Addition of anions derived from dialkyl methylphosphonates to (Ss)-N-tert-butanesulfinyl (3,3,3)-trifluoroacetaldimine afforded (Ss,R) addition adducts in moderate to good yield (53–75%) with excellent diastereoselectivity (94–95% de). After selective removal of the N-sulfinyl group, dipeptides containing enantiomerically pure diethyl 2-amino-3,3,3-trifluoropropylphosphonate were synthesized to investigate the influence of the trifluoromethyl substituent on N-terminal coupling.

Accurate full dimensional quantum dynamics calculations studying the photodissociation of CH₃[email protected][4]arene on an ab initio based potential energy surface (PES) model are reported. The converged 189D quantum dynamics calculations are facilitated by the multilayer multi-configurational time-dependent Hartree (ML-MCTDH) approach combined with the correlation discrete variable representation (CDVR) for the evaluation of potential energy matrix elements. The potential employed combines an established ab initio PES describing the photodissociation of methyl iodide in the A band with a harmonic description of the resorc[4]arene host and a bilinear modeling of the host-guest interaction. All potential parameters required in the description of the vibrations of the host molecule and the host-guest interaction are derived from ab initio calculations on the host-guest complex. Absorption spectra at $0\text{K}$ and $300\text{K}$ are calculated and the electronic population dynamics during the bond breaking process occurring in the first 20–30 fs after the photoexcitation is investigated. Weak but significant effects resulting from the host-guest interaction on this time scale are found and interpreted. The present study demonstrates that accurate fully quantum mechanical dynamics calculations can be preformed for systems consisting of more than 50 atoms using the ML-MCTDH/CDVR approach. Utilizing an efficient statistical approach for the construction of the ensemble of initial wavepackets, these calculations are not restricted to zero temperature but can also study the dynamics at 300 K.

This work was conducted to study the chemical composition, antioxidant, antibacterial, and antifungal activities of essential oil and hydrolat from Withania frutescens. The essential oil was extracted by hydrodistillation. The chemical characterization was performed using gas chromatography-mass spectrometry (GC/MS). The antioxidant activity was studied using four different assays (DPPH, TAC, FRAP, and β-carotene bleaching). The antibacterial activity test was carried out on multidrug-resistant bacteria including Gram-negative and Gram-positive strains. Antifungal activity was tested on Candida albicans and Saccharomyces cerevisiae. The yield of essential oil (EO) obtained by hydrodistillation of W. frutescens was 0.31% majorly composed of camphor, α-thujone, carvacrol, and thymol. Regarding the antioxidant activities, the concentration of the sample required to inhibit 50% of radicals (IC₅₀) of EO and hydrolat were 14.031 ± 0.012 and 232.081 ± 3.047 µg/mL (DPPH), 4.618 ± 0.045 and 8.997 ± 0.147 µg/mL (FRAP), 0.091 ± 0.007 and 0.131 ± 0.004 mg AAE/mg (TAC), 74.141 ± 1.040% and 40.850 ± 0.083% (β-carotene), respectively. Concerning the antibacterial activity of essential oil and hydrolat, the minimum inhibitory concentration (MIC) values found were 0.006 ± 0.001 and 6.125 ± 0.541 µg/mL (Escherichia coli 57), 0.003 ± 0.001 and 6.125 ± 0.068 µg/mL (Klebsiella pneumoniae), 0.001 ± 0.0 and 6.125 ± 0.046 µg/mL (Pseudomonas aeruginosa) and 0.012 ± 0.003 and 6.125 ± 0.571 µg/mL (Staphylococcus aureus), respectively. MIC values of essential oil and hydrolat vs. both C. albicans and S. cerevisiae were lower than 1/20,480 µg/mL. Based on the findings obtained, essential oils of Withania frutescens can be used as promising natural agents to fight free radical damage and nosocomial antibiotic-resistant microbes.