Comprehensive Characterization of Organic Light-Emitting Materials in Breast Milk by Target and Suspect Screening.

Organic light-emitting materials (OLEMs) are emerging contaminants in the environment and have been detected in various environment samples. However, limited information is available regarding their contamination within the human body. Here, we developed a novel QuEChERS (quick, easy, cheap, effective, rugged, and safe) method coupled with triple quadrupole/high-resolution mass spectrometry to determine OLEMs in breast milk samples, employing both target and suspect screening strategies. Our analysis uncovered the presence of seven out of the 39 targeted OLEMs in breast milk samples, comprising five liquid crystal monomers and two OLEMs commonly used in organic light-emitting diode displays. The cumulative concentrations of the seven OLEMs in each breast milk sample ranged from ND to 1.67 × 103 ng/g lipid weight, with a mean and median concentration of 78.76 and 0.71 ng/g lipid weight, respectively, which were higher compared to that of typical organic pollutants such as polychlorinated biphenyls and polybrominated diphenyl ethers. We calculated the estimated daily intake (EDI) rates of OLEMs for infants aged 0-12 months, and the mean EDI rates during lactation were estimated to range from 30.37 to 54.89 ng/kg bw/day. Employing a suspect screening approach, we additionally identified 66 potential OLEMs, and two of them, cholesteryl hydrogen phthalate and cholesteryl benzoate, were further confirmed using pure reference standards. These two substances belong to cholesteric liquid crystal materials and raise concerns about potential endocrine-disrupting effects, as indicated by in silico predictive models. Overall, our present study established a robust method for the identification of OLEMs in breast milk samples, shedding light on their presence in the human body. These findings indicate human exposure to OLEMs that should be further investigated, including their health risks.

Recent progress for chiral stationary phases based on chiral porous materials in high-performance liquid chromatography and gas chromatography separation.

Chirality is a fundamental property of nature. Separation and analysis of racemates are of great importance in the fields of medicine and the production of chiral biopharmaceutical intermediates. Chiral chromatography has the characteristics of a wide separation range, fast separation speed, and high efficiency. The development and preparation of novel chiral stationary phases with good chiral recognition and separation capacity is the core and key of chiral chromatographic separation and analysis. In this work, the representative research progress of novel chiral porous crystal materials including chiral covalent organic frameworks, chiral porous organic cages, chiral metal-organic frameworks, and chiral metal-organic cages used as chiral stationary phases of capillary gas chromatography and high-performance liquid chromatography over the last 4 years is reviewed in detail. The chiral recognition and separation properties of the representative studies in this review are also introduced and discussed.

Tröger's Base-Based Cuboid Constructed by Chiral Self-Discrimination.

Cuboid, a basic geometric structure, has been widely applied in architecture and mathematics. In chemistry, the introduction of cuboid structures always provides a specific structural shape, enhances the stability of the structure and improves the performance of materials. Herein, a simple strategy exploiting self-discrimination to construct a cuboid-stacking crystal material is proposed, in which a chiral macrocycle (TBBP) based on Tröger's base (TB) and benzophenone (BP) was synthesized as the building element of the cuboid. The cuboid is designed to be transformable compared with cuboid structures in previous work. For this reason, it is considered that the cuboid-stacking structure can be transformed through external stimulation. Iodine vapor is selected as the external stimulus to transform the cuboid-stacking structure due to the favorable interaction between iodine and the cuboid. The changes in the stacking mode of TBBP is studied by single-crystal X-ray diffraction (SCXRD) and powder X-ray diffraction (PXRD). To our surprise, this Tröger's base-based cuboid shows strong iodine adsorption capacity up to 3.43 g g-1 and exhibits potential as a crystal material for iodine adsorption.

Performance of quartz- and sapphire-based double-crystal high-resolution (∼10 meV) RIXS monochromators under varying power loads.

In the context of a novel, high-resolution resonant inelastic X-ray scattering spectrometer, a flat-crystal-based quartz analyzer system has recently been demonstrated to provide an unprecedented intrinsic-energy resolution of 3.9 meV at the Ir L3 absorption edge (11.215 keV) [Kim et al. (2018) Sci. Rep. 8, 1958]. However, the overall instrument resolution was limited to 9.7 meV because of an 8.9 meV incident band pass, generated by the available high-resolution four-bounce Si(844) monochromator. In order to better match the potent resolving power of the novel analyzer with the energy band pass of the incident beam, a quartz(309)-based double-bounce, high-resolution monochromator was designed and implemented, expected to yield an overall instrument resolution of 6.0 meV. The choice of lower-symmetry quartz is very attractive because of its wealth of suitable near-backscattering reflections. However, it was found that during room-temperature operation typical levels of incident power, barely affecting the Si monochromator, caused substantial thermal distortions in the first crystal of the quartz monochromator, rendering it practically unusable. Finite-element analyses and heat-flow analyses corroborate this finding. As a high-flux, lower resolution (15.8 meV) alternative, a two-bounce sapphire(078) version was also tested and found to be less affected than quartz, but notably more than silicon.

Crystal structure prediction of materials with high symmetry using differential evolution.

Crystal structure determines properties of materials. With the crystal structure of a chemical substance, many physical and chemical properties can be predicted by first-principles calculations or machine learning models. Since it is relatively easy to generate a hypothetical chemically valid formula, crystal structure prediction becomes an important method for discovering new materials. In our previous work, we proposed a contact map-based crystal structure prediction method, which uses global optimization algorithms such as genetic algorithms to maximize the match between the contact map of the predicted structure and the contact map of the real crystal structure to search for the coordinates at the Wyckoff positions (WP), demonstrating that known geometric constraints (such as the contact map of the crystal structure) help the crystal structure reconstruction. However, when predicting the crystal structure with high symmetry, we found that the global optimization algorithm has difficulty to find an effective combination of WP that satisfies the chemical formula, which is mainly caused by the inconsistency between the dimensionality of the contact map of the predicted crystal structure and the dimensionality of the contact map of the target crystal structure. This makes it challenging to predict the crystal structures of high-symmetry crystals. In order to solve this problem, here we propose to use PyXtal to generate and filter random crystal structures with given symmetry constraints based on the information such as chemical formulas and space groups. With contact map as the optimization goal, we use differential evolution algorithms to search for non-special coordinates at the WP to realize the structure prediction of high-symmetry crystal materials. Our experimental results show that our proposed algorithm CMCrystalHS can effectively solve the problem of inconsistent contact map dimensions and predict the crystal structures with high symmetry.

Infrared and Raman spectroscopy study of Si1-xGexO2 solid solutions with α-quartz structures.

Single crystals of α-quartz-type Si1-xGexO2 (x < 0.12), grown under hydrothermal conditions in NH4F solutions, were investigated using infrared (IR) and Raman spectroscopy. Compositional dependencies of the IR absorption spectra were found both for the fundamental and combination vibrations. With an increase in Ge content in the crystals, new absorption bands, corresponding to the vibrations of OGeO in the GeO4 tetrahedra (670, 930, 1010, 2125 cm-1), appeared, and the intensities of the absorption bands of OSiO in the SiO4 tetrahedra (263, 695, 2137, doublet at 2326 and 2333, 2499, 2599, 2673 cm-1) decreased. The shifts in the absorption bands at 354, 511, 2499 and 2673 cm-1 to lower wavenumbers linearly depends on the Ge content and are characteristic of vibrations in the SiOGe chains. The origin of some combinational vibrations is also clarified. A combination vibration that caused the band at 1395 cm-1 was formed by vibrations with wavenumbers of 263 (type E) and 1170 cm-1 (type E). The bands at 2499 and 2673 cm-1 were composed of the band at 354 cm-1 and two vibrations at 1083 cm-1 (type E) and by two vibrations at 1170 cm-1 (type E), respectively.

Preparation of Luminescent Thermotropic Liquid Crystal from Benzodiathiazole Derivatives.

Luminescent liquid crystal materials (LLCMs) have been a hot research topic in the field of fluorescent materials. In this study, we successfully designed and synthesized an intense fluorescence thermotropic liquid crystal material with a fluorescence quantum yield (Φ) of 0.26 in the solid state. Moreover, the alkyl chain attached to the terminus of the chromophore was able to promote the stability of electrochemical and thermal properties, which was beneficial to the device fabrication reproducibility and stability of the device performance.