Structural, Electronic, Reactivity, and Conformational Features of 2,5,5-Trimethyl-1,3,2-diheterophosphinane-2-sulfide, and Its Derivatives: DFT, MEP, and NBO Calculations.

In this study, we used density functional theory (DFT) and natural bond orbital (NBO) analysis to determine the structural, electronic, reactivity, and conformational features of 2,5,5-trimethyl-1,3,2-di-heteroatom (X) phosphinane-2-sulfide derivatives (X = O (compound 1), S (compound 2), and Se (compound 3)). We discovered that the features improve dramatically at 6-31G** and B3LYP/6-311+G** levels. The level of theory for the molecular structure was optimized first, followed by the frontier molecular orbital theory development to assess molecular stability and reactivity. Molecular orbital calculations, such as the HOMO-LUMO energy gap and the mapping of molecular electrostatic potential surfaces (MEP), were performed similarly to DFT calculations. In addition, the electrostatic potential of the molecule was used to map the electron density on a surface. In addition to revealing molecules' size and shape distribution, this study also shows the sites on the surface where molecules are most chemically reactive.

Intrinsic Dual-State Emission Zinc-Based MOF Rodlike Nanostructures with Applications in Smartphone Readout Visual-Based Detection for Tetracycline: MOF-Based Color Tonality.

Dual-state emitters (DSEs) are entities that exhibit fluorescence in both the solution and solid state, which open up a wide range of possibilities for their utilization in various fields. The development of detection platforms using intrinsic luminescent metal-organic frameworks (LMOFs) is highly desirable for a variety of applications. DSE MOFs as a subclass of intrinsic LMOFs are highly attractive due to no need for encapsulation/functionalization by fluorophores and/or using luminescent linkers. Herein, a highly stable intrinsic dual-state blue emission (λem = 425 nm) zinc-based MOF with rodlike nanostructures (denoted as UoZ-2) was synthesized and characterized. To the best of our knowledge, intrinsic DSE of Zn-MOFs with blue emission in the dispersed form in solution and solid-state fluorescence have not been reported yet. When tetracycline (TC) was added, a continuous color evolution from blue to greenish-yellow with dramatic enhancement was observed due to aggregation induced emission (AIE). Thus, a sensitive ratiometry-based visual detection platform, in solution and on paper independently, was designed for detection of TC exploiting the DSE and AIE properties of UoZ-2 alone and UoZ-2:TC. The detection limit was estimated to be 4.5 nM, which is considered to be one of the most sensitive ratiometric fluorescent probes for TC sensing. The ratiometry paper-based UoZ-2 sensor displays a reliable TC quantitative analysis by recognizing RGB values in the on-site TC detection with satisfactory recoveries.

Electrochemically Induced Mesomorphism Switching in a Chlorpromazine Hydrochloride Lyotropic Liquid Crystal.

The discovery of electrochemical switching of the Lα phase of chlorpromazine hydrochloride in water is reported. The phase is characterized using polarizing microscopy, X-ray scattering, rheological measurements, and microelectrode voltammetry. Fast, heterogeneous oxidation of the lyotropic liquid crystal is shown to cause a phase change resulting from the disordering of the structural order in a stepwise process. The underlying molecular dynamics is considered to be a cooperative effect of both increasing electrostatic interactions and an unfolding of the monomers from "butterfly"-shaped in the reduced form to planar in the oxidized form.