Organocatalytic acetylation of pea starch: Effect of alkanoyl and tartaryl groups on starch acetate performance.

Organocatalytic acetylation of pea starch was systematically optimized using tartaric acid as catalyst. The effect of the degree of substitution with alkanoyl (DSacyl) and tartaryl groups (DStar) on thermal and moisture resistivity, and film-forming properties was investigated. Pea starch with DSacyl from 0.03 to 2.8 was successfully developed at more efficient reaction rates than acetylated maize starch. Nevertheless, longer reaction time resulted in granule surface roughness, loss of birefringence, hydrolytic degradation, and a DStar up to 0.5. Solid-state 13C NMR and SEC-MALS-RI suggested that tartaryl groups formed crosslinked di-starch tartrate. Acetylation increased the hydrophobicity, degradation temperature (by ~17 %), and glass transition temperature (by up to ~38 %) of pea starch. The use of organocatalytically-acetylated pea starch with DSacyl ≤ 0.39 generated starch-based biofilms with higher tensile and water barrier properties. Nevertheless, at higher DS, the incompatibility between highly acetylated and native pea starches resulted in a heterogenous/microporous structure that worsened film properties.

An efficient and easily-accessible ligand for Cu(I)-catalyzed azide-alkyne cycloaddition bioconjugation.

A novel ligand (6) for copper-catalyzed azide-alkyne cycloaddition (CuAAC) in bioconjugation has been developed. Both in vitro and in vivo experiments indicate that 6 is more efficient and less cytotoxic than the canonical CuAAC ligands. Besides, 6 is easily accessible and can be prepared at gram scale. Our study reveals that 6 might be an ideal CuAAC ligand for bioconjugations.

Microwave-promoted facile and efficient preparation of N-(alkoxycarbonylmethyl) nucleobases--building blocks for peptide nucleic acids.

A simple, rapid, and regioselective approach for the synthesis of N-(methoxy-carbonylmethyl)- and N-(n-propoxycarbonylmethyl) nucleobases was developed. By using DMF as the solvent and in the presence of K2CO3 as the base, all the desired products were obtained in moderate yields within 8 min under microwave irradiation.

One-pot formation and characterization of macrocyclic aromatic tetrasulfonates.

Aromatic tetrasulfonate macrocycles were prepared in one pot by treating arenedisulfonyl chlorides with dihydroxyarenes. X-ray structures revealed that these cyclic molecules have noncollapsible cavities and well-defined conformations resembling the cone and partial cone conformations of calix[4]arenes. Incorporating aromatic residues of different sizes leads to macrocycles with different cavity sizes.