HIV-TAT Enhances the Transdermal Delivery of NSAID Drugs from Liquid Crystalline Mesophases

Sodium diclofenac (Na-DFC) and celecoxib (CLXB) are common nonsteroidal anti-inflammatory (NSAID) drugs which suffer from poor bioavailability and severe side effects when consumed orally, and their transdermal delivery might present important advantages. In this study, the drugs were solubilized in cubic and lamellar mesophases as transdermal delivery vehicles, and a cell-penetrating peptide, HIV-TAT (TAT), was examined as a skin penetration enhancer. SD-NMR, ATR-FTIR, and EPR measurements revealed that, in the cubic mesophase (which is rich in water content), TAT populates the aqueous cores and binds water, while in the dense lamellar system (with the lower water content) TAT is bound also to the glycerol monooleate (GMO) and increases the microviscosity and the order degree. TAT secondary structure in the cubic system was found to be a random coil while once it was embedded in the closely packed lamellar system it transforms to a more ordered compact state of β-turns arranged around the GMO headgroups. TAT remarkably increased the diffusion of Na-DFC and CLXB from the cubic systems by 6- and 9-fold enhancement, respectively. TAT effect on drug diffusion from the lamellar systems was limited to an increase of 1.3- and 1.7-fold, respectively. The dense packing and strong binding in the lamellar phase led to slow diffusion rates and slower drug release in controlled pattern. These effects of the chemical composition and vehicle geometry on drug diffusion are demonstrated with the impacts of TAT which can be specifically utilized for controlling skin delivery of drugs as required

Unusual Stabilization of Zinc Peroxide by Manganese Oxide: Mechanistic Understanding by Temperature-Dependent EPR Studies

Nanocrystalline zinc peroxide is passivated against further oxidation by the addition of minute, substoichiometric amounts of potassium permanganate, which also endows it with increased thermal stability. The oxidation state of manganese and the passivation mechanism are deciphered by a comparative electron paramagnetic resonance (EPR) study of the manganese-doped zinc peroxide nanoparticles and manganese oxide formed by reduction of permanganate by hydrogen peroxide as well as unmodified ZnO2 nanoparticles. Temperature-dependent in situ EPR studies at elevated temperatures allowed us to trace simultaneously the temperature-dependent changes in abundance of superoxide radicals and the formation of Mn­(IV) species and also to identify Mn­(III) species at cryotemperatures. We conclude that the passivation is caused by Mn­(III) complexes that act as antioxidants removing superoxide radicals, which are abundant in zinc peroxide and even more so in the manganese-doped zinc peroxide

Dynamic Thermodynamic Resolution of Racemic 1,1′-Binaphthyl-2,2′-diol (BINOL)

A dynamic thermodynamic resolution method for converting (R/S)-BINOL (1,1′-binaphthyl-2,2′-diol) into (R)-BINOL in 100% theoretical yield is reported. This technique involves mixing (R/S)-BINOL with N-benzyl cinchonidinium bromide (1 equiv) and a [Cu2(tmeda)2(μ-OH)2]Br2 (2.5 mol %) redox catalyst in acetonitrile. In the background of this process is the observation that the energy for atropoisomerization decreases significantly when an electron is removed from BINOL. Therefore, it is possible to convert both enantiomers into the thermodynamically favorable [N-benzyl cinchonidinium bromide·(R)-BINOL] adduct

Does Progressive Nitrogen Doping Intensify Negatively Charged Nitrogen Vacancy Emission from e‑Beam-Irradiated Ib Type High-Pressure–High-Temperature Diamonds?

Micron-sized samples of Ib type high-pressure–high-temperature diamonds synthesized with low and high substitutional nitrogen content and high energy e-beam irradiated to form luminescent negatively charged nitrogen-vacancy (NV^–) centers are studied by X-band electron paramagnetic resonance (EPR), photoluminescence (PL), and Raman techniques. High nitrogen doping leads to the appearance of paramagnetic centers characterized by strong interactions between unpaired spins of substitutional nitrogen defects. Actual concentrations of paramagnetic substitutional nitrogen and NV^– centers were obtained by EPR. The intensity of the PL emission from NV^– centers was analyzed as a function of the content of NV^– centers. We report that the NV^– PL intensity is controlled by both the content of NV^– centers and the presence of nitrogen-related crystal defects/imperfections. Increasing the nitrogen content increases the structural imperfections, which are responsible for the appearance of additional nonradiative recombination centers and significant intensification of PL quenching. It is suggested that PL intensity may be optimized by the appropriate choice of nitrogen doping and irradiation fluence

Multicopper Clusters Enable Oxidative Phenol Macrocyclization (OxPM) of Peptides

The biosynthesis of glycopeptide antibiotics such as vancomycin and other biologically active biaryl-bridged and diaryl ether-linked macrocyclic peptides includes key enzymatic oxidative phenol macrocyclization(s) of linear precursors. However, a simple and step-economical biomimetic version of this transformation remains underdeveloped. Here, we report highly efficient conditions for preparing biaryl-bridged and diaryl ether-linked macrocyclic peptides based on multicopper(II) clusters. The selective syntheses of ring models of vancomycin and the arylomycin cyclic core illustrate the potential of this technology to facilitate the assembly of complex antibiotic macrocyclic peptides, whose syntheses are considered highly challenging. The unprecedented ability of multicopper(II) clusters to chelate tethered diphenols and promote intramolecular over intermolecular coupling reactions demonstrates that copper clusters can catalyze redox transformations that cannot be accessed by smaller metal catalysts

Light-Induced Self-Assembled Polydiacetylene/Carbon Dot Functional “Honeycomb”

The design of functional supramolecular assemblies from individual molecular building blocks is a fundamental challenge in chemistry and material science. We report on the fabrication of “honeycomb” films by light-induced coassembly of diacetylene derivatives and carbon dots. Specifically, modulating noncovalent interactions between the carbon dots, macrocyclic diacetylene, and anthraquinone diacetylene facilitates formation of thin films exhibiting a long-range, uniform pore structure. We show that light irradiation at distinct wavelengths plays a key role in the assembly process and generation of unique macro-porous morphology, by both initiating interactions between the carbon dots and the anthraquinone moieties and giving rise to the topotactic polymerization of the polydiacetylene network. We further demonstrate utilization of the macro-porous film as a photocatalytic platform for water pollutant degradation and as potential supercapacitor electrodes, both applications taking advantage of the high surface area, hydrophobicity, and pore structure of the film

Light-Induced Self-Assembled Polydiacetylene/Carbon Dot Functional “Honeycomb”

The design of functional supramolecular assemblies from individual molecular building blocks is a fundamental challenge in chemistry and material science. We report on the fabrication of “honeycomb” films by light-induced coassembly of diacetylene derivatives and carbon dots. Specifically, modulating noncovalent interactions between the carbon dots, macrocyclic diacetylene, and anthraquinone diacetylene facilitates formation of thin films exhibiting a long-range, uniform pore structure. We show that light irradiation at distinct wavelengths plays a key role in the assembly process and generation of unique macro-porous morphology, by both initiating interactions between the carbon dots and the anthraquinone moieties and giving rise to the topotactic polymerization of the polydiacetylene network. We further demonstrate utilization of the macro-porous film as a photocatalytic platform for water pollutant degradation and as potential supercapacitor electrodes, both applications taking advantage of the high surface area, hydrophobicity, and pore structure of the film

Triphenyllead Hydroperoxide: A 1D Coordination Peroxo Polymer, Single-Crystal-to-Single-Crystal Disproportionation to a Superoxo/Hydroxo Complex, and Application in Catalysis

The synthesis, transformation, and application in catalysis of triphenyllead hydroperoxide, the first dioxygen lead complex, are described. Triphenyllead hydroperoxide is characterized by 207Pb nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and single-crystal X-ray diffraction, revealing the first one-dimensional (1D) coordination peroxo polymer. Photolytic isomorphous transformation of Ph3PbOOH yields a mixed hydroxo/superoxo crystalline structure, the first nonalkali superoxo crystalline metal salt, which is stable up to 100 °C. Upon further photolysis, another isomorphous transformation of the superoxide to hydroxide is observed. These are the first single-crystal-to-single-crystal hydroperoxide-to-superoxide and then to hydroxide transformations reported to date. Photolysis of triphenyllead hydroperoxide yields two forms of superoxide-doped crystalline structures that are distinguished by widely different characteristic relaxation times. The use of Ph3PbOOH as an easy-to-handle solid two-electron oxidant for the highly enantioselective epoxidation of olefins is described

Soluble Complexes of Cobalt Oxide Fragments Bring the Unique CO₂ Photoreduction Activity of a Bulk Material into the Flexible Domain of Molecular Science

The deposition of metal oxides is essential to the fabrication of numerous multicomponent solid-state devices and catalysts. However, the reproducible formation of homogeneous metal oxide films or of nanoparticle dispersions at solid interfaces remains an ongoing challenge. Here we report that molecular hexaniobate cluster anion complexes of structurally and electronically distinct fragments of cubic-spinel and monoclinic Co3O4 can serve as tractable yet well-defined functional analogues of bulk cobalt oxide. Notably, the energies of the highest-occupied and lowest-unoccupied molecular orbitals (HOMO and LUMO) of the molecular complexes, 1, closely match the valence- and conduction-band (VB and CB) energies of the parent bulk oxides. Use of 1 as a molecular analogue of the parent oxides is demonstrated by its remarkably simple deployment as a cocatalyst for direct Z-scheme reduction of CO2 by solar light and water. Namely, evaporation of an aqueous solution of 1 on TiO2-coated fluorinated tin oxide windows (TiO2/FTO), immersion in wet acetonitrile, and irradiation by simulated solar light under an atmosphere of CO2 give H2, CO, and CH4 in ratios nearly identical to those obtained using 20 nm spinel-Co3O4 nanocrystals, but 15 times more rapidly on a Co basis and more rapidly overall than other reported systems. Detailed investigation of the photocatalytic properties of 1 on TiO2/FTO includes confirmation of a direct Z-scheme charge-carrier migration pathway by in situ irradiated X-ray photoelectron spectroscopy. More generally, the findings point to a potentially important new role for coordination chemistry that bridges the conceptual divide between molecular and solid-state science