Femtosecond Transient Reflecting Grating Spectroscopy Using White-light Probe Pulses

Dynamics of photoexcited electrons are of considerable relevance for fundamental processes of various surface chemical reactions. Many studies on dynamics at solid surfaces have been reported using two photon photoemission (2PPE), transient reflectivity (TR) and transient reflecting grating (TRG) methods.     

Flow injection spectrophotometric determination of sub-mg dm(-3) silver(I) in a strongly acidic solution containing concentrated copper(II) using a pyridylazo reagent

A novel spectrophotometric flow injection method for determination of silver(I) in a strongly acidic solution containing concentrated copper(II) was developed using a coloring ligand, 4-(3,5-dibromo-2-pyridylazo)-N-ethyl-N-(3-sulfopropyl)aniline (3,5-diBr-PAESA). The method was first investigated by batch method. The interference from copper(II) chelate could be eliminated by the masking effect of EDTA. By utilizing the large formation constant (K = 12.3) of AgBr, one could determine silver(I) as a decrease of absorption by silver(I) chelate due to formation of AgBr by addition of KBr. Based on the results of batch experiments, two types of flow injection analysis (FIA) systems were constructed. Sub-mg dm(-3) determination of silver(I) was attained without interference from excess copper(II). The proposed method was successfully applied to determination of silver in a copper plating solution used in a plant to manufacture copper printed circuit boards, where the concentration of silver was critically important in the process control.     

Photo‐alignment material with azobenzene‐functionalized polymer linked in film

Application of a new azo‐polymer as a photo‐alignment material for liquid crystals (LCs) was demonstrated. 4‐(Vinyloxyethyloxy)azobenzene (VAZO), which has thermally reactive vinyl ether groups, reacted with the ? OH groups of poly(4‐hydroxystyrene) (PHS) during the baking process. The azo‐attached polymer (PHS‐VAZO) film showed anisotropic spectra after exposure to 365‐nm linear polarized light (LPL) unlike the VAZO‐doped poly(methylmethacrylate) (PMMA) film. The anisotropy of the film was small at high concentration of the azo‐chromophore because of thermal randomization of the polarized state. In the evaluation of photo‐alignment of the LC, the LC hybrid cell using the PHS‐VAZO film achieved high LC alignment. The azo‐attached polymer using the thermal reaction of vinyl ethers is useful for a photo‐alignment material. Copyright © 2002 John Wiley & Sons, Ltd.     

Molecular structure and electronic spectrum of ellagic acid: Semiempirical molecular orbital calculations

The molecular structure of ellagic acid has been optimized by using PM3 semiempirical MO method. Ellagic acid has been calculated to be planar with the molecular symmetry of C_2h. The lactone carbonyl groups are not tilted from the molecular plane. CNDO/S MO method has been used to interpret the experimental uv-vis spectroscopic data. The results of the PM3 and CNDO/S calculations have been in good agreement with the experimental data.     

Application of photopolymer to core‐hair type microgels with various hair length

The new microgels, called “core‐hair” type microgels, were synthesized. They have a hair moiety consisting of the oxyhexano‐1,7‐diyl (? O? (CH₂)₅? C(O)? ) group as a spacer and the acryloyl group for polymerization. The hair length depends on the number of spacer units, and affects the viscosity and the thixotropy index of the microgel. These core‐hair microgels show the pseudo‐plastic flow of a non‐Newtonian fluid with moderate to high dispersibility in water or alcoholic solvents. Due ­to their viscosities and dispersibilities, these core‐hair microgels are useful for photopolymer, e.g. for screen printing. Therefore, these microgels were actually applied to screen printing and confirmed pattern forming on a screen printing plate through water development. We now discuss the relation between the viscosity, the dispersibility, the photosensitivity, and the rate of photopolymerization to the hair length of the microgel. Copyright © 2001 John Wiley & Sons, Ltd.     

Molecular structure and electronic spectrum of taspine: Semiempirical calculations

AM1 calculations show that taspine has the three energy-minima along the rotation-like nuclear displacement of the dimethylaminoethyl group. They correspond to two enantiomeric structures and a Cs structure, which have nearly equal energies. The energy barrier between the enantiomeric structures and the Cs structure is calculated to be about 1 kcal/mol. The small barrier readily causes an intramolecular interconversion of the two enantiomers through the Cs structure and thus results in the optical inactivity of taspine. CNDO/S calculations show that the electronic spectra of the enantiomer and the Cs structure are quite similar. These calculated spectra are in good agreement with the observed electronic spectra.     

Figure Measurement of Concave Mirror by Fiber-Grating Hartmann Test

A new type of Hartmann test was developed using an optical fiber grating instead of the traditional Hartmann screen with multiple holes. A fiber-grating is made of short optical fibers arranged in single layers with no gaps between them. On illumination with laser light, the fiber-grating generates fan-like diverging multiple rays of almost equivalent intensities. Two gratings are overlapped at right angles to make multiple beams diverging in two directions. Rays reflected from test mirror surfaces converge to make a point focus provinding the sulface is free from aberrations. A CCD camera detects a spot pattern of beams near but out of focus, and a personal computer analyzes the spot patterns and calculates the figure error from a ideal surface. A few concave mirrors were analyzed by this method and the results compared with those obtained with a Fizeau interferometer. The data using the two systems were consistent with each other to within 1/10A.     

Polarography in polymer science

A review of polarography in polymer science is presented.     

Use of functional microgels with vinyl groups to accelerate photopolymerization reaction

Three types of functional microgels with vinyl groups on their surface were prepared. For the first type, the counter anion from clorin was exchanged with β-methacryloylethyl sulfonic acid, styrene sulfonic acid or allyl sulfonic acid in a microgel with ammonium anions. For the second and third types, a quaternization with N,N-dimethylaminoethyl methacrylate of 3-chloro-2-hydroxypropyl methacrylate in the presence of microgel particles was prepared by emulsion copolymerization of styrene, chloromethylstyrene or N,N-dimethylamino-methylbenzene, and divinylbenzene. The resulting samples show good dispersibility in organic solvents without an emulsifier. A functional microgel-based photopolymer combined with an acrylate monomer and ultraviolet (UV) or visible (VIS) light-absorbing photoinitiators provides oleophilic images when exposed to UV or VIS light and developed in tap water. This photopolymer has a higher sensitivity than those of photopolymers based on microgels with an analogous composition but without vinyl groups. Photopolymers pepared by using functional microgels with a methacryloyl group exhibited a higher rate of polymerization (R_p) than that of photopolymers based on microgels without a vinyl group. The R_p of photopolymers prepared by using a functional microgel with either an allyl group or vinylphenyl group was nearly equal to that of photopolymers based on microgels with ammonium ions. Their high sensitivities are attributed to the rapid photopolymerization in the methacryloyl group. To determine how the photoreaction mechanism enhances sensitivity, the photoreaction products were investigated using a model photopolymerization system. It was found that the gelation reactions enhancing sensitivity are predominantly the polymerization and crosslinking ones when a microgel with the methacryloyl group is used, and the graft copolymerization with acrylate monomers when a microgel with either the allyl group or vinylphenyl group is used.     

Thermal and acid-catalyzed reaction of bifunctional vinyl ether urethane in nonionic and ionic polymer matrices

A bifunctional vinyl ether urethane derivative (BVU) was synthesized and characterzed. Photoresist systems consisting of BVU and a photoacid generator (PAG) along with various matrix polymers were prepared and the photoresist characteristics were evaluated. In the presence of BVU and a PAG, poly(methylmethacrylate-co-acrylic acid) and poly(methylmethacrylate) exhibited positive and negative tone behavior, respectively, where as poly(p-hydroxystyrene) showed both positive and negative working properties depending on the prebake temperature of the system. The depandence of the photoresist behaviors on these matrix polymers was studied. The mechanism of the thermal and photochemical reactions was revealed.