H-α-Me-Tyr(tBu)-OH

Oriental lacquer sap is attracting considerable attention as a renewable and eco-friendly natural resin with high durability, heat resistance, insulation, insect repellency, and antiseptic and antibacterial properties. However, to ensure excellent coating performance, it is necessary to improve the drying/curing process of lacquer sap with a time-consuming drying time at high humidity [relative humidity (RH), 70-90%] and ambient temperature (20-30 °C). Drawing on an understanding of the polymerization mechanism of urushiol, the main component of the lacquer sap consisted of a water-in-oil (W/O) emulsion, and this study presents an eco-friendly additive that mimics the structure-function of urushiol composed of a polar catechol head group and a nonpolar hydrocarbon tail. A photo-curable lacquer sap was thus developed by adding a tyrosine amino acid-based lipid agent (denoted as Y-ADDA), which allows faster and more effective drying/curing at lower humidity while maintaining the nature-derived properties of lacquer sap. Y-ADDA easily coassembles with urushiol in the W/O emulsion droplets, thereby significantly accelerating the formation of a polymer network along with urushiol during water evaporation leading to fast drying/curing under ultraviolet (UV) light irradiation at low humidity (~50% RH). The UV-cured lacquer sap resins showed higher performance in terms of film processing and physicochemical properties compared with that of the lacquer containing only tyrosine amino acids without aliphatic tail conjugation, N-(9-fluorenylmethoxycarbonyl)-O-tert-butyl-l-tyrosine Fmoc-Tyr(tBu)-OH. Furthermore, the drying and curing times, film morphology, transmittance, hardness, and adhesion strength of the UV-cured lacquer were markedly superior compared to those of shellac, a general eco-friendly fast-drying primer. The study provides useful strategies and insights to promote the industrial application of lacquer sap resins by employing biocompatible nanoagents developed with an understanding of the curing mechanism of natural resins and from the viewpoint of green and sustainable chemistry perspective.

The synthesis of different diketomorpholines via N-acyl-3,4-dihydro-2 H-1,4-oxazine-3-carboxylic acids is reported in this article. The key intermediates were prepared using a convenient solid-phase synthesis starting from polymer-supported Ser( tBu)-OH. After subsequent sulfonylation with 4-nitrobenzenesulfonyl chloride (4-Nos-Cl), alkylation with an α-bromoketone, cleavage of the 4-Nos group and acylation with an α-halocarboxylic acids, acid-mediated cleavage from the resin yielded dihydrooxazine-3-carboxylic acids in high crude purities. Depending on the reaction conditions, exposure to base resulted in cyclization to either oxazino[3,4- c][1,4]oxazine-diones or 3-methylidenemorpholine-2,5-diones. Further reaction with triethylsilane-trifluoroacetic acid (TES/TFA) led to olefin reduction, in the case of oxazino[3,4- c][1,4]oxazine-dione with full control of the newly formed stereocenter.

The gelation of L-Tyr(tBu)-OH in tetrahydrofuran (THF) was discovered serendipitously. It was noted that this tremendously low molecular weight (LMW) compound has the ability to gel a wide variety of organic solvents (e.g., N,N-Dimetylformamide (DMF), THF, butanol, toluene), even in very low concentrations (i.e., 0.1 wt/v% in DMF). Addition of bases such as NaOH and piperidine enhanced the gel property. By changing the side-chain protecting group to tert-butyldimethylsilyl (TBDMS), a fluoride ion-responsive organogel was also acquired. This new organogelator responded fluoride ion concentration as low as 0.2 ppm. Characterization of microstructures and gel behaviours were studied by powder X-Ray diffraction spectroscopy (XRD), transmission electron microscopy (TEM), rheological measurements and molecular dynamics (MD) simulations. Experimental observations and theoretical simulations consistently show a fibre-like structure of the gel, in which the organogelator molecules are held together via a dense network of hydrogen bonds, and via van der Waals interactions between hydrophobic groups.