Synthesis of desmosine-d4: Improvement of isotopic purity by D-H exchange of amino groups

Desmosine is a crosslinking pyridinium amino acid of elastin, which is a useful biomarker for the diagnosis of chronic obstructive pulmonary disease (COPD) by LC–MS/MS analysis. We previously reported a synthesis of desmosine-d₄, which is useful as an internal standard for quantitative LC–MS/MS analysis of desmosines, by deuterogenation of an alkyne group; however, the isotopic purity of the desmosine-d₄ was only ca. 50%. The present report describes a new synthesis of desmosine-d₄ that improves the isotopic purity to ca. 90% by exchanging the protons of the amino groups to deuterium using deuterogenation.     

Studies toward the total synthesis of nakiterpiosin: construction of the CDE ring system by a transannular Diels-Alder strategy

The transannular Diels-Alder (TADA) reaction was applied to the synthesis of the CDE ring system of nakiterpiosin (1). Tetracyclic compound 25 may be a key intermediate in the total synthesis of 1.     

Ideal nonideality in adsorption of 2-aminoethanethiol and 2-mercaptoethane sulfonic acid to form electrostatically stabilized binary self-assembled monolayers on Au(111)

In formation of binary self-assembled monolayers (SAMs) composed of 2-aminoethanethiol (AET) and 2-mercaptoethane sulfonic acid (MES) by adsorption from an ethanol solution on Au(111), the adsorption shows nearly ideal nonideality in that the surface ratio of MES to AET in the SAM is unity and does not depend on the mixing ratio of MES to AET in the bathing ethanol solution used for preparing SAMs, chi(soln)MES, over the wide range of chi(soln)MES between 0.01 and 0.95. X-ray photoelectron spectroscopy confirms that at least 80% of AET molecules adsorbed are protonated in this range of chi(soln)MES, indicating that the electrostatic interaction between positively charged AET and negatively charged MES is responsible to the observed nonideality. Correspondingly, there appears only one cathodic peak in a linear-sweep voltammogram of the reductive desorption of the SAM, having a narrow full width at half-maximum of about 20 mV. This suggests the presence of strong lateral attractive interaction between the adsorbed thiolates.     

Planar chiral cyclic ether: asymmetric resolution and chirality transformation

Remarkably stable planar chirality was found in a nine-membered diallylic cyclic ether. Enantiomerically enriched ether was prepared by a kinetic resolution of a racemic one, which is valuable as a novel type of chiral building block.     

Design of New Reaction Fields for Spherical Polypyrrole Particle Synthesis

Summary: Polypyrrole conducting polymers have been investigated widely for various applications because of their thermal and environmental stability and good electrical conductivity. Using chemical oxidative polymerization for the synthesis of polypyrrole particles, the reaction rate is very fast. In this study, we designed two new reaction fields for the synthesis of spherical polypyrrole nanoparticles. In the first system, oxidative polymerization of monomer droplets infused in a water/oil (W/O) emulsion reaction field was investigated. The second system employed dispersed monomer in an aqueous solution with a low concentration of oxidant in which polymerization was augmented by ultrasonic irradiation. Effective control of the reaction rate was important for enabling the synthesis of fine spherical polypyrrole particles.     

Precise isomerization polymerization of alkenylcyclohexanes: stereoregular polymers containing six-membered rings along the polymer chain

Pd and Ni diimine complexes catalyze the isomerization polymerization of alkenylcyclohexanes to afford polymers composed of alternating trans-cyclohexane-1,4-diyl rings and oligomethylene spacers with high selectivity. The melting points of the polymers vary from 130 to 226 °C depending on length of the oligomethylene spacer.     

Glass transition temperature of polyurethane foams derived from lignin by controlled reaction rate

Sodium ligninosulfonate (LS)-based polyurethane (PU) foams were prepared using three kinds of ethylene glycols, diethylene glycol, triethylene glycol or polyethylene glycol. Two kinds of industrial NaLS, acid-based and alkaline-based NaLS, were mixed with various ratios, and foaming reactions were controlled. Mixing, cream, and rise time were used as an index of foaming reaction. Mixing time was defined as the time interval from adding isocyanate to detection of evolved heat under stirring, cream time as the time interval from termination of stirring to starting of foaming, and rise time as the time interval from starting to completion of foaming. The above reaction time increased with increasing amount of acid base NaLS content in polyols. Apparent density, compression strength and compression modulus of PU foams linearly increased with reaction time. Thermal decomposition temperature was measured by thermogravimetry and glass transition temperature by differential scanning calorimetry. Glass transition temperature can be controlled in a temperature range from 310 to 390 K by changing the mixing rate of two kinds of LS and molecular mass of ethylene glycols. It was found that mechanical and thermal properties of PU foams are controllable through the foaming reaction rate using two kinds of industrial lignin.