Design of a stabilized short helical peptide and its application to catalytic enantioselective epoxidation of (E)-chalcone

Stabilized short helical heptapeptides containing a combination of an α-aminoisobutyric acid as a helical promoter and l/d-serine derivatives to produce cross-linked units were synthesized. The cyclic peptide R₃,₇R-2, which had d-serine derivatives at its 3rd and 7th positions, formed a stable right-handed (P) α-helix in solution and the crystalline state. Furthermore, its N-terminal free helical peptide catalyzed the enantioselective epoxidation of (E)-chalcone to afford the epoxide in a high yield and moderate enantioselectivity.     

Enantioselective epoxidation of α,β-unsaturated ketones catalyzed by stapled helical l-Leu-based peptides

Stapled helical l-leucine-based heptapeptides were synthesized and used as catalysts for the enantioselective epoxidation of α,β-unsaturated ketones. All N-terminal free stapled peptides were successfully used as chiral catalysts. Among them, the use of H-hS₃,₇hS-10 gave epoxide products with high enantioselectivities of up to 99% ee. Furthermore, the dominant conformations of the N-terminal protected stapled peptides R₃,₇R-10 and hS₃,₇hS-10 were investigated by ¹H NMR, IR, CD spectra, and X-ray crystallographic analysis. The peptide R₃,₇R-10 formed a right-handed (P) α-helix in solution and in the crystalline state, while hS₃,₇hS-10 formed a right-handed (P) 3₁₀-helix in solution.     

Improving peptide fragmentation by N-terminal derivatization with high proton affinity

An improved method of de novo peptide sequencing based on mass spectrometry using novel N-terminal derivatization reagents with high proton affinity has been developed. The introduction of a positively charged group into the N-terminal amino group of a peptide is known to enhance the relative intensity of b-ions in product ion spectra, allowing the easy interpretation of the spectra. However, the physicochemical properties of charge derivatization reagents required for efficient fragmentation remain unclear. In this study, we prepared several derivatization reagents with high proton affinity, which are thought to be appropriate for peptide fragmentation under low-energy collision-induced dissociation (CID) conditions, and examined their usefulness in de novo peptide sequencing. Comparison of the effects on fragmentation among three derivatization reagents having a guanidino or an amidino moiety, which differ in proton affinity, clearly indicated that there was an optimal proton affinity for efficient fragmentation of peptides. Among reagents tested in this study, derivatization with 4-amidinobenzoic acid brought about the most effective fragmentation. This derivatization approach will offer a novel de novo peptide sequencing method under low-energy CID conditions.     

Production of a fluorescence probe in ion-beam radiolysis of aqueous coumarin-3-carboxylic acid solution—2: Effects of nuclear fragmentation and its simulation with PHITS

The G(OH) values in aqueous coumarin-3-carboxylic-acid (3-CCA) solutions irradiated with ¹²C⁶⁺ beams having the energies of 135, 290 and 400 MeV/u were measured by a fluorescent method around the Bragg peak, with 0.6 mm intervals, and quartz cells of 1 cm optical lengths, at the Heavy Ion Medical Accelerator in Chiba, National Institute of Radiological Sciences (NIRS). For each ion, the G(OH) has been calculated as a function of dose average LET and position. The calculated results have been compared to measurements, and the results, reproducibility and reliability of the calculations are discussed in the paper.     

Temperature effect on emission spectra and fluorescence lifetime of the ~4I_(13/2) state of Er~(3+)-doped Gd_2SiO_5 crystal

By measuring the emission spectra and the fluorescence lifetime of the 4 I 13 /2 state of Er 3+ ions in Gd 2 SiO 5 crystal at different temperatures,the effects of temperature on the spectra and the lifetime of the 4 I 13 /2 state are investigated. When the temperature increases,the emission line width for the 4 I 13 /2 → 4 I 15 /2 transition is broadened,and the main emission lines at 1 596,1 609,and 1 644 nm shifte toward shorter wavelengths. The measured lifetime of the 4 I 13 /2 state decreases from 13.2 to 8.4 ms with temperature increase from 13 to 300 K,which is mainly due to the temperature dependence of multiphonon relaxation between the 4 I 13 /2 and 4 I 15 /2 states and the changing population distribution among the Stark levels within the 4 I 13 /2 state. The experimental results imply that low temperature condition is better for the ～1.6-μm laser output.     

Cover Feature: O-Acylative Vinylation of Cyclodextrin-Based [3]Rotaxane Towards Rotaxane Crosslinkers (Eur. J. Org. Chem. 12/2023)

The acylation of a cyclodextrin-based [3]rotaxane was implemented with anhydride reagents following a facile procedure. Methacrylic anhydride facilitated the introduction of a vinyl-group into the rotaxane structure toward achieving a crosslinker. Interestingly, only a few methacrylic units were attached to the cyclodextrin at reaction temperatures of up to 60 °C even with an excess amount of the reagent, probably due to steric hindrance. Therefore, the number of vinyl groups on the [3]rotaxane framework was easily controlled to be approximately two units via a simple random acylation, which worked effectively as a facile synthesis route for the rotaxane crosslinker. The acylation behavior was investigated in detail by NMR and MALDI-TOF-MS analyses. Such a proposed approach will help overcome the trade-off between convenience and utility associated with the mono-modification of cyclodextrins.