A practical and scalable process to selectively monofunctionalize water-soluble α,ω-diols

A practical protocol for rapid and scalable synthesis of monofunctionalized α,ω-diols using a simple and inexpensive THP ether protection/deprotection strategy was described. Use of inexpensive DHP source and ease to remove excess water-soluble α,ω-diols and THP ether after deprotection render the process scale-friendly without need of column chromatographic separation. The application of present method was also illustrated in the preparation of heterobifunctional diols and well-defined extended oligo(ethylene glycol).     

Upper-lower solutions for nonlinear parabolic systems and their applications

The method of upper-lower solutions for nonlinear parabolic systems without the assumption of quasi-monotonicity is obtained. An application is provided, by using the method developed in this paper, involving the existence of positive solutions to certain time-dependent interaction systems arising in biological and medical sciences. Furthermore, the existence of the ω-limit of given system is studied.     

Effect of Oxyethylete Units on Adsorption and Micellization Properties of Novel Benzene Sulfonate Surfactants

The surface tension and fluorescence spectra of sodium octyl-[ω-octyloxy-poly(oxyethylene)]-yl-benzene sulfonates (APE_nBS) aqueous solutions have been investigated by Wilhelmy plate method and intrinsic probe methods, respectively to study the effect of EO units on their properties. It was discovered that the surface performance of these surfactants was greatly outstanding: the values of critical micelle concentration (CMC) reached to be of the order of magnitude of 10^?5 mol/L, the values of surface tension at CMC, γ_CMC, were between 25.79 to 31.02 mN/m, and the effectiveness and efficiency of surface tension reduction were excellent. The introduction of oxyethylene units to the surfactant molecule evidently improved the solubility of APE_nBS. With the increase in EO units, the CMC slightly changed after the first decreased. On the other hand, the surface excess concentration at saturation, Γ _max, decreased after the first increased and γ_CMC increased after the first decreased accordingly. The CMC determined by fluorescence spectra of intrinsic probe method were accorded with the CMC measured by surface tension method. The aggregation number N, characterized by quenching the fluorescence spectra with methyl viologen (MV²⁺) as the extrinsic quencher, gradually decreased first (from 0 to1) and then slightly changed (from 1 to 4) with increasing EO chain length. So we concluded that the appropriate number of EO units was the key factor to get the best physicochemical properties of APE_nBS.     

Use of an Internal Keto-Imino Compound as the Photoinitiator in the Polymerization of Methyl Methacrylate

Photopolymerization of MMA in visible light was studied at 40°C using acridone as the photoinitiator. The polymerization was found to proceed via a free radical mechanism and the radical generation process was considered to follow an initial complexation reaction between monomer and acridone. Kinetic data indicated a lower order dependence of R_p on the initiator concentration (initiator exponent < 0.5). Initiator-dependent chain termination was significant along with the usual bimolecular mode of chain termination. The monomer exponent varied from about 1.0 to 1.5, depending on the nature of the solvent used. The nonidealities in this case were also analyzed.     

Unexpected selective monoadduct formation from 2-methyl-3-butyn-2-ol and α,ω-diiodoperfluorobutane

Radical chain addition of α,ω-diiodoperfluorobutane to 2-methyl-3-buten-2-ol and 2-methyl-3-butyn-2-ol has been studied. The Huang sulfinatodehalogenation system, used as initiator, gave satisfactory conversion yields of the starting diiodide when compared to more classical initiators (AIBN, Fe, triethylborane). Addition to the alkenol yields classically the bis-adduct with variable amounts of the monoadduct. On the contrary the alkynol leads exclusively to the monoadduct formation, in high yield. Some considerations are proposed for interpreting this result. The monoadduct selectively obtained constitutes a powerful intermediate for synthesis.     

Transforming Inert Cycloalkanes into α,ω-Diamines by Designed Enzymatic Cascade Catalysis

Aliphatic α,ω-diamines (DAs) are important monomer precursors that are industrially produced by energy-intensive, multistage chemical reactions that are harmful to the environment. Therefore, the development of sustainable green DA synthetic routes is highly desired. Herein, we report an efficient one-pot in vivo biocatalytic cascade for the transformation of cycloalkanes into DAs with the aid of advanced techniques, including the RetroBioCat tool for biocatalytic route design, enzyme mining for finding appropriate enzymes and microbial consortia construction for efficient pathway assembly. As a result, DAs were successfully produced by the designed microbial consortia-based biocatalytic system. In particular, the highest biosynthesis productivity record of 1,6-hexanediamine was achieved when using either cyclohexanol or cyclohexane as a substrate. Thus, the developed biocatalytic process provides a promising alternative to the dominant industrial process for manufacturing DAs.     

Reflexivity of prodiscrete topological groups

We study the duality properties of two rather different classes of subgroups of direct products of discrete groups (protodiscrete groups): P-groups, i.e., topological groups such that countable intersections of its open subsets are open, and protodiscrete groups of countable pseudocharacter (topological groups in which the identity is the intersection of countably many open sets). It was recently shown by the same authors that the direct product Π of an arbitrary family of discrete Abelian groups becomes reflexive when endowed with the ω-box topology. This was the first example of a non-discrete reflexive P-group. Here we present a considerable generalization of this theorem and show that every product of feathered (equivalently, almost metrizable) Abelian groups equipped with the P-modified topology is reflexive. In particular, every locally compact Abelian group with the P-modified topology is reflexive. We also examine the reflexivity of dense subgroups of products Π with the P-modified topology and obtain the first examples of non-complete reflexive P-groups. We find as well that the better behaved class of prodiscrete groups (complete protodiscrete groups) of countable pseudocharacter contains non-reflexive members—any uncountable bounded torsion Abelian group G of cardinality ω² supports a topology τ such that (G,τ) is a non-reflexive prodiscrete group of countable pseudocharacter.     

Copolymers derived from rapeseed derivatives via ADMET and thiol-ene addition

Novel (co)polymers were synthesized from substances obtained from rapeseed via ADMET and thiol-ene additions. α,ω-Dienes derived from oleic and erucic acid were copolymerized with a ferulic acid derivative, a representative phenolic acid (p-hydroxycinnamic acid) present, for instance, in rapeseed cake. Copolymers with different ratios of these monomers were prepared via two different routes (ADMET and thiol-ene) and studied in detail. Both monomer and polymer synthesis were optimized in order to achieve high yielding synthetic procedures that meet the requirements of green chemistry. Some thermal properties of the resulting copolymer series were then studied and correlated to the co-monomer composition.