Charge transfer and intraligand excited state interactions in platinum-sensitized dithienylethenes

The photophysical behavior for two photochromic Pt-terpyridine acetylide complexes containing pendant dithienylethenes (DTEs) bound to the metal through the alkynyl linkage is presented. Selective excitation of the Pt complex with visible light resulted in the metal-sensitized ring closing of the DTE unit. The central purpose of this study was to understand how excited state interactions govern the photophysics by correlating differences in the linkage of the two components with differences in the intramolecular energy transfer processes that occur between the Pt complex and the DTE. A series of model complexes without photochromic ligands were prepared and studied to elucidate the contributions of the triplet metal-to-ligand charge transfer and triplet intraligand states. It is demonstrated that reducing the orbital overlap of the metal-based and intraligand states by lengthening the linkage and eliminating a conjugated pathway is effective at dramatically decreasing the efficiency of intramolecular energy transfer. This is evidenced by the appearance of Pt-terpyridine based phosphorescence and a significant decrease in the observed rate of metal-sensitized ring closing of the DTE.     

COOH-functionalisation of silica particles

In this study COOH-functionalised silica is synthesised using phosphonateN-(phosphonomethyl)iminodiacetic acid (PMIDA) in an aqueous solution. The presence of PMIDA on the silica particles was verified using Fourier Transform Infrared Spectroscopy, X-ray Photoelectron Spectroscopy and titration. Experimentally, surface concentrations of COOH functional groups of up to about 3 mmol/g_silica were achieved, whereas theoretical calculation of the maximum COOH functional group concentration gave about 1 mmol/g_silica. The discrepancy may be caused by PMIDA multilayer formation on the particle.     

Functional continuity and large deviations for the behavior of single-class queueing networks

We consider a single-class queueing network in which the functional network primitives describe the cumulative exogenous arrivals, service times and routing decisions of the queues. The behavior of the network consisting of the cumulative total arrival, cumulative idle time, and queue length developments for each node is specified by conditions which relate the network primitives to the network behavior. For a broad class of network primitives, including discrete customer and fluid models, a network behavior exists, but need not be unique. Nevertheless, the mapping from network primitives to the set of associated network behavior is upper semicontinuous at network primitives with continuous routing. As an application we consider a sequence of random network primitives satisfying a sample path large deviation principle. We take advantage of the partial functional set-valued upper semicontinuity in order to derive a large deviation principle for the sequence of associated random queue length processes and to identify the rate function. This extends the results of Puhalskii (Markov Process. Relat. Fields 13(1), 99–136, 2007) about large deviations for the tail probabilities of generalized Jackson networks. Since the analysis is carried out on the doubly-infinite time axis ?, we can directly treat stationary situations.     

Synthesis and characterization of monolayers and Langmuir-Blodgett films of an amphiphilic oligo(ethylene glycol)-C60-hexadecaaniline conjugate

A novel amphiphilic oligo(ethylene glycol)-C60-hexadecaaniline (A16) tricomponent conjugate, C60>(A16-EG43), possessing a well-defined number of repeating aniline donor units and a hydrophilic ethylene glycol oligomer chain was synthesized. The compound is composed of a covalently bound donor-acceptor chromophore structure. Molecular self-assembly of C60>(A16-EG43) at the air-water interface formed a densely packed Langmuir monolayer with all highly hydrophobic fullerene cages located above the liquid interface. The monolayer can then be transferred onto a glass substrate via Langmuir-Blodgett (LB) deposition. LB multilayered thin films formed by multiple deposition of the monolayer yielded broadened optical absorption peaks extending beyond 600 nm into the 950 nm region, suggesting strong intermolecular interactions among the C60 cages and the A16 moieties. An X-ray reflectometry study clearly reveals that the Langmuir film at the air-water interface consists of a C60 top layer and a bottom layer containing hexcadecaaniline and oligo(ethylene glycol) with gradually decreasing electron density over a distance of approximately 130 A above bulk water. The pressure isotherm shows that the packing density of the C60>(A16-EG43) monolayer, corresponding to a molecular area of approximately 95 A2/molecule, is similar to that of the surface area of the C60 monolayer. This result suggests that C60 packing plays a dominant role in guiding the formation of the monolayer structure. Further photoexcitation of hexadecaaniline moieties of aligned (C60>)-A16 layers by a flash light source induces cross linking between adjacent A16 segments forming an interlinked A16 array. Our results have demonstrated a unique fabrication method for preparing the aligned donor-acceptor array using strong intermolecular interactions between fullerenes as the molecular orientation guiding force in the Langmuir-Blodgett technique.     

Probing the local order of single phospholipid membranes using grazing incidence x-ray diffraction

We report the first grazing incidence x-ray diffraction measurements of a single phospholipid bilayer at the solid-liquid interface. Our grazing incidence x-ray diffraction and reflectivity measurements reveal that the lateral ordering in a supported DPPE (1, 2-Dipalmitoyl-sn-Glycero-3-Phosphoethanolamine) bilayer is significantly less than that of an equivalent monolayer at the air-liquid interface. Our findings also indicate that the leaflets of the bilayer are uncoupled in contrast to the scattering from free standing phosphatidylcholine bilayers. The methodology presented can be readily implemented to study more complicated biomembranes and their interaction with proteins.     

Multiplicities in highp t hadron-nucleus interactions

We present results obtained in π^? A (A=C, Cu, Pb) — collisions at 38 GeV/c. A single particle trigger selects events with one charged particle in the central region and large transverse momentum. The effect of this trigger on the multiplicities of all charged particles and of protons is shown.     

Remarks on positive semigroups

Let ℳ be a von Neumann algebra with a cyclic and separating vector Ω and let ω(·) denote the corresponding vector state, i.e., ω(A)=(Ω, AΩ) A ∈ ℳ. We have proved that a positive semigroup τ on ℳ can induce the dynamical semigroup in the GNS representation associated with ω if the state ω is a τ-invariant one. Some applications are given.     

Observation of a γ transition in the Λ4H hypernucleus

The γ spectra induced by stopped K^? mesons in a ⁷Li target were obtained in coincidence with the accompanying charged pions. A thorough analysis of these spectra indicates that the observed 1.09 MeV line can be ascribed to a γ transition in the ⁴_ΛH hypernucleus.     

Lipid corralling and poloxamer squeeze-out in membranes

Using x-ray scattering measurements we have quantitatively determined the effect of poloxamer 188 (P188), a polymer known to seal damaged membranes, on the structure of lipid monolayers. P188 selectively inserts into low lipid-density regions of the membrane and "corrals" lipid molecules to pack tightly, leading to unexpected Bragg peaks at low nominal lipid density and inducing lipid/poloxamer phase separation. At tighter lipid packing, the once inserted P188 is squeezed out, allowing the poloxamer to gracefully exit when the membrane integrity is restored.