Oxidative Addition vs. Ligand-Exchange: Fe(II)-Mixed-Phenylchalcogenolate Complexes fac-[PPN][Fe(CO)3(TePh)n(SePh)3-N] (n = 1, 2)

Diphenyldichalcogenides (PhE)₂ (E = Te, Se) react with Fe(0)-phenylchalcogenolate [PPN] [PhEFe(CO)₄] to yield the products of oxidative addition, Fe(II)-mixed-phenylchalcogenolate fac- [PPN][Fe(CO)₃(TePh)_n(ScPh)_3-n] (n = 1, 2). Reactions of [PPN][REFe(CO)₄] (E=Se, R=Me; E=S, R=Et) and diphenyldichalcogenides yielded ligand-exchange products [PPN][PhEFe(CO)₄] (E=Te, Se, S). The compounds [Fe(CO)₃(TePh)(ScPh)₂]^? (l) and [Fe(CO)₃(TePh)₂ (2) crystallize in the isomorphous monoclinic space group C_2/e, with a = 32.035(8), b = 11.708(6), c = 28.909(6) Å, Z = 8, R = 0.048, and R_w = 0.044 (1); with a = 32.089(5), b= 11.745(2), c = 28.990(8) Å, Z = 8, R = 0.048, and R_w = 0.048 (2). The complexes 1 and 2 crystallize as discrete cations of PPN⁺ and anions of [Fe(CO)₃(TcPh)_u(ScPh)_3-n] (n=1, 2), and one half solvent molecule THF. The geometry around Fe(II) is a distorted octahedron with three carbonyl groups and three phenylchalcogenolate ligands occupying facial positions.     

Facile synthesis of monodisperse MnO nanoparticles from bulk MnO

A simple method is presented for the one-pot synthesis of monodisperse MnO nanoparticles (NPs) using bulk MnO as the starting material. In the proposed approach, bulk MnO powder is dissolved in hot oleic acid to form manganese oleate (Mn(RCOO)₂) and a decomposition process is then performed to obtain MnO NPs. The proposed method is environmentally friendly in that the only by-product is water, which can be easily distilled out. Conceptually, the synthesis method can be viewed as a controlled dissolution recrystallization process. It is shown that the size of the NPs can be controlled over the range of 6–32 nm via an appropriate specification of the precursor-to-oleic acid ratio and the reaction temperature (by the choice of an appropriate high b.p organic solvent). Finally, the size-dependent magnetic properties of three different monodisperse MnO NPs (7.7 nm, 19.4 nm and 31.7 nm) are studied. It is shown that the monodisperse MnO NPs exhibit a weak ferromagnetic behavior due to uncompensated surface spins at low temperatures.     

Antiplatelet aggregation coumarins from the leaves of Murraya omphalocarpa

Using a bioactivity-guided fractionation method, two coumarins: minumicroline acetonide (1) and epimurpaniculol senecioate (2), were isolated from the leaves of Murraya omphalocarpa Hayata (Rutaceae). Compound 1 had been previously synthesized and was now isolated from natural sources for the first time, and compound 2, possessing a negative optical rotation value, is new. The structures and their stereochemistry were fully elucidated on the basis of spectroscopic and X-ray crystallographic techniques. Both compounds 1 and 2 are active in the antiplatelet aggregation assay. Interestingly, the possible acetonide artifact 1 displayed significant antiplatelet aggregation induced not only by AA and collagen but also by platelet activating factor (PAF).     

Effects of SDS on the thermo- and pH-sensitive structural changes of the poly(acrylic acid)-based copolymer containing both poly(N-isopropylacrylamide) and monomethoxy poly(ethylene glycol) grafts in water

The effects of SDS on the structural changes of the thermally induced polymeric micelles from a graft copolymer comprising poly(acrylic acid) (PAAc) as the backbone and poly(N-isopropylacrylamide) (PNIPAAm) and monomethoxy poly(ethylene glycol) (mPEG) as the grafts in aqueous solution are studied. At low temperature, SDS micelles form via the hydrophobic association of SDS molecules with the PNIPAAm grafts at a critical aggregation concentration of SDS (cac(SDS)) much lower than its critical micelle concentration. Consequently, the critical aggregation temperature of the graft copolymer is elevated. The corresponding structure of the thermally induced polymeric micelles is characterized by an abrupt reduction in the particle size and an increased tendency toward formation of the monocore structure with a more compact and hydrophobic PNIPAAm microdomain being developed. On the other hand, upon the polymeric micelle formation at high temperature, the copolymer-bound SDS micelle structure is disrupted and the dissociated SDS molecules migrate to the core-shell interface with their alkyl chains residing in the liquidlike region of the hydrophobic PNIPAAm microdomain. The correlation between the polymeric particles and copolymer-bound micelles is further substantiated by showing the change of the colloidal particle size in response to changes in cac(SDS) via adjusting the pH of the aqueous copolymer/SDS solutions.     

Visible‐Light‐Induced [4+2] Annulation of Thiophenes and Alkynes to Construct Benzene Rings

The [4+2] annulation represents an elegant and versatile synthetic protocol for the construction of benzene rings. Herein, a strategy for visible‐light induced [4+2] annulation of thiophenes and alkynes, to afford benzene rings, is presented. Under simple and mild reaction conditions, the ready availability and structural diversity of thiophenes and alkynes permit the facile synthesis of several substituted aromatic rings. Valuable drugs and amino acids are also well tolerated. Moreover, DFT calculations explain the high regioselectivity of the reaction.     

New strategies to study the chemical nature of wine oligomeric procyanidins

Tannins represent a key element in red wine flavors, so researchers have made a lot of effort to try to understand the role of their structure in wine taste in recent decades. We report some new routes to achieve a true structure–taste relationship for the major tannins found in wine, which are procyanidins in their monomeric or oligomeric state. All these routes use synthetic standards. New advances in their synthesis and their analyses using chromatographic methods, NMR spectroscopy, and mass spectrometry to obtain more precise information about their chemical structure, including their stereochemistry and their precise degree of polymerization and galloylation, are described.     

Persistence Length of Cartilage Aggrecan Macromolecules Measured via Atomic Force Microscopy

Tapping mode atomic force microscopy (TMAFM) was employed to directly calculate the persistence length of individual fetal bovine epiphyseal and mature nasal cartilage aggrecan monomers, as well as their constituent chondroitin sulfate glycosaminoglycan chains.