well with experimental results.

Strength design of composite beam using gradient and particle swarm optimization

This work addresses the optimum design of a composite box-beam structure subject to strength constraints. Such box-beams are used as the main load carrying members of helicopter rotor blades. A computationally efficient analytical model for box-beam is used. Optimal ply orientation angles are sought which maximize the failure margins with respect to the applied loading. The Tsai-Wu-Hahn failure criterion is used to calculate the reserve factor for each wall and ply and the minimum reserve factor is maximized. Ply angles are used as design variables and various cases of initial starting design and loadings are investigated. Both gradient-based and particle swarm optimization (PSO) methods are used. It is found that the optimization approach leads to the design of a box-beam with greatly improved reserve factors which can be useful for helicopter rotor structures. While the PSO yields globally best designs, the gradient-based method can also be used with appropriate starting designs to obtain useful designs efficiently. (C) 2006 Elsevier Ltd. All rights reserved.

The dynamics of solvation of an electron in the image potential state by a layer of polar adsorbates

Recently, ultrafast two-photon photoemission has been used to study electron solvation at a two-dimensional metal/polar adsorbate interfaces [A. Miller , Science 297, 1163 (2002)]. The electron is bound to the surface by the image interaction. Earlier we have suggested a theoretical description of the states of the electron interacting with a two-dimensional layer of the polar adsorbate [K. L. Sebastian , J. Chem. Phys. 119, 10350 (2003)]. In this paper we have analyzed the dynamics of electron solvation, assuming a trial wave function for the electron and the solvent polarization and then using the Dirac-Frenkel variational method to determine it. The electron is initially photoexcited to a delocalized state, which has a finite but large size, and causes the polar molecules to reorient. This reorientation acts back on the electron and causes its wave function to shrink, which will cause further reorientation of the polar molecules, and the process continues until the electron gets self-trapped. For reasonable values for the parameters, we are able to obtain fair agreement with the experimental observations. (c) 2005 American Institute of Physics.

Electron temperature distribution across a shock wave in a partially ionized gas

The electron temperature structure in a weakly ionized plasma is studied allowing the degree of ionization to vary across the shock wave. The values of the electron temperature and the downstream equilibrium temperature obtained with variable ionization are less than those for frozen ionization. The electron temperature rises sharply behind the shock for variable ionization while a gradual increase is predicted by frozen ionization.

Seeing is Believing: Electron Microscopy for Investigating Nanostructures

Controlling the properties of nanostructures requires a detailed understanding of structure, microstructure, and chemistry at ever-decreasing length scales. The modern day transmission electron microscope has thus become an indispensable tool in the study of nanostructures. In this Perspective, we present a brief account of the capabilities of the TEM with some typical examples for characterizing nanostructures. The modern-day TEM has moved from a simple characterization tool to a nanoscale laboratory enabling in situ observation of several fundamental processes at unprecedented resolution levels.

A model to similate the strength and deformation of concrete in compression

A simple model is developed to represent the strength and deformational characteristics of concrete when subjected to a rate of strain or rate of stress or creep or relaxation testing under uniaxial compression.

Spectroscopic studies of n-donor-σ-acceptor systems: pyridines

The Charge-transfer equilibria of a number of substituted pyridines with iodine have been investigated. Solvent effects on the charge-transfer equilibrium of the pyridineiodine system have been examined. Hydrogen bonding data of substituted pyridines with phenol have been reported.

Spectroscopic studies of n-donor - σ-acceptor systems: Carbonyl and thiocarbonyl compounds as donors

The interaction of ketones and various thiocarbonyl derivatives with iodine has been examined. The thermodynamics of the interaction of carbonyl and thiocarbonyl donors have been discussed and compared.

Spectroscopic studies on n-donor + σ-acceptor systems: Alkylthioureas and thiocarbanilides

The donor-acceptor interactions of alkylthioureas and thiocarbanilides with halogens have been investigated in detail employing electronic and infra-red spectroscopy. Various correlations of the spectroscopic and thermodynamic data have been presented. Alkylthioureas are by far the strongest donors known, and give high equilibrium constants (10,000-40,000 l. mole-1) and enthalpies of formation (9-18 kcal mole-1). The perturbation of the various vibrational frequencies due to charge transfer have also been studied. Hydrogen bonding of thioureas with hydroxylic compounds have been reported.

Spectroscopic studies of the donor properties of triphenyl-amine, -phosphine, -arsine and -stibine interaction with iodine and phenol

The interaction of iodine with triphenylamine ,tripheny lphosphine, triphenylarsine and triphenystibine has been investigated by electronic spectroscopy. Transformation of the outer charge-transfer complexes to the inner complexes (quarternary salts) has been examined. The relations of the ionization potentials of the donors with the hvc.t have been discussed and various c.t. parameters have been estimated. Hydrogen bonding of these donors with phenol have been reported.