Block copolymers of acrylic acid and butyl acrylate prepared by reversible addition–fragmentation chain transfer polymerization: Synthesis,characterization, and use in emulsion polymerization

Amphiphilic block copolymers of poly(acrylic acid‐b‐butyl acrylate) were prepared by reversible addition–fragmentation chain transfer polymerization in a one‐pot reaction. These copolymers were characterized by NMR, static and dynamic light scattering, tensiometry, and size exclusion chromatography. The aggregation characteristics of the copolymers corresponded to those theoretically predicted for a star micelle. In a butyl acrylate and methyl methacrylate emulsion polymerization, low amounts of these copolymers could stabilize latices with solid contents up to 50%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 684–698, 2003     

Water adsorption in disordered mesoporous silica (Vycor) at 300 K and 650 K: a Grand Canonical Monte Carlo simulation study of hysteresis

This numerical simulation paper focuses on the adsorption/desorption of water in disordered mesoporous silica glasses (Vycor-like). The numerical adsorbent was previously obtained by off lattice method, and was shown to reproduce quite well the micro- and mesotextural properties of real Vycor, as well as morphological (pore size distribution) and topological (pore interconnections) disorder. The water-water interactions are described by the SPC model while water-silica interactions are calculated in the framework of the PN-TrAZ model. The water adsorption/desorption isotherms and the configurational energies are calculated by the Grand Canonical Monte Carlo simulation method. The low pressure results compare well with experiments, showing the good transferability of the intermolecular potential. It is shown that if the hysteresis loop observed in the adsorption/desorption isotherm is considered as a true phase transition (which is actually still an open question in the case of disordered porous materials), then it is possible to calculate the grand potential by applying the thermodynamic integration scheme. The grand potential is shown to be multivalued for low (subcritical) temperature, and continuous for high (supercritical) temperature. A coexistence point is found within the hysteresis loop, actually close to the vertical desorption line. Below the equilibrium chemical potential, the gaslike branch is stable whereas the liquidlike branch is metastable. The situation is reversed above the coexistence point.     

Time-Resolved Fluorescence and Transient Spectroscopy in Determining Photochemical and Photophysical Channels in Reacting Systems in Solutions and Microheterogeneous Media

Abstract— Characterization of short-lived intermediates in homogeneous and microheterogeneous systems has been carried out using time-resolved spectroscopic techniques. The data obtained from these techniques have been analyzed in a relatively unconventional manner to elucidate complex transient behavior for two reactive systems. The highly nonexponential fluorescence decay for a series of fraws-stilbene-derivatized amphiphiles that readily form bilayer systems in aqueous media has been analyzed using a distribution of lifetimes analysis (DLA). The utility of DLA for quantitative studies was first determined by simulation of artificial decay data. Despite some limitations in DLA, qualitative conclusions as to the nature of the fluorescing species may be drawn when supplementary information such as steady-state spectroscopic data are also considered. The results indicate that the observed fluorescence originates from different types of excited-state species that consist of two or more trans-stilbene units; one of the emissions is attributed to the excited state of a ground-state aggregate while the other is assigned to an excimer that may arise from a 'defect'in the bilayer. The nonexponential nature of the decays is attributed to distributions of environments experienced by the fluorescing species. Electron transfer (ET) reactions between several excited pinacols and carbon tetrachloride in solution have been found to yield products with quantum yields that are higher than unity in the presence of oxygen, suggesting a chain mechanism for product formation. In these systems both the donor and the acceptor undergo bond fragmentation following the initial ET step. The individual steps involved in the proposed mechanism for these systems have been investigated in part using different steady-state and time-resolved laser spectroscopic techniques. However, it was also necessary to utilize pulse radiolysis in order to confirm the involvement of certain radical intermediates that were not observable by the usual flash photolysis techniques.     

Development of enzyme biosensor based on pH-sensitive field-effect transistors for detection of phenolic compounds.

This article describes a biosensor based on pH-sensitive field-effect transistors (pH-FETs) as transducer, and immobilised enzyme tyrosinase as biorecognition element, which was used for the determination of phenolic compounds in water solutions. The biologically active membrane was formed by cross-linking of tyrosinase with bovine serum albumin (BSA) in saturated glutaraldehyde (GA) vapours on the sensitive transducer surface. The main analytical characteristics were studied under different conditions as well as the possibility to optimise these working parameters. Different factors such as the pH of immobilisation, the enzyme loading, the time of exposition to glutaraldehyde vapours were investigated in regards to the influence on sensitivity, limit of detection, dynamic range, and operational and storage stability.     

Aspects of the grand unification of strong,weak and electromagnetic interactions

We study issues arising in attempts to unify strong and other elementary particle interactions. The proton lifetime is estimated in theories with second-order baryon number violation, and found to be O(10³–10⁴) longer than naive dimensional counting suggested. The renormalization of quark and lepton masses below the grand unification mass is considered in some detail. Application is made to the SU(5) model of Georgi and Glashow, and we find strange and bottom quark masses:

$\text{m}{}_{\mathrm{<mtext>s</mtext>}}\text{≈ 0.4–0.5}\text{GeV}\text{, m}{}_{\mathrm{<mtext>b</mtext>}}\text{≈ 4.8–5.6}\text{GeV}$

. Inputs are the values of the strong interactions coupling constant favoured by electroproduction and charmonium analyses, and the observed muon and heavy lepton (τ) masses. These estimates are substantially increased if there are more than six flavours of quark. Symmetry breaking in the SU(5) model is studied, including radiative corrections to the effective Higgs potential.     

Synthesis, characterization and optical properties of pi-conjugated systems incorporating closo-dodecaborate clusters: new potential candidates for two-photon absorption processes

Non-centrosymmetric pi-conjugated systems incorporating closo-dodecaborate clusters, [NC-C6H4-C(H=N(H)-B12H11]-(2), [NC-C6H4-C(H)=C(H)-C(6)H(4)-C(H)=N(H)-B12H11]-(3), and [NC-C6H4-C(H)=C(H)-C6H4-C(H)=C(H)-C6H4-C(H)=N(H)-B12H11]-(4) have been synthesized by reaction of the monoamino derivative of B12, [B12H11NH3]-(1), with various arylaldehydes, R-C6H4-CHO. These Schiff base-like compounds were fully characterized by multinuclear NMR spectroscopy and mass spectrometry. In order to evaluate these boron rich pi-systems as potential materials for two-photon absorption (TPA) processes, UV linear absorption curves were recorded for 3 and 4, and comparatively studied with those of the boron-free pi-systems NC-C6H4-C(H)=N-CH3(5) and NC-C6H4-C(H)=C(H)-C6H4-C(H)=N-CH3(6). The donor effect of the boron cluster was evidenced by a shift to the lower energy of the absorption band in the spectra of systems incorporating B12. The two photon absorption (TPA) spectrum of compound , obtained by the up-conversion method, shows a resonance at 720 nm with a cross-section sigma(TPA) of 35 x 10(-50) cm(4) s photon(-1) molecule(-1). This value suggests the potential of B12 clusters to be used as new donor groups for the synthesis of non-linear materials.     

Studies of all-trans-retinal as a photooxidizing agent

The photophysical properties of all-trans-retinal (RAL) have been extensively studied because of the importance of the retinoids in the visual process. However, little information is available regarding the participation of RAL in photochemical transformations such as photoxidation. RAL is one of several native chromophores that have been suggested to act as photosensitizers of damage in the human retina, and this damage would likely occur through oxidative pathways. Time-resolved and steady state techniques have been used to examine the photoreactivity of RAL toward several suitable substrates. The lifetime of the RAL triplet excited state is observed to decrease with increasing concentration of the well-known electron and hydrogen atom donors, 2,3,5,6-tetramethyl-1,4-phenylenediamine (DAD), hydroquinone (HQ), methylhydroquinone (MHQ), 2,3-dimethylhydroquinone (DMHQ) and trimethylhydroquinone (TMHQ), although the bimolecular rate constants for the reaction are much less than that of diffusion controlled (2.9 x 10(7) M-1 s-1, 1.2 x 10(5) M-1 s-1, 1.2 x 10(5) M-1 s-1, 1.5 x 10(5) M-1 s-1 and 1.6 x 10(6) M-1 s-1, for DAD, HQ, MHQ, DMHQ and TMHQ, respectively). In the presence of the donors, new absorptions grow concomitant with the decay of the triplet excited state, and for DAD and TMHQ, the observed spectra are similar to the spectra of p-phenylenediamine and TMHQ radicals. Irradiation of RAL in argon-saturated methanol results in fairly efficient photobleaching of RAL and in the formation of two new compounds having absorption spectra that are shifted below 300 nm. Irradiation of RAL in argon-saturated acetonitrile also results in photobleaching of RAL, but the reaction proceeds at a slower rate.