Matched Ligands for Small, Stable Colloidal Nanoparticles of Copper, Cuprous Oxide and Cuprous Sulfide.

This work applies organometallic routes to copper(0/I) nanoparticles and describes how to match ligand chemistries with different material compositions. The syntheses involve reacting an organo-copper precursor, mesitylcopper(I) [CuMes]z (z=4, 5), at low temperatures and in organic solvents, with hydrogen, air or hydrogen sulfide to deliver Cu, Cu2 O or Cu2 S nanoparticles. Use of sub-stoichiometric quantities of protonated ligand (pro-ligand; 0.1-0.2 equivalents vs. [CuMes]z ) allows saturation of surface coordination sites but avoids excess pro-ligand contaminating the nanoparticle solutions. The pro-ligands are nonanoic acid (HO2 CR1 ), 2-[2-(2-methoxyethoxy)ethoxy]acetic acid (HO2 CR2 ) or di(thio)nonanoic acid, (HS2 CR1 ), and are matched to the metallic, oxide or sulfide nanoparticles. Ligand exchange reactions reveal that copper(0) nanoparticles may be coordinated by carboxylate or di(thio)carboxylate ligands, but Cu2 O is preferentially coordinated by carboxylate ligands and Cu2 S by di(thio)carboxylate ligands. This work highlights the opportunities for organometallic routes to well-defined nanoparticles and the need for appropriate ligand selection.

Structural expression of bovine milk and meat factors in tissues of colorectal, lung and pancreatic cancer patients.

Chronic inflammation, linked to the presence of bovine milk and meat factors (BMMFs) and specific subsets of macrophages, results in oxygen radical synthesis and induction of mutations in DNA of actively replicating cells and replicating single stranded DNA. Cancers arising from this process have been characterized as indirect carcinogenesis by infectious agents (without persistence of genes of the agent in premalignant or cancers cells). Here, we investigate structural properties of pleomorphic vesicles, regularly identified by staining peritumor tissues of colorectal, lung and pancreatic cancer for expression of BMMF Rep. The latter represents a subgroup of BMMF1 proteins involved in replication of small single-stranded circular plasmids of BMMF, but most likely also contributing to pleomorphic vesicular structures found in the periphery of colorectal, lung and pancreatic cancers. Structurally dense regions are demonstrated in preselected areas of colorectal cancer, after staining with monoclonal antibodies against BMMF1 Rep. Similar structures were observed in human embryonic cells (HEK293TT) overexpressing Rep. These data suggest that Rep or Rep isoforms contribute to the structural formation of vesicles.

Block Poly(carbonate-ester) Ionomers as High-Performance and Recyclable Thermoplastic Elastomers.

Thermoplastic elastomers based on polyesters/carbonates have the potential to maximize recyclability, degradability and renewable resource use. However, they often underperform and suffer from the familiar trade-off between strength and extensibility. Herein, we report well-defined reprocessable poly(ester-b-carbonate-b-ester) elastomers with impressive tensile strengths (60 MPa), elasticity (>800 %) and recovery (95 %). Plus, the ester/carbonate linkages are fully degradable and enable chemical recycling. The superior performances are attributed to three features: (1) Highly entangled soft segments; (2) Fully reversible strain-induced crystallization and (3) Precisely placed ZnII -carboxylates dynamically crosslinking the hard domains. The one-pot synthesis couples controlled cyclic monomer ring-opening polymerization and alternating epoxide/anhydride ring-opening copolymerization. Efficient convresion to ionomers is achieved by reacting vinyl-epoxides to install ZnII -carboxylates.

Triplet Energy and π-Conjugation Effects on Photoisomerization of Chiral N,C-Chelate Organoborons with PAH Substituents.

Chiral, PAH substituted N,C-chelate boron compounds are systematically investigated to establish the effect of triplet energy and substitution position on their photoreactivity. They all undergo regioselective photoisomerization, forming new dark isomers with quantum efficiencies reflecting these various factors. New PAH fused 4bH-azaborepins are obtained via thermal isomerization of the dark isomers. These results further implicate a photoactive triplet state in the photoisomerization process and its utility in achieving rare PAH-fused azaborepin-like heterocycles.