Chalcogeno-Morita-Baylis-Hillman Reaction of Chalcogenide-Enones with Carbonyl Compounds

Abstract

The Chalcogeno-Morita-Baylis-Hillman reaction was achieved by the reactions of 2-(methylchalcogeno)phenyl vinyl ketones with carbonyl compounds or acetals in the presence of BF₃· Et₂O. This reaction proceeds via the intramolecular Michael addition of the chalcogenide group to an enone moiety followed by the aldol reaction of the resulting chalcogenonio-enolate with an aldehyde. The reactions were worked up with triethylamine or saturated aqueous NaHCO₃ to give the α -methylene aldols (the Morita-Baylis-Hillman adducts).     

Unexpected Behavior of Diastereomeric Ions in the GasPhase: A Stimulus for Pondering on ee Measurements by ESI-MS

The most common protocols for the quantitative determination of the enantiomeric excess (ee) of raw mixtures by ESI-MS reveal inadequate in cases where the distribution of diastereomeric derivatives diverges from the ee of original solutions. This phenomenon is attributable to a matrix effect, i.e., to the stereospecific formation of high order noncovalent adducts in the ESI droplets, which alters the actual availability of the diastereomeric species under MS analysis. In this frame, the assumption of classic protocols that the ionization correction factor q is independent on the composition of the mixture submitted to analysis is questionable. An alternative methodology is presented in this paper, which is aimed at circumventing the problem by excluding any chemical derivatization of the original raw mixture. It is based on the measurement of the actual distribution of ESI-formed proton-bound diastereomeric complexes from the enantiomeric mixture through a careful analysis of their reaction kinetics with a suitable reactant.      

Excess enthalpies of binary mixtures of butylamines + propanols at 298.15 K

The molar excess enthalpies of eight systems of butylamines + propanols were determined at 298.15 K using a twin-microcalorimeter. All excess enthalpies were exothermic and large. An equilibrium constant K ₁ expressed in terms of mole fractions and standard thermodynamic properties of formation (Δ_f H, Δ_f G, Δ_f S) of 1:1 complex were evaluated by ideal mixtures of monomeric molecules and their associated complexes. Concentration dependence of the FT-Raman spectrum showed systematic changes of bands. Spectroscopic considerations based on this and ab initio calculations on molecules were performed at the Mp2/6-311G(d,p) level of theory. Interaction energies between butylamine and propanol were calculated by the supermolecular and NBO methods. The results were discussed with previous results to clarify the steric and positional effect of the amino and hydroxyl group.     

Reactions of Thiazolo[3,2-b]-1,2,4-triazolium N-Ylides with Electron-deficient Acetylenes: Novel Benzoyl Migration of Intermediary 1:1-Adducts and Michael Addition to the Acetylenes

Abstract

Reactions of thiazolo[3,2-b]-1,2,4-triazolium N-methylides with electron-deficient acetylenes gave the thiazole ring-opened products as a mixture of the E-and Z-isomers. In contrast, the N-phenacylides reacted with dimethyl acetylenedicarboxylate to give the thiobenzoates together with the thiazole ring-opened products. The mechanism for formation of these compounds is described.     

Fully automated reagent peak‐free liquid chromatography fluorescence analysis of highly polar carboxylic acids using a column‐switching system and fluorous scavenging derivatization

In this study, we combined a column‐switching system with a fluorous scavenging derivatization method to develop a fully automated reagent peak‐free LC fluorescence detection protocol for the analysis of highly polar carboxylic acids. In this method, highly polar carboxylic acids were derivatized with fluorescent 1‐pyrenemethylamine in the presence of 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide and 1‐hydroxy‐1H‐benzotriazole. Residual excess of the unreacted reagent was tagged with 2‐(perfluorooctyl)ethyl isocyanate and then removed selectively using a fluorous column‐switching system placed in front of an analytical reversed‐phase column. The signal of the fluorous‐tagged unreacted reagent was completely absent in the resulting chromatograms; therefore, it did not interfere with the quantification of each acid especially those eluted before 20 min. The detection limits (S/N = 3) for the examined acids were in the range from 4.0 to 22 fmol per injection. We have applied this method to comparative analysis of highly polar carboxylic acids in urine samples obtained from diabetes mellitus type‐II model mice and their control.     

Preparation of Molecule‐Responsive Microsized Hydrogels via Photopolymerization for Smart Microchannel Microvalves

Microdevices designed for practical environmental pollution monitoring need to detect specific pollutants such as dioxins. Bisphenol A (BPA) has been widely used as a monomer for the synthesis of polycarbonate and epoxy resins. However, the recent discovery of its high potential ability to disrupt human endocrine systems has made the development of smart systems and microdevices for its detection and removal necessary. Molecule‐responsive microsized hydrogels with β‐cycrodextrin (β‐CD) as ligands are prepared by photopolymerization using a fluorescence microscope. The molecule‐responsive micro‐hydrogels show ultra‐quick shrinkage in response to target BPA. Furthermore, the flow rate of a microchannel is autonomously regulated by the molecule‐responsive shrinking of their hydrogels as smart microvalves.

     

Dynamical study of femtosecond-laser-ablated liquid-aluminum nanoparticles using spatiotemporally resolved x-ray-absorption fine-structure spectroscopy

We study the temperature evolution of aluminum nanoparticles generated by femtosecond laser ablation with spatiotemporally resolved x-ray-absorption fine-structure spectroscopy. We successfully identify the nanoparticles based on the L-edge absorption fine structure of the ablation plume in combination with the dependence of the edge structure on the irradiation intensity and the expansion velocity of the plume. In particular, we show that the lattice temperature of the nanoparticles is estimated from the L-edge slope, and that its spatial dependence reflects the cooling of the nanoparticles during plume expansion. The results reveal that the emitted nanoparticles travel in a vacuum as a condensed liquid phase with a lattice temperature of about 2500 to 4200 K in the early stage of plume expansion.     

Intermittent transport associated with the geodesic acoustic mode near the critical gradient regime

Turbulent transport near the critical gradient in toroidal plasmas is studied based on global Landau-fluid simulations and an extended predator-prey theoretical model of ion temperature gradient turbulence. A new type of intermittent transport associated with the emission and propagation of a geodesic acoustic mode (GAM) is found near the critical gradient regime, which is referred to as GAM intermittency. The intermittency is characterized by new time scales of trigger, damping, and recursion due to GAM damping. During the recursion of intermittent bursts, stationary zonal flow increases with a slow time scale due to the accumulation of undamped residues and eventually quenches the turbulence, suggesting that a nonlinear upshift of the critical gradient, i.e., Dimits shift, is established through such a dynamical process.     

Dependences of structural and electrical properties on thickness of polycrystalline Ga-doped ZnO thin films prepared by reactive plasma deposition

Polycrystalline Ga-doped (Ga content: 4 wt%) ZnO (GZO) thin films were deposited on glass substrates at 200 C by a reactive plasma deposition with DC arc discharge technique. The dependences of structural and electrical properties of GZO films on thickness, ranging from 30 to 560 nm, were investigated. Carrier concentration, n, and Hall mobility, μ, increases with increasing film thickness below 100 nm, and then the n remains nearly constant and the μ gradually increases until the thickness reaches 560 nm. The resistivity obtained of the order of 10⁻⁴ Ω cm for these films decreases with increasing film thickness: The highest resistivity achieved is 4.4×10⁻⁴ Ω cm with n of 7.6×10²⁰ cm⁻³ and μ of 18.5 cm²/V s for GZO films with a thickness of 30 nm and the lowest one is 1.8×10⁻⁴ Ω cm with n of 1.1×10²¹ cm⁻³ and μ of 31.7 cm²/V s for the GZO film with a thickness of 560 nm. X-ray diffraction pattern for all the films shows a hexagonal wurtzite structure with its strongly preferred orientation along the c-axis. Full width at half maximum of the (002) preferred orientation diffraction peak of the films decreases with increasing film thickness below 100 nm.     

2′,4′-BNA/LNA with 9-(2-Aminoethoxy)-1,3-diaza-2-oxophenoxazine Efficiently Forms Duplexes and Has Enhanced Enzymatic Resistance**

Artificial nucleic acids are widely used in various technologies, such as nucleic acid therapeutics and DNA nanotechnologies requiring excellent duplex-forming abilities and enhanced nuclease resistance. 2′-O,4′-C-Methylene-bridged nucleic acid/locked nucleic acid (2′,4′-BNA/LNA) with 1,3-diaza-2-oxophenoxazine (BNAP ( B^H )) was previously reported. Herein, a novel B^H analogue, 2′,4′-BNA/LNA with 9-(2-aminoethoxy)-1,3-diaza-2-oxophenoxazine (G-clamp), named BNAP-AEO ( B^AEO ), was designed. The B^AEO nucleoside was successfully synthesized and incorporated into oligodeoxynucleotides (ODNs). ODNs containing B^AEO possessed up to 10⁴-, 152-, and 11-fold higher binding affinities for complementary (c) RNA than those of ODNs containing 2′-deoxycytidine ( C ), 2′,4′-BNA/LNA with 5-methylcytosine ( L ), or 2′-deoxyribonucleoside with G-clamp ( P^AEO ), respectively. Moreover, duplexes formed by ODN bearing B^AEO with cDNA and cRNA were thermally stable, even under molecular crowding conditions induced by the addition of polyethylene glycol. Furthermore, ODN bearing B^AEO was more resistant to 3′-exonuclease than ODNs with phosphorothioate linkages.