CRYSTAL STRUCTURES OF [N′-(2- OXIDOBENZYLIDENE)-N-(PROP-2-EN-1-YL)- CARBAMOHYDRAZONOTHIOATO(2-)](1,10- PHENANTHROLINE)COPPER AND [N′-(2- OXIDOBENZYLIDENE)-N-(PROP-2-EN-1-YL)- CARBAMOHYDRAZONOTHIOATO(2-)](2,2′- BIPYRIDINE)COPPER HEMIHYDRATES

Journal of Structural Chemistry - The crystal structures and biological properties of [N′-(2-oxidobenzylidene)-N-(prop-2-en-1-yl)-carbamohydrazonothioato(2-)](1,10-phenanthroline)copper...     

Macroscopic Polarization Change of Mononuclear Valence Tautomeric Cobalt Complexes Through the Use of Enantiopure Ligand

The crystallization of a complex having electron transfer properties in a polar space group can induce the polarization switching of a crystal in a specific direction, which is attractive for the development of sensors, memory devices, and capacitors. Unfortunately, the probability of crystallization in a polar space group is usually low. Noticing that enantiopure compounds crystallize in Sohncke space groups, this paper reports a strategy for the molecular design of non-ferroelectric polarization switching crystals based on the use of intramolecular electron transfer and chirality. In addition, this paper describes the synthesis of a mononuclear valence tautomeric (VT) cobalt complex bearing an enantiopure ligand. The introduction of enantiomer enables the crystallization of the complex in the polar space group (P2₁). The polarization of the crystals along the b-axis direction is not canceled out and the VT transition is accompanied by a change in the macroscopic polarization of the polar crystal. Polarization switching via electron transfer is realized at around room temperature.     

Dendritic polyurethane-based prodrug as unimolecular micelles for precise ultrasound-activated localized drug delivery

Ultrasound has been recognized as an exciting tool to enhance the therapeutic efficacy in tumor chemotherapy owing to the triggered drug release, facilitated intracellular drug delivery, and improved spatial precision. Aiming for a precise localized drug delivery, novel dendritic polyurethane-based prodrug (DOX-DPU-PEG) was fabricated with a drug content of 18.9% here by conjugating DOX onto the end groups of the functionalized dendritic polyurethane via acid-labile imine bonds. It could easily form unimolecular micelles around 38 nm. Compared with the non-covalently drug-loaded unimolecular micelles (DOX@Ph-DPU-PEG), they showed excellent pH/ultrasound dual-triggered drug release performance, with drug leakage of only 4% at pH 7.4, but cumulative release of 14% and 88% at pH 5.0 without and with ultrasound, respectively. The ultrasound responsiveness was attributed to the unique strawberry-shaped topological structure of the DOX-DPU-PEG, in which DOX was embedded in the skin layer of the hydrophobic DPU cores. With ultrasound, the DOX-DPU-PEG unimolecular micelles possessed enhanced tumor growth inhibition than free DOX but showed no obvious cytotoxicity on the tumor cells without ultrasound. Such feature makes them promising potential for precise localized drug delivery.     

Catalytic Nitrene Transfer by an FeIV-Imido Complex Generated by a Comproportionation Process

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe^II and Fe^III precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an Fe^IV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the Fe^II precursor was expected by a two-electron oxidative addition, its formation from an Fe^III precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the Fe^III precursor, an Fe^III tosyliodinane adduct was formed and decomposed into an Fe^V tosylimido species which generated the catalytically active Fe^IV tosylimide through a comproportionation process with the Fe^III precursor.     

Meniscus-Induced Thinning of Smectic Nanofilms

JETP Letters - A new mechanism of thinning of smectic nanofilms is discovered, differing from that previously described in experimental and theoretical works. The size and shape of a meniscus...     

Regularities of Structure Formation in AA2024 Alloy During High-Intensity Plastic Deformation Under Conditions of Adhesion-Diffusion Friction Interaction

Russian Physics Journal - The results of model experimental studies of structural-phase changes in an AA2024 aluminum alloy after friction with a counter-body of a complex configuration are...     

Anisotropy of Microhardness and Fracture of Langasite Crystal and Its Structural Basis

Crystallography Reports - The anisotropy of microhardness and fracture of the (0001) basal plane of langasite crystal has been studied using Berkovich indentation under a load of 100 g at different...     

Three-Dimensional Structure of Recombinant Thermophilic Ribokinase from Thermus speсies 2.9 in Complex with Adenosine Diphosphate

Crystallography Reports - The three-dimensional structure of recombinant thermophilic ribokinase from Thermus speсies 2.9 was determined at 2.4 Å resolution using crystals, which were...     

COMPENSATING ROLE OF SELF-EQUILIBRATED STRESS FIELDS IN CONSTRUCTING NON-SINGULAR SOLUTIONS USING A NON-EUCLIDEAN CONTINUUM MODEL FOR AN INCOMPRESSIBLE SPHERE

Journal of Applied Mechanics and Technical Physics - A self-equilibrated stress field for an incompressible sphere is constructed based on a non-Euclidean continuum model. The...