Michael addition of P-nucleophiles to azoalkenes provides simple access to phosphine oxides bearing an alkylhydrazone moiety

β-Hydrazonophosphine oxides are precursors of useful organophosphorus compounds, including phosphorylated N-heterocycles, α-aminophosphonates, and vinylphosphonates. In this work, a general transition metal-free synthesis of β-hydrazonophosphine oxides was developed. The method relies on the Michael addition of phosphine oxides R2P(O)H to reactive azoalkenes (1,2-diaza-1,3-butadienes), which are generated in situ from α-halohydrazones and Hunig’s base. The reaction stereoselectively leads to Z-isomers of β-hydrazonophosphine oxides that are stabilized by intramolecular hydrogen bonding. The conversion of the products thus obtained into potential chelating ligands was showcased

Delivery and reveal of localization of upconversion luminescent microparticles and quantum dots in the skin in vivo by fractional laser microablation, multimodal imaging, and optical clearing

Delivery and spatial localization of upconversion luminescent microparticles [Y 2 O 3 ;Yb, Er] (mean size ~1.6 μm) and quantum dots (QDs) (CuInS 2 ZnS nanoparticles coated with polyethylene glycol-based amphiphilic polymer, mean size ~20 nm) inside rat skin was studied in vivo using a multimodal optical imaging approach. The particles were embedded into the skin dermis to the depth from 300 to 500 μm through microchannels performed by fractional laser microablation. Low-frequency ultrasound was applied to enhance penetration of the particles into the skin. Visualization of the particles was revealed using a combination of luminescent spectroscopy, optical coherence tomography, confocal microscopy, and histochemical analysis. Optical clearing was used to enhance the image contrast of the luminescent signal from the particles. It was demonstrated that the penetration depth of particles depends on their size, resulting in a different detection time interval (days) of the luminescent signal from microparticles and QDs inside the rat skin in vivo. We show that luminescent signal from the upconversion microparticles and QDs was detected after the particle delivery into the rat skin in vivo during eighth and fourth days, respectively. We hypothesize that the upconversion microparticles have created a long-time depot localized in the laser-created channels, as the QDs spread over the surrounding tissues

In vivo optical monitoring of transcutaneous delivery of calcium carbonate microcontainers

We have developed a method for delivery of biocompatible CaCO3 microcontainers (4.0 ± 0.8 µm) containing Fe3O4 nanoparticles (14 ± 5 nm) into skin in vivo using fractional laser microablation (FLMA) provided by a pulsed Er:YAG laser system. Six laboratory rats have been used for the microcontainer delivery and weekly monitoring implemented using an optical coherence tomography and a standard histological analysis. The use of FLMA allowed for delivery of the microcontainers to the depth about 300 μm and creation of a depot in dermis. On the seventh day we have observed the dissolving of the microcontainers and the release of nanoparticles into dermis

Resultative Compound Verb in Modern Chinese : A Comment on Imai(1985) and Lu(1986)

<p>A. API and DMO suppresses NF-κB DNA binding ability in HCT116 cells. HCT116 cells were treated with DMO and API at indicated doses, nuclear extracts were prepared, and 20 μg of the nuclear extract protein was used for the ELISA-based DNA-binding assay *p<0.05; **p<0.005). B & C. NF-κB responsive elements linked to a luciferase reporter gene were transfected with wild-type or dominant-negative IκB and transfected cancer cells were treated at indicated doses for 6 h and luciferase activity was measured as described in Materials and Methods section. All luciferase experiments were done in triplicate and repeated twice (*p<0.05; **p<0.005). D. API abrogates constitutive IκBα phosphorylation in dose-dependent manner in HCT116 cells. HCT116 cells were treated with different concentrations of API (0, 5, 10 and 20 μM) for 6 h and cytoplasmic extract was prepared. Lysates were resolved on SDS gel and electrotransferred to a nitrocellulose membrane and probed with anti-phospho-IκBα/IκBα. The blot was washed, exposed to HRP-conjugated secondary antibodies for 1 h, and finally examined by chemiluminescence. GAPDH was used as loading control.</p

Interrupted Nef and Meyer Reactions: A Growing Point for Diversity-Oriented Synthesis Based on Nitro Compounds

The Nef reaction (nitro to carbonyl group conversion) and related Meyer reaction are among the key transformations of aliphatic nitro compounds. The interrupted versions of these reactions in which the normal pathway is redirected to a different end product by an external nucleophile are much less common, albeit these processes substantially increase the synthetic potential of nitro compounds. In this review, examples of interrupted Nef and Meyer reactions are summarized, and the prospects of this methodology in diversity-oriented organic synthesis are analyzed. The bibliography contains 90 references

DataSheet1_Michael addition of P-nucleophiles to azoalkenes provides simple access to phosphine oxides bearing an alkylhydrazone moiety.pdf

β-Hydrazonophosphine oxides are precursors of useful organophosphorus compounds, including phosphorylated N-heterocycles, α-aminophosphonates, and vinylphosphonates. In this work, a general transition metal-free synthesis of β-hydrazonophosphine oxides was developed. The method relies on the Michael addition of phosphine oxides R2P(O)H to reactive azoalkenes (1,2-diaza-1,3-butadienes), which are generated in situ from α-halohydrazones and Hunig’s base. The reaction stereoselectively leads to Z-isomers of β-hydrazonophosphine oxides that are stabilized by intramolecular hydrogen bonding. The conversion of the products thus obtained into potential chelating ligands was showcased.</p

An Intramolecular Nitroso-Meerwein–Ponndorf–Verley–Oppenauer Reaction to Access Fused Pyrrolidine Scaffolds

δ-Hydroxy chloronitroso compounds generated in situ from 1,2-oxazine N-oxides undergo a 1,5-hydride transfer related to the Meerwein–Ponndorf–Verley–Oppenauer reaction. Based on the process discovered, a three-step access to fused pyrrolidine scaffolds containing up to four contiguous stereogenic centers starting from simple nitrostyrenes and cycloalkenes or cyclodienes has been developed. The suggested reaction mechanism was confirmed by in situ UV–vis and ATR FT-IR monitoring and DFT calculations