Quasiparticle spectra, charge-density waves, superconductivity, and electron-phonon coupling in 2H-NbSe2

High-resolution photoemission has been used to study the electronic structure of the charge-density wave (CDW) and superconducting dichalcogenide, 2H-NbSe2. From the extracted self-energies, important components of the quasiparticle interactions have been identified. In contrast to previously studied TaSe2, the CDW transition does not affect the electronic properties significantly. The electron-phonon coupling is identified as a dominant contribution to the quasiparticle self-energy and is shown to be very anisotropic (k dependent) and much stronger than in TaSe2.     

Thermolysis of vic-dihydroxybacteriochlorins: effect of the nature of substrates in directing the formation of chlorin-chlorin dimers with fixed and flexible orientations and their preliminary in vitro photosensitizing efficacy

The thermolysis products obtained by refluxing a series of vic-dihydroxychlorins in o-dichlorobenzene are characterized. Depending on the nature of substrates, this methodology provides an access for novel carbon-carbon linked chlorin-chlorin dimers and chlorin-porphyrin dimers with fixed and flexible orientations. The configuration of the linkers in the symmetrical and unsymmetrical dimers was confirmed by extensive NMR (COSY, ROESY) and molecular modeling studies. The molecular modeling studies of the energy-optimized dimers with flexible orientation confirmed that one of the chlorin units of the dimeric structure is tilted toward the opposite ring as evident by the shielding effect in the resonances of some of the protons in the (1)H NMR spectroscopy. Among the dimers with fixed orientation, compared to the free-base analogues, the related mono- and di-Zn(II) complexes produced a decreased fluorescence intensity, suggesting a possibility of the faster energy transfer via intersystem crossing (ISC) in the metalated derivatives than the corresponding free-base analogues to produce the corresponding excited triplet states. The photosensitizing efficacy of the monomers and the related dimers was also compared in radiation-induced fibrosarcoma (RIF) tumor cells at variable drug/light doses. In preliminary screening, compared to monomers, the corresponding carbon-carbon linked dimers produced enhanced photosensitizing efficacy.     

Microscopic approach to the pseudo-spin-1/2 Hamiltonian for Kramers doublets in exchange coupled Co(II) pairs

The microscopic theory of the magnetically anisotropic effective pseudo-spin-(1)/(2) Hamiltonian for a pair of Co(2+) ions is reported. In the framework of the second-order perturbation approach, the analytical expressions are found for the components of the tensor of the exchange interaction, g-tensor, and the factor in the temperature independent paramagnetic contribution. The parameters of the Hamiltonian are expressed in terms of the basic intra- and intercenter parameters of the pair, namely, the spin-orbit coupling constant, orbital reduction factor, exchange integral, and low symmetry crystal field parameters including axial and rhombic terms.     

Application of isomorphous replacement in the structure determination of a cubic liquid crystal phase and location of counterions

A second generation monodendron with dodecyl end-groups based on the AB(3) monomer 3,4,5-trihydroxy benzoate has previously been shown to form a thermotropic cubic phase with Pmthremacr;n symmetry (Balagurusamy et al., J. Am. Chem. Soc. 1997, 119, 1539). A structure consisting of spherical "micelles" was proposed originally, but an alternative choice of structure factor phases, giving a structure of interlocked squashed columns, could not be ruled out by diffraction data on the original material alone. We have therefore synthesized two selectively fluorinated equivalent compounds, the carboxylic acid and its Rb salt, to be able to apply a variant of the isomorphous replacement crystallographic technique. On the basis of the electron density maps of the new labeled compounds, reconstructed using small-angle X-ray diffraction intensities, the interlocking columns model is unequivocally rejected and the spheres model is upheld. Furthermore, the location of the metal cation in the center of the "micelles" is directly confirmed. Micellar diameter was shown to decrease on fluorination of the dodecyl chain ends, and increase significantly on introduction of Rb. This is interpreted in terms of changes in the number of wedge-shaped dendrons fitting into a spherical micelle due to their changing taper angle. It was found that the Rb-rich regions at the centers of six out of eight "micelles" in the unit cell are elongated in the direction of their closest packing. This adds support to the suggestion of a partial "column-like" character of stacked rows of such micelles, consistent with the position of the Pmthremacr;n phase next to the columnar phase in the phase sequence of most taper-shape compounds. The results illustrate the potential of isomorphous replacement, used a great deal in protein crystallography, in structure investigation of liquid crystals and supramolecular soft matter.     

Random Skew Plane Partitions and the Pearcey Process

We study random skew 3D partitions weighted by q ^vol and, specifically, the q → 1 asymptotics of local correlations near various points of the limit shape. We obtain sine-kernel asymptotics for correlations in the bulk of the disordered region, Airy kernel asymptotics near a general point of the frozen boundary, and a Pearcey kernel asymptotics near a cusp of the frozen boundary.     

Non-linear applications of microstructured optical fibres

The enhancement of different non-linear processes in microstructured optical fibres can be achieved through manipulation of the dispersion characteristics of the fibre. This is demonstrated by extending the region of short wavelength operation of high power supercontinuum generation through four wave mixing in a cascaded fibre geometry where the dispersion of each fibre decreased on propagation. The technique is further refined in a demonstration utilizing long lengths of dispersion decreasing tapered microstructured fibres, where the supercontinuum extends to around 300 nm with spectral power densities in excess of 2 mW/nm in the uv. These long length tapers can also be utilized for adiabatic soliton pulse compression in new spectral regions, allowing the compression of 655 fs pulses to 45 fs.     

Transfection and imaging of diamond nanocrystals as scattering optical labels

We report on the first demonstration of nanodiamond (ND) as a scattering optical label in a biological environment. NDs were efficiently transfected into cells using cationic liposomes, and imaged using differential interference and Hoffman modulation ‘space’ contrast microscopy techniques. We have shown that 55 nm NDs are biologically inert and produce a bright signal compared to the cell background. ND as a scattering label presents the possibility for extended biological imaging with relatively little thermal or biochemical perturbations due to the optical transparency and biologically inert nature of diamond.     

Synthesis of Highly Substituted Cyclobutane Fused‐Ring Systems from N‐Vinyl β‐Lactams through a One‐Pot Domino Process

In this contribution, aminocyclobutanes, as well as eight‐membered enamide rings, have been made from N‐vinyl β‐lactams. The eight‐membered products have been formed by a [3,3]‐sigmatropic rearrangement, whereas the aminocyclobutanes have been derived from a domino [3,3]‐rearrangement/6π‐electrocyclisation process. The aminocyclobutanes have been obtained in a highly diastereoselective fashion. The cyclobutane ring system tolerates fusion even if adjacent quaternary centres are present. Systems containing up to four fused rings are readily accessible. The reaction profile has been investigated by using Gaussian 03. This study suggests that two reaction pathways for aminocyclobutane formation are possible. In one pathway the [3,3]‐sigmatropic rearrangement is the rate‐limiting step and in the second pathway the electrocyclisation is rate limiting. Taken together, these reactions should facilitate the construction of fused heterocycles.     

Comparison of the stability of multiwalled carbon nanotube dispersions in water

Continuous real-time monitoring of the nanotube concentration in aqueous solution using UV-Vis spectroscopy allows quantitative comparison of the stability of different types of nanotube dispersions. Systematic investigation of the effects of nanotube length and functionalisation for thin multiwalled carbon nanotubes (MWNT) has revealed that shorter MWNT form more stable dispersions than longer nanotubes of the same diameter. MWNT shortened to an average length of approximately 1 microm form stable dispersions in water with concentrations up to 0.013 mg ml(-1) in the absence of surfactants or solubilising functional groups. The introduction of carboxylic or thiol groups on the surface of shortened nanotubes further increases the stability of MWNT dispersions (up to 0.24 mg ml(-1)). The introduction of surfactant or surface charge on MWNT has contrasting effects on functionalised and non-functionalised nanotubes, destabilising and stabilising their dispersions, respectively.