Efficiently Synthesizing Lacto-Ganglio-Series Gangliosides by Using a Glucosyl Ceramide Cassette Approach: The Total Synthesis of Ganglioside X2

The first total synthesis of the hybrid ganglioside X2, which consisted of a highly branched octasaccharide and ceramide moieties, was accomplished by using a glucosyl ceramide cassette approach. With a disaccharyl donor, the heptasaccharide could not be constructed by glycosylation of the C4 hydroxy group of galactose at the reducing end of the pentasaccharide. In contrast, through an alternative approach with two branched glycan units, a GM2-core trisaccharide, and a lacto-ganglio tetrasaccharide, the heptasaccharyl donor could be prepared and subsequently joined with a glucosyl ceramide cassette to afford the protected ganglioside, X2. Finally, global deprotection completed the synthesis, thus affording the pure ganglioside X2.     

Development of a stable isotope dilution UPLC‐MS/MS method for quantification of dexmedetomidine in a small amount of human plasma

Dexmedetomidine (Dex) is a selective central α2‐agonist with anesthetic properties and has been used in clinical practice for sedation in the intensive care unit (ICU) after operations. In this study, an analytical assay for the determination of Dex in a small amount of plasma was developed for the application to pediatric ICU trials. The quantification of Dex was constructed using the original stable isotope Dex‐d₃ for electrospray ionization‐tandem mass spectrometry (ESI‐MS/MS) in the selected reaction monitoring mode. A rapid ultra‐performance liquid chromatography technique was adopted using ESI‐MS/MS with a runtime of 3 min. Efficacious concentration levels (50 pg/mL to 5 ng/mL) could be evaluated using a very small amount of plasma (10 μL) from patients. The lower limit of the quantification was 5 pg/mL in the plasma (100 µL). For sample preparation, a solid‐phase extraction was used along with the OASIS‐HLB cartridge type. Recovery values ranged from 98.8 to 100.3% for the intra‐ [relative standard deviation (RSD), 0.9–1.3%] and inter‐ (RSD, 0.9–1.5%) day assays. A stable test had recovery values that ranged from 97.8 to 99.7% with an RSD of 1.0–1.9% for the process/wet extract, bench‐top, freeze–thaw and long‐term tests. This method was used to measure the Dex levels in plasma from pediatric ICU patients. In the clinical ICU trial, the small amount of blood (approximate plasma volume, 200 μL) remaining from blood gas analysis was reused and targeted for the clinical analysis of Dex in plasma. Copyright © 2013 John Wiley & Sons, Ltd.     

Methylol‐functional benzoxazines as precursors for high‐performance thermoset polymers: Unique simultaneous addition and condensation polymerization behavior

A new class of high‐performance resins of combined molecular structure of both traditional phenolics and benzoxazines has been developed. The monomers termed as methylol‐functional benzoxazines were synthesized through Mannich condensation reaction of methylol‐functional phenols and aromatic amines, including methylenedianiline (4,4′‐diaminodiphenylmethane) and oxydianiline (4,4′‐diaminodiphenyl ether), in the presence of paraformaldehyde. For comparison, other series of benzoxazine monomers were prepared from phenol, corresponding aromatic amines, and paraformaldehyde. The as‐synthesized monomers are characterized by their high purity as judged from ¹H NMR and Fourier transform infrared spectra. Differential scanning calorimetric thermograms of the novel monomers show two exothermic peaks associated with condensation reaction of methylol groups and ring‐opening polymerization of benzoxazines. The position of methylol group relative to benzoxazine structure plays a significant role in accelerating polymerization. Viscoelastic and thermogravimetric analyses of the crosslinked polymers reveal high T_g (274–343 °C) and excellent thermal stability when compared with the traditional polybenzoxazines. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Surface modification for nano‐lignocellulose fiber through vapor‐phase‐assisted surface polymerization

This study addresses the inherent issues surrounding surface modification methods of nanofibers and proposes an environmentally friendly and less toxic strategy for the surface modification of hydrophilic nanofiber. From the continuation of our previous work, which discussed the easy production of nanofiber (average size: 127 nm) from oil palm mesocarp fiber (OPMF), in this work, the surface of nanofibers (M‐IL‐OPMF) were modified through vapor‐phase‐assisted surface polymerization (VASP) to improve the affinity of interface between the polymer grafted M‐IL‐OPMF and non‐polar matrix. VASP of ε‐caprolactone was successfully proceeded from the [M‐IL‐OPMF] at 70 °C for 24 h and 72 h, and compositions were estimated to be 35.7% fiber/64.3% polymer and 27.8% fiber/72.2% polymer. To confirm the grafting of PCL, size‐exclusion chromatography (SEC) and Fourier transform infrared (FT‐IR) spectroscopy, thermogravimetry (TG), and dispersibility test in hydrophobic solvent were carried out. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2575–2580     

Total synthesis of pleurolactone

The stereoselective total synthesis of pleurolactone has been accomplished in 7 steps. The key synthetic features were the construction of four contiguous stereocenters using an endo-selective Diels-Alder reaction and high diastereoselective dihydroxylation.     

Synthesis of oligo(spiroketal)s by polycondensation of silyl ethers derived from naturally occurring myo‐inositol with 1,4‐cyclohexanedione

Oligo(spiroketal)s (OSKs) were synthesized from myo‐inositol, a naturally occurring cyclic compound bearing six hydroxyl groups. The successful synthesis of OSKs was achieved using silyl ethers 2 derived from 1,4‐di‐O‐alkylated myo‐inositol 1 as monomers, which underwent polycondensation with 1,4‐cyclohexanedione (CHD) at 0 °C in the presence of trimethylsilyl triflate as a catalyst. Because of the irreversible nature of the condensation reaction of silyl ethers with ketones, the resulting OSKs 7 had higher molecular weights than previously reported OSKs that were obtained by polycondensation of tetraols 1 with CHD, where backward hydrolysis of the ketal functions occurred. In addition, another series of OSKs, 8, were synthesized using silyl ethers 3 derived from 2,5‐di‐O‐alkylated myo‐inositol 6 , which are more symmetric monomers than silyl ethers 2 . Silyl ethers 3 underwent efficient polycondensation with CHD, whereas tetraol 6 did not, demonstrating that the derivation of such tetraols into the corresponding silyl ethers is a powerful strategy to access OSKs. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2407–2414