Formal total synthesis of fostriecin via 1,4-asymmetric induction using cobalt-alkyne complex

The synthesis of a protected dephosphofostriecin, and thereby a formal synthesis of fostriecin, has been accomplished. Two of the four chiral centers are controlled by an external chiral auxiliary and the other two are synthesized stereoselectively, one by a novel 1,4-asymmetric induction using cobalt-alkyne complex, and the other by 1,3-asymmetric induction.     

Amphiphilic block copolymer-stabilized gold nanoparticles for aerobic oxidation of alcohols in aqueous solution

Stable Au nanoparticles in P123 aqueous solution using a simple method have been developed and the colloidal Au nanoparticles were successfully applied for the effective oxidation of various alcohols using molecular O(2) as oxidant at 30 degrees C in aqueous solution.     

Solvent, anion, and structural effects on the redox potentials and UV-visible spectral properties of mononuclear manganese corroles

A series of manganese(III) corroles were investigated as to their electrochemistry and spectroelectrochemistry in nonaqueous solvents. Up to three oxidations and one reduction were obtained for each complex depending on the solvents. The main compound discussed in this paper is the meso-substituted manganese corrole, (Mes 2PhCor)Mn, and the main points are how changes in axially coordinated anion and solvent will affect the redox potentials and UV-vis spectra of each electrogenerated species in oxidation states of Mn(III), Mn(IV), or Mn(II). The anions OAc (-), Cl (-), CN (-), and SCN (-) were found to form five-coordinate complexes with the neutral Mn(III) corrole while two OH (-) or F (-) anions were shown to bind axially in a stepwise addition to give the five- and six-coordinate complexes in nonaqueous media. In each case, complexation with one or two anionic axial ligands led to an easier oxidation and a harder reduction as compared to the uncomplexed four-coordinate species.     

Transition-Metal-Free One-Pot [3+3] Heteroannulative Coupling of Thioamides with Epichlorohydrin: Access to Diverse 1,3-Thiazinanes

An operationally simple and efficient cascade approach to access a series of 1,3-thiazinanes has been developed through intermolecular [3+3] heteroannulative coupling employing β-ketothioamide as a C1 N1S1 unit and epichlorohydrin as a C3 unit at room temperature for the first time. The reaction proceeds by nucleophilic attack of thiocarbonyl sulfur to less hindered primary carbon of oxirane followed by sequential intramolecular N-cyclization and dehydrochlorination enabling the coupling by cleavage of C−O bond and formation of two new C−S and C−N bonds in one stretch. This protocol not only avoids potential toxicity and tedious work up procedures, but also features open atmosphere, good to high yields, gram-scalability, and easy performance from inexpensive, readily available starting materials under transition-metal-free conditions. A probable mechanism for the formation of 1,3-thiazinanes has been suggested.     

Sponge-nested polymer monoliths: Versatile materials for the solid-phase extraction of bisphenols

Polymer monoliths are promising materials for sample preparation due to their high porosity, pH stability, and simple preparation. The use of melamine formaldehyde foams has been reported as an effective support to prepare highly robust silica and polymer monoliths. Herein, divinylbenzene monoliths based on a 50:50 (%, w/w) crosslinker/porogen ratio have been nested within a melamine-formaldehyde sponge, resulting in monoliths with a surface area higher than 400 m²/g. The extraction performance of these monoliths was evaluated for the extraction of endocrine-disrupting bisphenols from aqueous solutions. We evaluated for the first time the versatility of sponge-nested polymer monoliths by comparing three different extraction modes (vortex mixing, magnetic stirring, and orbital shaking). Vortex mixing showed a comparable recovery of bisphenols (39%–81%) in a shorter extraction time (30 min, instead of 2 h). In addition, the robustness of the sponge-nested polymer monoliths was demonstrated for the first time by reshaping a larger monolithic cube (0.125 cm³) into four smaller pieces (4 × 0.03125 cm³) leading to a 16%–21% increase in extraction efficiency. This effect was attributed to an increase in the effective contact area with the sample, obtaining a higher analyte extraction capacity.     

Fault‐tolerant sampled‐data mixed ℋ∞ and passivity control of stochastic systems and its application

This article addresses the problem of fault‐tolerant sampled‐data mixed and passivity control for a class of stochastic system with actuator failures, where the plant is modeled as a continuous‐time one and the control inputs are implemented as discrete‐time signals. Sufficient conditions for the reliable sampled‐data mixed and passivity performance control law is established for the considered systems by constructing an appropriate Lyapunov–Krasovskii functional together with the Newton–Leibniz formula and free‐weighting matrix technique. More precisely, linear matrix inequality based sampled‐data methodology is employed to design the mixed and passivity formation controller to reject the impact of the formation changes being treated as disturbances. Simulation studies are performed based on the flight control model to verify the stability, performance, and effectiveness of the proposed design strategy. © 2015 Wiley Periodicals, Inc. Complexity 21: 420–429, 2016     

Monochromatic Cycle Partitions in Local Edge Colorings

An edge coloring of a graph is said to be an r‐local coloring if the edges incident to any vertex are colored with at most r colors. Generalizing a result of Bessy and Thomassé, we prove that the vertex set of any 2‐locally colored complete graph may be partitioned into two disjoint monochromatic cycles of different colors. Moreover, for any natural number r, we show that the vertex set of any r‐locally colored complete graph may be partitioned into disjoint monochromatic cycles. This generalizes a result of Erd?s, Gyárfás, and Pyber.     

Highly enantioselective organocatalytic direct aldol reaction in an aqueous medium

We have demonstrated that small organic molecules 1 and 2 catalyzed the direct aldol reaction of both acyclic and cyclic ketones with different aldehydes in an excess of water/brine. Excellent enantioselectivities up to >99% and diastereoselectivities up to 99% with very good yields were obtained by using much lower catalyst loadings (0.5 mol %).     

Monitoring chemical and physical changes on sub-nanogram quantities of platinum dioxide

We have measured in real-time the chemical reaction-induced weight loss and variation in physical and mechanical properties of sub-nanogram quantities of deposits utilizing the resonance response of microcantilevers. The hydrogen reduction of sub-nanogram quantities of alpha platinum oxide deposited on micromachined silicon cantilevers and resultant weight loss, as well as the kinetics of this process, were investigated. Comparison with theory suggests that this technique could be a powerful tool to measure physical and chemical changes occurring on sub-nanogram deposits.