ESR imaging of polymers and solid materials

EPR imaging was applied to the study of several important processes in polymers and materials. The solvent diffusion and induced swelling was visualized in the water/DMF or toluene/DMF interactions with polycarbonate or polystyrene molded rods. The cross-sectional images revealed non-homogeneous solute/solvent diffusion, rod expansion and crack development. The ESR lineshapes in all cases above confirmed that the nitroxide imaging agent did not interact significantly with the polymer matrix; thus the paramagnetic distribution reflected bulk solvent distribution quite well. The diffusion of an electrolyte buffer (Krebs) solution containing a nitroxide spin probe was followed in a cross-sectional image of a polyacrylamide gel rod. A one-dimensional radial diffusion constant was calculated for the solvent piperidinol nitroxide spin probe, TEMPOL. Lastly, solid coal rods were monitored during mild pyrolysis at 150°C in air. Here the naturally occurring organic radical composition was imaged. Even with the increase in total ESR signal and subsequent decline to ca. the initial levels, the coal rod cross-section was essentially homogeneous in paramagnetic centers throughout the heating process. All of the imaging above utilized a homemade L-band, flat loop surface coil spectrometer.     

Biodetergent IV. Monolayers of corynomycolic acids at the air-water interface

The effects of alkyl chain length and of differences in the length of the two alkyl chains on the formation of a monolayer of chemically synthesized corynomycolic acid (2-alkyl-3-hydroxy fatty acid) at the air-water interface were examined. Hydrophobic interactions between the two alkyl chains are required for the formation of a condensed film, which is most stable when the total number of carbon atoms in the two alkyl chains is 25 or more and the difference in their lengths is one. Syn-isomers form condensed films but usually not anti-isomers. However, films may also be formed by the anti-isomer when the alkyl chain at the carboxy group (the 2-position) is longer than the alkyl chain at the hydroxy group (the 3-position). That is, the contribution of anti-isomers to condensed film formation depends on the polar carboxy group which has greater involvement in this formation. The extrapolated area for the condensed film of corynomycolic acid was 40 Ų per molecule, thus confirming that both the carboxy and hydroxy groups are present on the water surface when a bipolar monolayer is formed.     

Targeted 1,3-dipolar cycloaddition with acrolein for cancer prodrug activation

Cytotoxic anticancer drugs used in chemotherapy are often antiproliferative agents that preferentially kill rapidly growing cancer cells. Their mechanism relies mainly on the enhanced proliferation rate of cancer cells and is not genuinely selective for cancer cells. Therefore, these drugs can also significantly affect healthy cells. Prodrug therapy provides an alternative approach using a less cytotoxic form of anticancer drug. It involves the synthesis of inactive drug derivatives which are converted to an active form inside the body and, preferably, only at the site of cancerous tissues, thereby reducing adverse drug reaction (ADR) events. Herein, we demonstrate a prodrug activation strategy by utilizing the reaction between aryl azide and endogenous acrolein. Since acrolein is generally overproduced by most cancer cells, we anticipate our strategy as a starting point for further applications in mouse models with various cancers. Furthermore, cancer drugs that have had therapeutic index challenges might be reconsidered for application by utilizing our strategy.

Prodrug activation strategy by utilizing the reaction between aryl azide and endogenous acrolein that is generally overproduced by cancer cells.     

Functional one,two, and three-dimensional ZnO structures by solvothermal processing

Crystalline zinc oxide (ZnO) has been fabricated by solvothermal techniques under quite different temperature and pressure environment stretching from sub- to supercritical conditions. Among them, one-step processing of inorganic–inorganic hybrid ZnO structures based on ZnO substrate with attached ZnO nanocrystals has been challenged. Combination of doping ions was made to yield ZnO structures with luminescent properties of high potential for application in fast-decay devices. The room temperature decay of antimony, lithium (Sb, Li) codoped homoepitaxial films is reported.     

Production of micron-sized, monodispersed, multihollow polystyrene/poly(3,5-xylidine) composite particles by chemical oxidative seeded polymerization

 Micron-sized, monodispersed polystyrene/poly(3,5-xylidine) composite polymer particles were produced by chemical oxidative seeded polymerization of 3,5-xylidine with 1.37-μm-sized, monodispersed polystyrene seed particles. The chemical oxidative seeded polymerization was conducted in an aqueous medium at 25 °C in the presence of poly(vinyl alcohol) as a stabilizer using ammonium persulfate as an oxidant. The composite particles had a multihollow structure. Received: 30 June 1999/Accepted in revised form: 21 October 1999     

Efficient synthesis of 2-oxazolidinones and quinazoline-2,4(1H,3H)-diones from CO2 catalyzed by tetrabutylammonium fluoride

By employing tetrabutylammonium fluoride (TBAF) as a catalyst, the various carboxylative cyclizations of the propargylic amines having internal alkynes with CO₂ proceeded to afford the corresponding 2-oxazolidinones. In this case, it was also found that the generated 2-oxazolidinones were tautomerized into the corresponding 2-oxazolones due to the basicity of TBAF. In addition, we performed the synthesis of quinazoline-2,4(1H,3H)-dione from 2-aminobenzonitrile and CO₂ by using TBAF as a catalyst.     

Hydration of the organized molecular assembly of ionic surfactants as studied by vapor pressure and x-ray diffraction

Equilibrium vapor pressure of water was measured for ionic surfactant-water binary systems as a function of water content over the temperature range 5–11°C. The measurement of x-ray powder diffraction has also been performed to characterize the microscopic structures of these two-component systems. Examined surfactants were the homologs of sodium alkyl sulfate and alkyltrimethylammonium bromide. It was found that dodecyl and decyl sulfate formed solid di-and trihydrate respectively, while octyl sulfate and the cationic surfactants formed lyotropic liquid crystal instead. The x-ray long spacing of the liquid crystals scarcely varied with water content.Enthalpy of vaporization was calculated for both solid hydrates and lyotropic liquid crystals.     

Quantitative determination of amorphous nicardipine hydrochloride in long acting formula (NIC-LA) using light anhydrous silicic acid

We investigated a method to quantitatively determine amorphous nicardipine hydrochloride (NIC) in the NIC-long acting formula (LA) model formulas prepared using NIC, light anhydrous silicic acid (LASA) and carboxymethylethylcellulose (CMEC). Consequently, since the quantity of total NIC in the formula can be determined by means of HPLC and crystal NIC can be determined by the differential scanning calorimetry (DSC) method because the heat of fusion (85.08 J/g) of NIC is constant and unaffected by excipients, we developed the HPLC-DSC method by which the quantity of amorphous NIC is calculated as the difference between the quantity of total NIC determined by HPLC and the quantity of crystal NIC determined by DSC. This practical HPLC-DSC method was confirmed to have good accuracy and reproducibility.     

Homochirality and life

Before the emergence of life, left-handed amino acids (L-enantiomers) were selected and right-handed amino acids (D-enantiomers) were eliminated on the primal earth. Nevertheless, with the progress of analytical methods, D-amino acids have recently been found in higher order living organisms in the form of free amino acids, peptides, and proteins. Free D-amino acids have numerous physiological functions. D-amino acids containing animal peptides are well known as opioid peptides. D-amino acids in protein are related to aging. In this review, we describe the D-amino acids that are present and function as D-amino acid biosystems in our bodies.