Changes in the near-edge X-ray absorption fine structure spectra of long-chain diacetylene derivatives through photopolymerization in Langmuir–Blodgett films

Photopolymerization of cadmium 10,12-pentacosadiynoate (CdDA) in Langmuir–Blodgett (LB) films, with the molecular packing well arranged by moderate preannealing, was investigated with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Greenish films of polydiacetylene with an absorption wavelength of 705 nm were obtained through the photopolymerization of preannealed monomer LB films, and this resulted in an extended π-conjugate system based on the well-ordered monomer in a two-dimensional arrangement. The electronic structures of the polydiacetylenes were found to be correlated to the variation of the molecular arrangements in the films from the changes in the NEXAFS spectra through photopolymerization in the LB films. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2329–2336, 2004     

Crystallization in poly(n-octadecyl methacrylate) monolayers

The crystallization kinetics of poly(n-octadecyl methacrylate) has been studied at the air–water interface. The rate of the crystallization has been measured by the decrease in the area of monolayers with time at various temperatures and surface pressures. The crystallization isotherms have been analyzed by the general mathematical treatment of the kinetics of phase changes, and the results show linear growth to be dominant. The variation of the rate constant with temperature and pressure has been illustrated by the difference in the supersaturation defined by introducing the equilibrium pressure-area isotherms.     

Mass spectra of perfluoroalkyl and perfluoroalkylether nitriles and acyl halides

Electron impact fragmentation patterns were obtained for perfluoroalkylether nitriles, C,F,O[CF(CF₃)CFIO]ICF(CF₃)CN (x = 1 and 2), perfluoroalkylether acyl halides, CSF,OCF(CF,)-CF₂OCF(CF₃)COX (X = F and Cl), n-perfluorooctanonitrile and n-perfiuorooctanoyl chloride. The perfluoroalkyl and perfluoroalkylether nitriles afforded ions characteristic of the nitrile function. The major fragment from the acyl chlorides was the [COClJ]+ ion; the presence of chlorine was evidenced also by rearrangement ions of the general form [R_fCl] t. The perfluoroalkylether compounds appeared to undergo a typical fragmentation governed by the cleavage of the carbon-oxygen bond.     

Syntheses and degradations of fluorinated heterocyclics III. Perfluoroalkyl and perfluoroalkylether-1,3,4-oxadiazoles

2,5-Bis(perfluoro-n-heptyl)-, 2-perfluoroalkylether-5-perfluoro-n-heptyl-, and 2,5-bisperfluoroalkylether-1,3,4-oxadiazoles were synthesized and characterized. 2,5-Bis(perfluoro-n-heptyl)-1,3,4-oxadiazole was thermally and hydrolytically stable at 325°C; however, in the presence of air, degradation took place at 235°C. The perfluoroalkylether analogue exhibited thermal and hydrolytic stability at 325°C; it was found to be unaffected by Jet-A fuel and air at 235°C. At 325°C in air some degradation occured as evidenced by volatiles production, oxygen consumption, and 96% starting material recovery.     

IN SITU OBSERVATION OF 2-DIMENSIONAL TEXTURE OF EUROPIUM COMPLEX ON WATER SURFACE BY BREWSTER ANGLE MICROSCOPY

Monolayers of europium complexes on water surface have been directly visualized in the gas-liquid expanded region at different temperatures using Brewster angle microscopy (BAM). The film texture with network patterns of the complex (C₁₈)₂ Eu(DBM)₄ and hs evolution with time and temperature of the subphase were examined. The average linear cell dimension and the polygon areas have been analyzed as a function of time and the temperature. The mechanism of the domain growth is qualitatively discussed.     

Second-harmonic generation in thermally poled chalcohalide glass

Second-harmonic generation in 60GeS(2)-20Ga(2)S(3)-20KBr chalcohalide glass was investigated by the thermal poling method. A large second-order nonlinear susceptibility, as high as 7.0 pm/V, was obtained in a poled sample by Maker fringe analysis. We believe this to be the first time that a clear second-harmonic wave was observed in chalcohalide glasses containing large amount of alkali ions (6.25 at. %). Such observation is of great potential use in all optical waveguide devices.     

In vivo assessment of the permeability of the blood--brain barrier and blood-retinal barrier to fluorescent indoline derivatives in zebrafish

ABSTRACT: BACKGROUND: Successful delivery of compounds to the brain and retina is a challenge in the development of therapeutic drugs and imaging agents. This challenge arises because internalization of compounds into the brain and retina is restricted by the blood--brain barrier (BBB) and blood-retinal barrier (BRB), respectively. Simple and reliable in vivo assays are necessary to identify compounds that can easily cross the BBB and BRB. METHODS: We developed six fluorescent indoline derivatives (IDs) and examined their ability to cross the BBB and BRB in zebrafish by in vivo fluorescence imaging. These fluorescent IDs were administered to live zebrafish by immersing the zebrafish larvae at 7--8 days post fertilization in medium containing the ID, or by intracardiac injection. We also examined the effect of multidrug resistance proteins (MRPs) on the permeability of the BBB and BRB to the ID using MK571, a selective inhibitor of MRPs. RESULTS: The permeability of these barriers to fluorescent IDs administered by simple immersion was comparable to when administered by intracardiac injection. Thus, this finding supports the validity of drug administration by simple immersion for the assessment of BBB and BRB permeability to fluorescent IDs. Using this zebrafish model, we demonstrated that the length of the methylene chain in these fluorescent IDs significantly affected their ability to cross the BBB and BRB via MRPs. CONCLUSIONS: We demonstrated that in vivo assessment of the permeability of the BBB and BRB to fluorescent IDs could be simply and reliably performed using zebrafish. The structure of fluorescent IDs can be flexibly modified and, thus, the permeability of the BBB and BRB to a large number of IDs can be assessed using this zebrafish-based assay. The large amount of data acquired might be useful for in silico analysis to elucidate the precise mechanisms underlying the interactions between chemical structure and the efflux transporters at the BBB and BRB. In turn, understanding these mechanisms may lead to the efficient design of compounds targeting the brain and retina.     

Determination of the change of nuclear charge radius of the119Sn Mössbauer transition by internal conversion

Radioactive¹¹⁹Sb was implanted into six host matrices (CaSnO₃, Pt, Y, Au,-Sn, Pb) and internal conversion electrons of the 23.87 keV transition in¹¹⁹Sn were measured with an iron-free magnetic spectrometer as well as Mössbauer spectra. In the analysis of the conversion spectra of outermost electrons, the overlapping K-LM Auger lines were subtracted using the Auger spectrum of tin measured with another source of^117mSn, and the shake-off effect accompanying the conversion process was considered. From the correlation between the Mössbauer isomer shifts and the intensity ratios of O-shell to N₁-shell conversion electrons, the change of the nuclear charge radius of the 23.87 keV transition of¹¹⁹Sn was deduced to be R/R=(0.87 ± 0.25) × 10^–4 for a uniform charge distribution ofR= 1.2 ×A ^1/3 fm or, equivalently, r²>—=(3.6 ± 1.0) ×10^–3 fm².     

Contact density and number of 5s electrons inβ-Sn

Lifetimes and feeding times of high spin states in ¹⁵⁶ Er have been measured employing the recoil distance method in the reaction ¹²³ Sb(³⁷ Cl,4n) at bombarding energies of 158 and 166 MeV. The yrast states up to spin 20 ? were found to be collective. These levels are fed, however, from long-lived high spin states, causing time delays up to ～ 100 ps, the existence of which is interpreted as a signature for an oblate shape at high spin.