Meridional (mer) coordination promotes the generation of larger and lower-symmetry prismatic metallosupramolecular structures, in contrast with the facial (fac) coordination common to smaller and higher-symmetry polyhedra. Here, we describe a general route to the selective formation of large metallosupramolecular prisms that contain exclusively mer-coordinated metal vertices. The use of 2-formylpyridine subcomponents that contain perfluorophenylene substituents at their 5-positions resulted in stereoselective formation of the iron(II) complexes from these subcomponents. Only mer vertices were observed, as opposed to the statistical fac/mer mixture otherwise generated. This mer-selective self-assembly could be used to prepare tetragonal (M8L12), pentagonal (M10L15), and hexagonal (M12L18) prisms by taking advantage of the subtle selectivities imposed by the different anilines and counterions employed. The equilibrium between the tetragonal and pentagonal prism followed a linear free-energy relationship, with the ratio between structures correlating with the Hammett σp(+) parameter of the incorporated aniline. The contrasting preferences of the fluorinated and nonfluorinated ligands to generate prisms and tetrahedra, respectively, were quantified energetically, with the destabilization increasing linearly for each "incorrect ligand" incorporated into either structure.
A new method has been developed for ttw svntlwsis of 2-phenylproline and its derivatives by intramolecular cw'lization of the corresponding derivatives of N-(3-cldoro-or l-o.to-3-chloropropyl)-c~-phenylglycine under phase transfer catalysis conditions.
In this paper, the ZnO<La> target was synthesized by the solid-state reaction method and a nanostructured thin film was deposited by the RF (radio frequency) magnetron sputtering method on a Multi-Sensor-Platform. The obtained ZnO<La> nanostructured film was investigated as the sensing material. Energy-Dispersive X-ray (EDX) analysis indicated the existence of La in the synthesized ZnO<La> material. Scanning Electron Microscope (SEM) images of the film showed the grain sizes in the range of 20–40 nm. Sensor performance characteristics such as a dynamic response, response and recovery times, and ethanol detection range were investigated at 50–300 °C. A sensitivity was observed at extremely low concentrations of ethanol (0.7 ppm). The minimum response and recovery times of the sensor corresponding to 675 ppm ethanol vapor concentration at 250 °C were found to be 14 s and 61 s, respectively. The sensor showed a high response, good selectivity, fast response/recovery behavior, excellent repeatability toward ethanol vapor, and low sensitivity toward humidity. These characteristics enable the use of a ZnO<La> based sensor for ethanol detecting applications.
Light can effectively interrogate biological systems providing control over complex cellular processes. Particularly advantageous features of photo-induced processes are reversibility, physiological compatibility, and spatiotemporal precision. Understanding the underlying biophysics of light-triggered changes in bio-systems is crucial for cell viability and optimizing clinical applications of photo-induced processes in biotechnology, optogenetics and photopharmacology. Employing membranes doped with the photolipid azobenzene-phosphatidylcholine (azo-PC), we provide a holistic picture of light-triggered changes in membrane morphology, mechanics and dynamics. We combine microscopy of giant vesicles as minimal cell models, Langmuir monolayers, and molecular dynamics simulations. We employ giant vesicle elelctrodeformation as a facile and accurate approach to quantify the magnitude, reversibility and kinetics of light-induced area expansion/shrinkage as a result of azo-PC photoisomerization and content. Area increase as high as ~25% and a 10-fold decrease in the membrane bending rigidity is observed upon trans-to-cis azo-PC isomerization. These results are in excellent agreement with simulations data and monolayers. Simulations also show that trans-to-cis isomerization of azo-PC decreases the membrane leaflet coupling. We demonstrate that light can be used to finely manipulate the shape and mechanics of photolipid-doped minimal cell models and liposomal drug carriers, thus, presenting a promising therapeutic alternative for the repair of cellular disorders.
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