Simultaneous spectrophotometric analysis of aliphatic amines utilizing thermochromism of charge-transfer complexes with tetrabromophenolphthalein ethyl ester.

Aliphatic amines, such as n-hexylamine (primary), di-n-hexylamine (secondary) and tri-n-hexylamine (tertiary amine), react with tetrabromophenolphthalein ethyl ester molecules (TBPEH) to form reddish or red-violet charge-transfer complexes (CT complexes) in 1,2-dichloroethane (DCE). The absorption maxima of the CT complexes with all primary amines occur at around 560 nm, with secondary amines at 570 nm and, with tertiary amines at 580 nm. The CT complex formation constants with TBPEH in DCE increase in the order of the primary, secondary and tertiary amines, but their constants decrease quantitatively with an increase in temperature. This phenomenon (thermochromism) could be applied to the simultaneous spectrophotometric determination of primary amine and secondary amine, or secondary amine and tertiary amine in a mixed solution utilizing the difference of absorbance with temperature changes.     

Specific removal of o-methoxybenzyl protection by DDQ oxidation.

Methoxybenzyl protecting groups of alcohols were readily and efficiently removed with DDQ in CH₂Cl₂-H₂O at room temperature. Under these neutral conditions, other usual protecting groups, isopropylidene, methoxymethyl, benzyloxymethyl, tetrahydropyranyl, acetyl, t-butyldimethylsilyl, benzyl, benzoyl, and tosyl, as well as functional groups, epoxide, double bond, and ketone, were remained unchanged.     

Emulsifier-free emulsion polymerization of tetrafluoroethylene by radiation. II. Effects of reaction conditions on polymer particle size and number

The size, distribution, and number of PTFE particles formed by radiation-induced emulsifier-free polymerization were measured by electron microscope and automatic particle analyzer (centrifugation method). From the electron micrographs we found that the particles are formed within 5 min. The change in the number of polymer particles (n_p) with reaction time (t) depends on the relative concentration of growing polymer chains to stabilizing species produced by the radiolysis of water and monomer; that is, it was governed by TFE pressure/dose rate ratio and classified into three cases: case I, dn_p/dt = 0 (e.g., at 3 × 10⁴ rad/hr and 20 kg/cm²); case II, dn_p/dt < 0 (e.g., at dose rate below 1.9 × 10⁴ rad/hr and 20 kg/cm²); case III, dn_p/dt > 0 (e.g., at 3 × 10⁴ rad/hr and 2 kg/cm²). The polymer molecular weight above 10⁶ is almost independent of the particle size. The polymerization loci are mainly on the surface of polymer particles dispersed in the aqueous phase in cases I and II except in the initial stage. In case III new particles are formed successively during polymerization. Therefore the polymerization loci are mainly in the aqueous phase. Especially in case I, we concluded that after the generation of particles the propagation proceeds mainly on the surface of polymer particles like the core shell model proposed by Granico and Williams.     

Effect of molecular weight on the crystalline structure of polytetrafluoroethylene as-polymerized

Melting and crystallization behavior of polytetrafluoroethylene as polymerized in emulsion and suspension is shown to depend on molecular weight. DSC heating curves for virgin PTFE with low molecular weight below 3 × 10⁵ have a single peak, whereas curves for higher molecular weight samples have double peaks. With increasing heating rate the areas of higher melting peaks become larger than the lower melting peaks. The morphology of polymer exhibiting double melting peaks is mainly folded ribbons or granular particles. The phenomenon of double melting is explained on the basis of two different crystalline states which correspond to the “fold regions” and the “linear segments” in a folded ribbon. The melting temperature of virgin PTFE is almost constant at ca. 330°C for molecular weights below 1 × 10⁶, and rises as the molecular weight increases above 1 × 10⁶. The heat of melting of virgin PTFE is nearly independent of molecular weight. On the basis of these results, we propose a model for melting and crystallization of low and high molecular weight PTFE and for the crystal structure.     

Enantioselective aldol reaction of trimethoxysilyl enol ether catalyzed by lithium binaphtholate

[reaction: see text] An aldol reaction of trimethoxysilyl enol ether catalyzed by lithium binaphtholate, in which water serves as an additive and plays a pivotal role in stereoselectivities, was developed. This is the first example of an aldol reaction of trimethoxysilyl enol ether catalyzed by a chiral base.     

Quantification of cerebral metabolites in glioma patients with proton MR spectroscopy using T2 relaxation time correction

This study was aimed to investigate the significance of absolute concentration of metabolites in glioma patients using proton MR spectroscopy (MRS) with T2 relaxation time correction using three different echo times. The absolute concentrations of metabolites in 7 normal subjects and in 23 gliomas (10 low-grade, 13 high-grade) were obtained by proton MRS using a tissue water signal as an internal standard. The signal intensities of metabolites and tissue water were corrected by T2 relaxation time. In low-grade glioma, the T2 relaxation time of NAA was shorter, and T2 relaxation time of water was prolonged as compared to normal subjects (p < 0.001). In high-grade glioma, the T2 relaxation time of NAA (p < 0.001) and T2 relaxation time of Cr (p < 0.01) were shorter, and T2 relaxation time of water (p < 0.001) was prolonged as compared to normal subjects. Moreover, high-grade gliomas revealed a shorter T2 relaxation time of Cr than low-grade gliomas (p < 0.05). In glioma, NAA and Cr concentration were decreased, and Cho were increased as compared to normal subjects. Moreover, high-grade glioma revealed a significant lower Cr (p < 0.001) and Cho (p < 0.01) concentration compared to low-grade gliomas. Low Cr concentration is the most reliable indicator of malignancy in glioma. Cho concentration did not correlate with malignancy in gliomas.     

Electron spin resonance study on chemical‐crosslinking reaction mechanisms of polyethylene using a chemical agent. VI. Effect of α‐methyl styrene dimer

The effect of α‐methyl styrene dimer (AMSD), which is used as a scorch retarder, on the reaction mechanisms of the chemical crosslinking of polyethylene (PE) with dicumyl peroxide (DCP) at high temperatures was investigated using electron spin resonance. When AMSD was added to PE containing DCP, the AMSD radical was observed; however, the PE alkyl radical or allyl radical presence was not detected. At 145 °C, crosslinking was obstructed as a result of the reaction between AMSD and alkyl radicals. As the temperature increased, AMSD fragmented to form 2‐phenyl‐2‐propyl and double bonds in PE. This generation of double bonds, however, accelerated crosslinking at 180 °C and was more effective than when AMSD was not present. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2151–2156, 2001     

Helically Assembled Pyrene Arrays on an RNA Duplex That Exhibit Circularly Polarized Luminescence with Excimer Formation

Circularly polarized luminescence (CPL) was observed in pyrene zipper arrays helically arranged on an RNA duplex. Hybridization of complementary RNA strands having multiple (two to five) 2′‐O‐pyrenylmethyl modified nucleosides affords an RNA duplex with normal thermal stability. The pyrene fluorophores are assembled like a zipper in a well‐defined helical manner along the axis of RNA duplex, which, upon 350 nm UV illumination, resulted in CPL emission with pyrene excimer formation. CPL (g_lum) levels observed for the pyrene arrays in dilute aqueous solution were +2×10^?2–+3.5×10^?2, which are comparable with |g_lum| for chiral organic molecules and related systems. The positive CPL signals are consistent with a right‐handed helical structure. Temperature dependence on CPL emission indicates that the stable rigid RNA structure is responsible for the strong CPL signals. The single pyrene‐modified RNA duplex did not show any CPL signal.