Conformational disorder of organic cations tunes the charge carrier mobility in two-dimensional organic-inorganic perovskites

The chemical nature of the organic cations governs the optoelectronic properties of two-dimensional organic-inorganic perovskites. But its mechanism is not fully understood. Here, we apply femtosecond broadband sum frequency generation vibrational spectroscopy to investigate the molecular conformation of spacer organic cations in two-dimensional organic-inorganic perovskite films and establish a correlation among the conformation of the organic cations, the charge carrier mobility, and broadband emission. Our study indicates that both the mobility and broadband emission show strong dependence on the molecular conformational order of organic cations. The gauche defect and local chain distortion of organic cations are the structural origin of the in-plane mobility reduction and broad emission in two-dimensional organic-inorganic perovskites. Both of the interlayer distance and the conformational order of the organic cations affect the out-of-plane mobility. This work provides molecular-level understanding of the conformation of organic cations in optimizing the optoelectronic properties of two-dimensional organic-inorganic perovskites.

Lipid Conformational Order and the Etiology of Cataract and Dry Eye

Lens and tear film lipids are as unique as the systems they reside in. The major lipid of the human lens is dihydrosphingomylein, found in quantity only in the lens. The lens contains a cholesterol to phospholipid molar ratio as high as 10:1, more than anywhere in the body. Lens lipids contribute to maintaining lens clarity, and alterations in lens lipid composition due to age are likely to contribute to cataract. Lens lipid composition reflects adaptations to the unique characteristics of the lens: no turnover of lens lipids or proteins; the lowest amount of oxygen than any other tissue and contains almost no intracellular organelles. The tear film lipid layer (TFLL) is also unique. The TFLL is a thin, 100 nm layer of lipid on the surface of tears covering the cornea that contributes to tear film stability. The major lipids of the TFLL are wax esters and cholesterol esters that are not found in the lens. The hydrocarbon chains associated with the esters are longer than those found anywhere in the body, as long as 32 carbons, and many are branched. Changes in the composition and structure of the 30,000 different moieties of TFLL contribute to the instability of tears. The focus of the current review is how spectroscopy has been used to elucidate the relationships between lipid composition, conformational order and function and the etiology of cataract and dry eye.

Sum-Frequency Generation Vibrational Spectroscopy Investigations of Phosphonic Acids on Anodic Aluminum Oxide Films

Self-assembled monolayers of alkyl phosphonic acids on anodic aluminum oxide (AlOx) surfaces are important as dielectric layers in thin film electronic devices. Assessing the properties and quality of these monolayers on amorphous AlOx is limited to a few surface-sensitive methods. In this work, we study using nonlinear optical measurements the molecular ordering in n-alkyl phosphonic acids with various alkyl chain lengths (6 to 18 carbons) deposited on AlOx and show the influence of temperature on stability and conformational order. The results demonstrate that the octadecylphosphonic acid has fewest defects in the chain orientation. A detailed comparison of the longest and the shortest alkyl chain revealed different behavior in conformational ordering upon annealing.

Water soluble hydrophobic peptoids via a minor backbone modification

The incorporation of piperazine or homopiperazine within hydrophobic peptoid scaffolds leads to their water solubility while increasing their overall conformational order in water.

Comparison of hydration behavior and conformational preferences of the Trp-cage mini-protein in different rigid-body water models

Trp-cage unfolds at different temperatures in different water models revealing the sensitivity of conformational order metrics to the choice of water models.