Roles of rhenium diimine complexes as metal‐ion probes and photosensitizers in functional polyurethanes

Polyurethanes incorporated with rhenium diimine complexes were synthesized. The polymers exhibited interesting morphologies and solution properties. Results from gel permeation chromatography suggested the formation of polymer aggregates in solutions. The polymers could act as probes for metal ions. The addition of metal ions to polymer solutions led to significant changes in the electronic absorption properties of the polymer solutions. This was attributed to the interactions between the polyether moieties and metal ions. The metal complexes could also act as efficient photosensitizers. After doping with charge‐transport viologens, the photoconductivity of the polymers was greatly enhanced. The experimental quantum efficiency was simulated with Onsager's theory. The thermalization distances and the primary yields were typically 12–14 Å and 10^?3, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1708–1715, 2003     

On division rings with algebraic commutators of bounded degree

We shall answer several questions concerning additive or multiplicative commutators in a division ring which are algebraic of bounded degree over its center.     

A high sensitivity titration calorimeter using pyroelectric sensor

A new sensitive isothermal titration microcalorimeter using polyvinylidene difluoride (PVDF) as detector has been developed. Heat pulses of less than 0.4 μJ can be detected and the baseline noise level (p-p) is 40 nW. The calorimeter is constructed with one reaction cell (0.7 ml) insulated by several radiation shields inside a vacuum chamber. The performance of the instrument was examined by measuring the heat of protonation of Tris with HCl. The enthalpy of reaction was found to be ?49±1 kJ·mol^?1, in good agreement with the reported value of ?47.5 kJ·mol^?1.     

Profile empirical likelihood for parametric and semiparametric models

This paper introduces a profile empirical likelihood and a profile conditionally empirical likelihood to estimate the parameter of interest in the presence of nuisance parameters respectively for the parametric and semiparametric models. It is proven that these methods propose some efficient estimators of parameters of interest in the sense of least-favorable efficiency. Particularly, for the decomposable semiparametric models, an explicit representation for the estimator of parameter of interest is derived from the proposed nonparametric method. These new estimations are different from and more efficient than the existing estimations. Some examples and simulation studies are given to illustrate the theoretical results. The first author is supported by NNSF projects (10371059 and 10171051) of China. The second author is supported by a grant from The Research Grants Council of the Hong Kong Special Administrative Region, China (#HKU7060/04P). The third author is supported by the University Research Committee of the University of Hong Kong and a grant from the Research Grants Council of the Hong Kong Special Administrative Region, China (Project No. HKU7323/01M).     

Improved estimation of a covariance matrix in an elliptically contoured matrix distribution

In this paper, the problem of estimating the covariance matrix of the elliptically contoured distribution (ECD) is considered. A new class of estimators which shrink the eigenvalues towards their arithmetic mean is proposed. It is shown that this new estimator dominates the unbiased estimator under the squared error loss function. Two special classes of ECD, namely, the multivariate-elliptical t distribution and the ε-contaminated normal distribution are considered. A simulation study is carried out and indicates that this new shrinkage estimator provides a substantial improvement in risk under most situations.     

Output dynamics and stabilisation of a multi-mode double-clad Yb-doped silica fibre laser

The intensity dynamics of the double-clad Yb fibre laser have been characterised. Stabilisation of the fibre laser intensity by using uniform bi-directional pumping is demonstrated. For the single-end-pumped Yb fibre laser, the output becomes more stable for the shorter fibre length due to the higher threshold of stimulated Brillouin scattering, SBS, and Kerr effects and the reduction of saturated absorber effects caused by any unpumped fibre section. By additional pumping in a double-end-pumped configuration, the output power can be scaled higher before detecting high intensity pulses initiated by SBS in the Yb fibre laser due to the reduction of saturable absorption effect. It is confirmed that uniform pumping enhances the stability of the laser output.     

A multipolymer system for organocatalytic alcohol oxidation

A system involving two polymer-supported reagents for the selective and organocatalytic oxidation of alcohols to aldehydes or ketones has been developed in which both polymeric reagents can be recovered and reused.     

Ultrafast time-resolved study of photophysical processes involved in the photodeprotection of p-hydroxyphenacyl caged phototrigger compounds

A combined femtosecond Kerr gated time-resolved fluorescence (fs-KTRF) and picosecond Kerr gated time-resolved resonance Raman (ps-KTR(3)) study is reported for two p-hydroxyphenacyl (pHP) caged phototriggers, HPDP and HPA, in neat acetonitrile and water/acetonitrile (1:1 by volume) solvents. Fs-KTRF spectroscopy was employed to characterize the spectral properties and dynamics of the singlet excited states, and the ps-KTR(3) was used to monitor the formation and subsequent reaction of triplet state. These results provide important evidence for elucidation of the initial steps for the pHP deprotection mechanism. An improved fs-KTRF setup was developed to extend its detectable spectral range down to the 270 nm UV region while still covering the visible region up to 600 nm. This combined with the advantage of KTRF in directly monitoring the temporal evolution of the overall fluorescence profile enables the first time-resolved observation of dual fluorescence for pHP phototriggers upon 267 nm excitation. The two emitting components were assigned to originate from the (1)pipi (S(3)) and (1)npi (S(1)) states, respectively. This was based on the lifetime, the spectral location, and how these varied with the type of solvent. By correlating the dynamics of the singlet decay with the triplet formation, a direct (1)npi --> (3)pipi ISC mechanism was found for these compounds with the ISC rate estimated to be approximately 5 x 10(11) s(-)(1) in both solvent systems. These photophysical processes were found to be little affected by the kind of leaving group indicating the common local pHP chromophore is largely responsible for the fluorescence and relevant deactivation processes. The triplet lifetime was found to be approximately 420 and 2130 ps for HPDP and HPA, respectively, in the mixed solvent compared to 150 and 137 ns, respectively, in neat MeCN. The solvent and leaving group dependent quenching of the triplet is believed to be associated with the pHP deprotection photochemistry and indicates that the triplet is the reactive precursor for pHP photorelease reactions for the compounds examined in this study.     

Relations on the period mapping giving extensions of mixed hodge structures on compact Riemann surfaces

We consider a period map from Teichmüller space to , which is a real vector bundle over the Siegel upper half space. This map lifts the Torelli map. We study the action of the mapping class group on this period map. We show that the period map from Teichmüller space modulo the Johnson kernel is generically injective. We derive relations that the quadratic periods must satisfy. These identities are generalizations of the symmetry of the Riemann period matrix. Using these higher bilinear relations, we show that the period map factors through a translation of the subbundle and is completely determined by the purely holomorphic quadratic periods. We apply this result to strengthen some theorems in the literature. One application is that the quadratic periods, along with the abelian periods, determine a generic marked compact Riemann surface up to an element of the kernel of Johnson's homomorphism. Another application is that we compute the cocycle that exhibits the mapping class group modulo the Johnson kernel as an extension of the group SP _g () by the group .