Synthesis and spectrophotometric study of 2-[2-(3,5-dibromopyridyl,)azo] -5-dimethylaminobenzoic acid as an analytical reagent: Determination of nickel

2-[2-(3,5-Dibrornopyridyl)azo]-5-dimethyIam;nobenzoic acid (3,5-diBr-PAMB) has been synthesized and its potential for the spectrophotometric determination of metals studied. It reacts sensitively with nickel, cobalt, iron and copper, and is particularly useful for nickel. The apparent molar absorptivity in chloroform is 1.50 × 10⁵ l mol^-1 cm^-1 and the Sandell sensitivity is 0.4 ng Ni cm^-2. Nickel reacts with 3.5-diBr-PAMB at pH 4–10; at pH 4–7 the complex can be extracted into chloroform to give a stable purple solution. The optimal calibration range is 0.04–0.4 ppm Ni. Only Cu, Co, Fe, Pd and V interfere seriously but Pd, Cu and V can be masked by thiourea.     

Kinetics and thermodynamics of hexameric capsule formation

Resorcinarene 1b forms a hexameric assembly in water-saturated CDCl(3) that encapsulates one tetraalkylammonium salt (2(+)Br(-)). The remaining space is occupied by coencapsulated solvent molecules. A maximum of three and minimum of one CHCl(3) molecule were found inside of capsules with tetrapropyl- and tetraheptylammonium bromide, respectively. The encapsulation of the salt is endothermic and entropically favored by the liberation of the solvent molecules. The stabilities of the encapsulation complexes and the rates of guest exchange decrease for larger cations. The higher activation barriers for in/out exchange of the larger guests suggest tight conformational restraints in the transition state. It is likely that complete dissociation of one resorcinarene molecule is necessary for the exchange of the alkylammonium salts.     

Palladium-catalyzed asymmetric synthesis of axially chiral allenylsilanes and their application to SE2' chirality transfer reactions

Stepwise application of the Pd-catalyzed S(N)2' reaction and the desilylative S(E)2' reaction to the ambivalent 2-bromo-1-silyl-1,3-dienes provides a novel route to the highly enantioselective construction of tertiary and quaternary propargylic stereogenic centers via axially chiral allenylsilanes.     

Structural phase transition in ferroelectric fluorine polymers: X-ray diffraction and infrared/Raman spectroscopic study

The structural phase transition has been investigated by X-ray diffraction and infrared and Raman spectroscopic measurements for ferroelectric fluorine polymers, including poly(vinylidene fluoride) and its copolymers with trifluoroethylene or tetrafluoroethylene. One of the most characteristic features of this ferroelectric transition is the large conformational change of the molecular chains between the trans and gauche rotational isomers, quite different from the structural change observed generally in the usual ionic ferroelectric materials. The crystallization and transition behaviors depend sensitively on the monomer composition in the copolymers as well as on the sample preparation conditions. The roles of the optic and acoustic phonons in the ferroelectric phase transition have been discussed based on the temperature dependences of the far-infrared spectra and the ultrasonic velocity.     

Optimum Seeding Particles for Successful Laser Doppler Velocimeter Measurements

Seeding particles for laser Doppler velocimeter (LDV) measurement have been developed which are of uniform diameter, spherical shape, low loose weight and high melting temperature. Evaluation test results show that the use of the particles can increase the signal quality substantially and extend the measurable field of the LDV, which can hardly be accessed by conventional measurement methods.     

Structure and thermochromic solid-state phase transition of poly (3-alkylthiophene)

In order to clarify the structural changes that occur in the thermochromic phase transition of poly (3-dodecylthiophene) [P3DT] and poly (3-hexylthiophene) [P3HT], the temperature dependence of x-ray diffraction and Fourier transform infrared spectra was measured. (1) Orthogonal unit-cell parameters were determined at room temperature: a=25.83 Å, b=7.75 Å, c (fiber axis)=7.77 Å for P3DT and a=16.63 Å, b=7.75 Å, and c=7.77 Å for P3HT. A large variation of the a-axis length between P3DT and P3HT indicates the extended trans conformation for the alkyl side chains which are oriented along the lateral a-axis direction. (2) The interplanar spacing, intensity, and integral width of the x-ray (h00) and (00l) reflections were found to change drastically in the transition region. (3) Polarized infrared measurements at high temperature revealed a marked increase of the gauche band intensity for the alkyl side group modes followed by a decrease in the band intensity of the thiophene ring modes. (4) The layer reflections of the x-ray fiber diagram become diffuse at high temperatures, indicating that the transition occurs in a liquidcrystalline manner with the orientation of the main chain axes preserved but with almost no axial correlation between the neighboring main chains. These results provide experimental support for the structural model proposed earlier: as the temperature increases, the trans-type side chains begin to disorder by introduction of gauche bonds. This disordering disrupts the regularity of the main chain conformation and decreases the effective length of the polythiophene conjugated system.     

Molecular pattern formation using chemically modified cytochrome c

Molecular pattern formation using chemically modified cytochrome c and green fluorescent protein (GFP) was presented for the application as a bioelectronic device. A protein conjugate was synthesized by the formation of disulfide bridges. In order to make molecular assembly onto the gold-coated substrate, cytochrome c was cross-linked with N-succinimidyl-3-(2-pyridyldithio)propionate (SPDP). After the modification of cytochrome c, it was spontaneously deposited, so that it could be adsorbed onto the gold-coated substrate by self-assembly (SA) technique. Using the cellulose membrane, cytochrome c molecules were deposited onto the gold-coated substrate with the spatial resolution of ca. 0.2 μm. In order to verify the modified cytochrome c, UV absorption spectrum was measured. GFP was adsorbed onto the cytochrome c monolayer by electrostatic force. Fluorescence emission spectrum was investigated to verify the existence of the GFP molecule onto the cytochrome c monolayer. To verify the adsorption of cytochrome c molecules onto the gold-coated substrate and GFP molecules onto the cytochrome c monolayer, the atomic force microscopy and lateral force microscopy investigations were performed. Molecular pattern formation of cytochrome c and GFP molecules were successfully performed by chemical means and electrostatic force.     

On the pinched circle model and the absence of wandering domains for a topological polynomial

We shall construct a pinched circle model of the Julia set of a topological polynomial without recourse to the theory of analytic functions. By using this model, we study conditions under which a topological polynomial has no wandering domain.     

Analysis of a biopolymer by capillary electrophoresis with a chemiluminescence detector using a polymer solution as the separation medium.

We developed capillary electrophoresis with a chemiluminescence detector using a polymer solution as the separation medium for the analysis of biopolymers, such as DNA and protein. A peroxyoxalate chemiluminescence reagent of bis(2,4,6-trichlorophenyl)oxalate was used together with fluorescein-labeling reagent. When a migration buffer solution containing carboxylmethylcellulose was used, the flow-type chemiluminescence detection cell was found to give a better resolution than the batch-type one. Fluorescein-labeled adenosine triphosphate of 1.0 x 10(-4) M was examined by means of capillary electrophoresis with absorption (260 nm), fluorescence (ex. 496 nm and em. 517 nm), and chemiluminescence detectors. The chemiluminescence detection showed the highest sensitivity among them; the S/N ratios obtained by absorption, fluorescence, and chemiluminescence detections were 4, 38, and 130, respectively. Fluorescein-labeled DNA was prepared through a polymerase chain reaction using fluorescein-labeled deoxyadenosine triphosphate. A mixture of the labeled DNA fragments (500, 600, 700, 800, 900, and 993 bp) was successfully separated and detected by the present system. A mixture of proteins (lysozyme, cytochrome C, and ribonuclease A) which were labeled with fluorescein isothiocyanate was also separated and detected.     

Reversible sol-gel transition of a tris-urea gelator that responds to chemical stimuli

Tris-urea 1 functioned as a low-molecular-weight gelator for a variety of polar organic solvents. An acetone gel of 1 became a homogeneous solution in response to the addition of anions. The minimum amount of anion necessary for the gel-sol transition was specific to the anion species. A linear relationship was demonstrated between the amount of anion required and the total binding constant of 1 with the anion. Re-gelation occurred by addition of BF₃·OEt₂ and with ultrasound irradiation of the acetone solution of 1 and F⁻.