Chiral Mesoporous Silica Materials: A Review on Synthetic Strategies and Applications

Because of its tunable textural properties and chirality feature, chiral mesoporous silica (CMS) gained significant consideration in many fields and has been developed rapidly in recent years. In this review, we provide an overview of synthesis strategies for fabricating CMS together with its main applications. The properties of CMS, including morphology and mesostructures and enantiomer excess (ee), can be altered according to the synthetic conditions during the synthesis process. Despite its primary stage, CMS has attracted extensive attention in many fields. In particular, CMS nanoparticles are widely used for enantioselective resolution and adsorption of chiral compounds with desirable separation capability. Also, CMS acts as a promising candidate for the effective delivery of chiral or achiral drugs to produce a chiral-responsive manner. Moreover, CMS also plays an important role in chromatographic separations and asymmetric catalysis. There has been an in-depth review of the synthetic methods and mechanisms of CMS. And this review aims to give a deep insight into the synthesis and application of CMS, especially in recent years, and highlights the significance that it may have in the future.

Chiral recognition and enantiomer excess determination based on emission wavelength change of AIEgen rotor

Chiral recognition, such as enantioselective interactions of enzyme with chiral agents, is one of the most important issues in the natural world. But artificial chiral receptors are much less efficient than natural ones. For tackling the chiral recognition and enantiomer excess (ee) analysis, up until now all the fluorescent receptors have been developed based on fluorescence intensity changes. Here we report that the chiral recognition of a large number of chiral carboxylic acids, including chiral agrochemicals 2,4-D, is carried out based on fluorescent colour changes rather than intensity changes of AIEgen rotors. Moreover, the fluorescence wavelength of the AIEgen rotor linearly changes with ee of the carboxylic acid, enabling the ee to be accurately measured with average absolute errors (AAE) of less than 2.8%. Theoretical calculation demonstrates that the wavelength change is ascribed to the rotation of the AIEgen rotor upon interaction with different enantiomers.

Development and Validation of RP-Chiral HPLC Method for Determination of (R)-Enantiomer Excess Content in Efavirenz

simple, specific, linear, accurate and precise reverse phase chiral HPLC method was developed for the separation of efavirenz enantiomers by using the Lux Amylose-2 column containing amylose tris(5-chloro-2-methyl phenyl carbamate) as a stationary phase. The mobile phase consists of 0.1 % formic acid in water and acetonitrile (55:45, v/v). The flow rate was kept at 1.0 mL/min and the detection wavelength used 252 nm and the column temperature was set at 25 ºC. The limit of detection was 0.01 mg/mL and the limit of quantification was 0.04 mg/mL. The linearity calibration curve of (R)-enantiomer was shown well from the range of 0.04 mg/mL to 0.4 mg/mL. The values of the correlation coefficient were 0.999 and 0.999 for (R)-enantiomer and (S)-efavirenz, respectively. The percentage recoveries of (R)-enantiomer from efavirenz drug substance were ranged from 93.5% to 107.5%. The results demonstrated that developed RP-chiral HPLC method was simple, precise, robust and applicable for the estimation of (R)-enantiomer in efavirenz API. This method was validated in as per ICH Q2 (R1) and USP validation of compendial methods <1225>.

Urea-Derivative Catalyzed Enantioselective Hydroxyalkylation of Hydroxyindoles with Isatins

The enantioselective transformations of indoles preferentially take place in the more-reactive azole ring. However, the methods for the enantioselective functionalization of the indole benzene ring are scarce. In this paper, a series of bifunctional (thio)urea derivatives were used to organocatalyze the enantioselective Friedel−Crafts hydroxyalkylation of indoles with isatins. The resulting products were obtained in good yields (65–90%) with up to 94% enantiomer excess (ee). The catalyst type and the substrate scope were broadened in this methodology.

Organic molecules in meteorites

The analysis of the organic content of meteorites provides a window into the conditions of the early solar system, such as the extension of aqueous alteration or thermal metamorphism on the meteorite parent bodies. The analysis of the soluble organic content of CM chondrites indicates that extensive aqueous alteration on their meteorite parent body may result on 1) the decomposition of α-amino acids; 2) synthesis of β- and γ-amino acids; 3) higher relative abundances of alkylated polycyclic aromatic hydrocarbons (PAHs); and 4) higher L-enantiomer excess (Lee) value of isovaline. Exogenous delivery of organic matter by meteorites may have contributed to the organic inventory of the early Earth, providing a diversity of resources to the first living organisms on Earth and on other places of our solar system where life could have potentially originated.

Chiral molecule in the Standard Model

This paper is based on the talk at the conference of "Spectroscopic Studies on Molecular Chirality" held on December 20–21, 2013. The objects of the present paper are to (1) derive the energy difference between Laevorotatory, or left-handed, (L-) and Dextrorotatory, or right-handed, (D-) molecules and to (2) discuss how this tiny energy difference leads us to the observed enantiomer excess. Relations with other parity violating phenomena in molecules, electric dipole moment (EDM) and natural optical activity, are also discussed.