Compounds having thiourea moiety as derivatization reagents in liquid chromatography/electrospray ionization–tandem mass spectrometry (LC/ESI‐MS/MS): synthesis of derivatization reagents for carboxylic acids

The derivatization reagents for carboxylic acids, N‐(Pyridin‐3‐yl)hydrazinecarbothioamide, N‐[4‐(dimethylamino)phenyl]hydrazinecarbothioamide, 1‐(2‐aminoethyl)‐3‐(pyridin‐3‐yl)thiourea, 1‐(2‐aminoethyl)‐3‐[4‐(dimethylamino)phenyl]thiourea and 4‐(2‐aminoethyl)‐N‐phenylpiperazine‐1‐carbothioamide were synthesized. These reagents reacted with carboxylic acids at 60°C for 45 min in the presence of the condensation reagents. The generated derivatives were favorably separated on the reversed‐phase column and sensitively detected by electrospray ionization tandem mass spectrometry. These reagents enhanced the electrospray ionization response of the analyte and generated a particular product ion efficiently by collision‐induced dissociation, and thus they were suitable for MS/MS detection. Copyright © 2010 John Wiley & Sons, Ltd.     

Fractional order Sobolev spaces on Wiener space

Summary Fractional order Sobolev spaces are introduced on an abstract Wiener space and Donsker's delta functions are defined as generalized Wiener functionals belonging to Sobolev spaces with negative differentiability indices. By using these notions, the regularity in the sense of Hölder continuity of a class of conditional expectations is obtained.     

Synthesis and characterization of crosslinked uniform polymeric microspheres containing a polyimide prepolymer by a new emulsification process

A highly crosslinked poly(styrene–divinyl benzene–trimethyolpropane trimethacrylate) microsphere containing a polyimide prepolymer (PIP) was prepared by a new emulsification method, Shirasu porous glass (SPG) membrane emulsification, and a subsequent radical suspension polymerization. That is, a mixture of styrene, divinyl benzene, trimethyol propane trimethacrylate (TMPTMA), and PIP containing an initiator was permeated through the uniform pores of the SPG membrane into a continuous phase containing a stabilizer to form uniform droplets. Then, the suspension polymerization was carried out at 65 °C for 24 h. The trifunctional crosslinker TMPTMA was added to enhance the destructive strength of the microsphere, and PIP was incorporated into the microsphere to provide an adhesion force by a known self‐curing reaction at 220 °C. The effects of the feed amounts of TMPTMA and PIP on the monomer conversion, size distribution, and destructive strength of the microsphere were investigated. The monomer conversion increased with an increase in TMPTMA. The particle size distribution became narrower as the TMPTMA feed amount increased, but it became broader with an increase in PIP. The destructive strength increased with increases in TMPTMA and PIP. After a heat treatment at 220 °C, the destructive strength decreased because of the heat degradation of the polymer. The addition of TMPTMA suppressed the heat degradation, and PIP could undergo self‐curing at 220 °C. The obtained highly crosslinked uniform microsphere containing PIP has potential applications in liquid‐crystal displays. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2588–2598, 2003     

NMR study of one-dimensional ionic conductor with hollandite-type structure. II. Frequency dependence of spin-lattice relaxation time of 27Al

Frequency dependence of spin-lattice relaxation time T₁ of ²⁷Al in one-dimensional K⁺ ion conductor, K-Al-priderite, was measured at 45 K in the frequency range from 10.1 MHz to 55 MHz. It is found that T₁ is proportional to ω^1.49±0.05 and agrres well with the $\text{ω}{}^{\mathrm{<mtext>3</mtext><mtext>4</mtext>}}$ dependence derived by the continuum diffusion model. The intrinsic activation energy is determined to be 0.058 eV by doubling the slope E_NMR=0.029 eV of the d(ln T₁)/dT curve in the low temperature region. The frequency dependence of T₁ in the high temperature region measured in the frequency range from 11.5 MHz to 20.8 MHz shows a tendency that the frequency dependence becomes smaller than the $\text{ω}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ dependence as temperature is raised above 450 K.     

Incoherent-to-coherent conversion by use of the photorefractive fanning effect

A dynamic incoherent-to-coherent converter using the photorefractive fanning effect is demonstrated in a BaTiO(3):Ce crystal, and high-quality positive replicas of the incoherent image are obtained with a resolution of 32line pairs/mm. In this method the incoherent image-bearing beam modulates the transmission intensity of the coherent beam directly, and no readout beam is required. When the intensity ratio of the incoherent beam to the coherent beam is smaller than 5, the transmission intensity of the coherent beam increases almost linearly with increased intensity of the incoherent beam.     

Image transmission through a thick dynamic distorter by the photorefractive fanning effect

A new method of one-way image transmission through a thick dynamic distorter without the need for a reference beam or four-wave mixing is demonstrated. In this method there are only one object beam and one sampling beam. The response time of the photorefractive crystal must be much longer than the fluctuation period of the dynamic distorter. Thus the crystal responds only to the time-averaged intensity pattern of a rapidly varying object beam. The images, reconstructed with high fidelity, are picked up through the photorefractive fanning effect.     

Preparation of high performance nanocomposite elastomer: effect of reaction conditions on in situ silica generation of high content in natural rubber

Effect of amines on an in situ silica generation in natural rubber was investigated, and n-hexylamine, n-heptylamine and n-octylamine were found to increase the in situ silica content. The nanometer sized silica particles up to ca. 80 parts per hundred rubber by weight were generated in situ in the rubber matrix via a sol–gel reaction of tetraethoxysilane. Additionally, dispersion of the silica in the rubbery matrix was more homogeneous than that of commercial silica dispersed by a conventional mechanical mixing. In this in situ silica generation, the polarity and solubility in water of amine were influential factors for controlling the in situ silica content in the rubbery matrix. The obtained high in situ silica filled natural rubber was useful to prepare high performance nanocomposite elastomers.