Fmoc-L-tryptophanol

An analytical methodology based on an O-[2-(methacryloyloxy)-ethylcarbamoyl]-10,11-dihydroquinidine (MQD)-silica hybrid monolithic column was developed for the enantioseparation of 9-fluorenylmethoxycarbonyl (FMOC) derivatized amino acids by nano-liquid chromatography. The mobile phase was optimized including the apparent pH, content of ACN, and concentration of the buffer to obtain a satisfactory enantioresolution performance. 27 FMOC derivatized amino acids including 19 protein and 8 non-protein amino acids were tested, and 19 out of them were enantiomerically discriminated obtaining baseline separation for 11 of them. Analytical characteristics of the method were evaluated for norvaline and tryptophan in terms of linearity, precision, accuracy, limits of detection (LOD) and quantitation (LOQ) showing good performance to be applied to the enantiomeric determination of these amino acids in dietary supplements. LOD and LOQ values were 9.3 and 31 μM for norvaline enantiomers and 7.5 and 25 μM for tryptophan enantiomers, respectively. The contents of d-norvaline and d-tryptophan were below their respective LODs in all the analyzed samples. Quantitation of l-tryptophan and l-norvaline showed good agreement with the labeled contents except for one sample which did not show presence of l-norvaline, contrary to the label indication.

Bio-endogenous peptide molecules are ideal components for fabrication of biocompatible and environmentally friendly semiconductors materials. However, to date, their applications have been limited due to the difficulty in obtaining stable, high-performance devices. Herein, simple amino acid derivatives fluorenylmethoxycarbonyl-leucine (Fmoc-L) and fluorenylmethoxycarbonyl-tryptophan (Fmoc-W) are utilized to form long-range ordered supramolecular nanostructures by tight aromatic stacking and extensive hydrogen bonding with mechanical, electrical and optical properties. For the first time, without addition of any photosensitizers, pure Fmoc-L microbelts and Fmoc-W microwires exhibit Young's modulus up to 28.79 and 26.96 GPa, and unprecedently high values of photocurrent responses up to 2.2 and 2.3 μA/cm2, respectively. Meanwhile, Fmoc-W microwires with stable blue fluorescent emission under continuous excitation are successfully used as LED phosphors. Mechanism analysis shows that these two amino acids derivatives firstly formed dimers to reduce the bandgap, then further assemble into bioinspired semiconductor materials using the dimers as the building blocks. In this process, aromatic residues of amino acids are more conducive to the formation of semiconducting characteristics than fluorenyl groups. STATEMENT OF SIGNIFICANCE: Long-range ordered amino acid derivative assemblies with mechanical, electrical and optical properties were fabricated by a green and facile biomimetic strategy. These amino acid assemblies have Young's modulus comparable to that of concrete and exhibit typical semiconducting characteristics. Even without the addition of any photosensitizer, pure amino acid assemblies can still produce a strong photocurrent response and an unusually stable photoluminescence. The results suggest that amino acid structures with hydrophilic C-terminal and aromatic residues are more conducive to the formation of semiconducting characteristics. This work unlocks the potential for amino acid molecules to self-assemble into high-performance bioinspired semiconductors, providing a reference for customized development of biocompatible and environmentally friendly semiconductor materials through rational molecular design.

Due to their structural characteristics at the nanoscale level, single-walled carbon nanotubes (SWNTs), hold great promise for applications in biomedicine such as drug delivery systems. Herein, a novel single-walled carbon nanotube (SWNT)-based drug delivery system was developed by conjugation of various Fmoc-amino acid bearing polyethylene glycol (PEG) chains (Mw = 2,000, 5,000, and 12,000). In the first step, full-atom molecular dynamics simulations (MD) were performed to identify the most suitable Fmoc-amino acid for an effective surface coating of SWNT. Fmoc-glycine, Fmoc-tryptophan, and Fmoc-cysteine were selected to attach to the PEG polymer. Here, Fmoc-cysteine and -tryptophan had better average interaction energies with SWNT with a high number of aromatic groups, while Fmoc-glycine provided a non-aromatic control. In the experimental studies, non-covalent modification of SWNTs was achieved by Fmoc-amino acid-bearing PEG chains. The remarkably high amount of Fmoc-glycine-PEG, Fmoc-tryptophan-PEG, and Fmoc-cysteine-PEG complexes adsorbed onto the SWNT surface, as was assessed via thermogravimetric and UV-vis spectroscopy analyses. Furthermore, Fmoc-cysteine-PEG5000 and Fmoc-cysteine-PEG12000 complexes displayed longer suspension time in deionized water, up to 1 and 5 week, respectively, underlying the ability of these surfactants to effectively disperse SWNTs in an aqueous environment. In vitro cell viability assays on human dermal fibroblast cells also showed the low cytotoxicity of these two samples, even at high concentrations. In conclusion, synthesized nanocarriers have a great potential for drug delivery systems, with high loading capacity, and excellent complex stability in water critical for biocompatibility.