Thiophenium-ylides: Synthesis and reactivity

The reaction of propanedioic acid, 2-diazo-1,3-bis(1,1-dimethylethyl) ester (di-tert-butyl diazomalonate) with a series of cyclopenta[b]thiophenes in the presence of catalytic rhodium acetate was studied. The resulting S—C ylides underwent a rearrangement to form a heterocycle with different topology; thialene, in very low yields. Experimental and spectral data for all compounds are provided.     

Palladium-catalysed Claisen rearrangement of 6-allyloxypurines

6-Allyloxypurines readily undergo palladium-catalysed Claisen rearrangement under mild conditions affording N ¹-substituted hypoxanthines. In contrast with the previously reported protocol, the Claisen rearrangement can be performed using Pd(PPh₃)₄ or Pd(dba)₂/dppf in dry THF at 60°C. The reaction can accommodate variously substituted allyl fragments to position N ¹ of the hypoxanthine skeleton with high yields. Retention of the double bond configuration during rearrangement was observed.     

Applicability of photochemically generated pendant benzoyl peroxides in both “grafting from” and “grafting to” techniques

Methyl methacrylate and styrene copolymers containing pendant benzil groups, such as 1-[4-(2-methacroyloxyethoxy)phenyl]-2-phenyl-1,2-ethanedione-co-methyl metacrylate (BzMA/MMA), 1-[4-(2-methacroyloxyethoxy)phenyl]-2-phenyl-1,2-ethanedione-co-styrene (BzMA/S), and 1-phenyl-2-(4-propenoylphenyl)-1,2-ethanedione-co-styrene (PCOCO/S), were prepared and used as precursors for photochemically generated pendant benzoyl peroxides. Decomposition of the pendant benzoyl peroxides was subsequently used in grafting processes. Either irradiation or a combination of irradiation with subsequent thermal treatment was adopted for grafting a thin layer of BzMA/MMA copolymer onto the surface of LDPE films. The grafting resulted in a significant decrease in contact angle of the film surface. The same activation strategy was successfully adopted to initiate the polymerisation of acrylic or methacrylic acids from the surface of styrene copolymer films containing the initiator precursor in the polymer side chains (BzMA/S and PCOCO/S). The successful surface grafting was proved by contact angles measurement as well as by infrared spectroscopic analysis.     

Spectral characterisation of new organic fluorescent dyes with an alkoxysilane moiety and their utilisation for the labelling of layered silicates

New fluorescence dyes with an alkoxysilane moiety were synthesised by the condensation of 3-(triethoxysilyl)-1-propanamine (3-aminopropyltriethoxysilane) with 4,10-benzothioxanthene-3,1′-dicarboxylic acid anhydride (BTXA) and N,N-dimethylaminonaphthalene-1,8-dicarboxylic acid anhydride (DMANA), which was accompanied by the formation of an imidic bridge. The compounds N-(3-(triethoxysilyl)propyl)-thioxantheno[2,1,9-dej]isoquinoline-1,3-dione (BTX-S) and 4-(N′, N′-dimethyl)-N-(triethoxysilyl)propyl-1,8-naphthalene dicarboxylic acid imide (DMAN-S) were characterised by steady-state and time-resolved fluorescence spectroscopy in chloroform and ethanol. Both conjugates (BTX-S and DMAN-S) exhibited absorption and emission bands in the same region as the un-substituted BTXA and DMANA. An important Stokes shift was observed for DMAN-S in ethanol. A high fluorescence quantum yield was observed for BTX-S in both solvents and for DMAN-S in chloroform. In addition, the newly developed fluorescent silane dyes were covalently attached to the microscopic particles of layered silicates and on the surface of SiO₂ wafers as a proof of concept for fluorescence particle (surface) visualisation. The surface wafer modification was precisely characterised by X-ray photoelectron spectroscopy (XPS). Successful covalent linkage onto the particles of layered silicates was proved by confocal laser scanning microscopy technique.     

Synthesis and properties of macrocyclic diazene switch with binaphthalene unit attached via acrylamide linkers

2,2′-Diiodo-1,1′-binaphthalene undergoes a tandem Heck reaction with methyl acrylate to afford methyl 2-(7H-dibenzo[c,g]fluoren-7-ylidene)acetate. As a consequence, the target macrocyclic diazene with binaphthalene unit attached via acrylamide linker was prepared by the stepwise building of acrylamide at a binaphthalene moiety, including the Doebner modification of the Knoevenagel condensation, and completed by oxidative macrocyclisation of aniline end-groups. Despite being an equimolar mixture of monomer and dimer, it exhibited remarkable changes in CD spectra due to reversible (E/Z) isomerisation of N=N diazene bonds upon irradiation at 365/465 nm. Although the dimer isomerises from (E) to (Z) isomer 7.4 times faster than the monomer, the latter’s contribution to the change in ellipticity at 307 nm in the photostationary state is 2.4 times greater.     

Biologically Active 1-Aminodeoxy and 1-O-Alkyl Derivatives of The Powerful D-Glucosidase Inhibitor 2,5-Dideoxy-2,5-Imino-D-Mannitol

ABSTRACT

By an Amadori rearrangement of easily available 5-azido-5-deoxy-D-glucofuranose with dibenzylamine and subsequent catalytic hydrogenation of the resulting 5-azido-1-(N,N-dibenzyl)amino-1,5-dideoxy-D-fructopyranose, 1-amino-1,2,5-trideoxy-2,5-imino-D-mannitol was obtained in only two steps and in excellent overall yield. Likewise, other amines were employed to introduce extended side chains ultimately suitable for attachment of the inhibitor to solid supports. The reported rearrangement reaction is a high yielding, convenient and apparently general entry to 1-aminodeoxyketopyranoses modified at C-5, facilitated by the ring enlargement of the aldofuranose to the ketopyranose as an additional driving force. A range of selected chain extended analogues was prepared by acylation of N-1. Inhibitors obtained exhibit K _i-values with D-glucosidases in the micromolar range. Interestingly, 1-N-acylation resulted in superior inhibitory activities, as did the addition of a hexyl chain.     

Controlled Click‐Assembly of Well‐Defined Hetero‐Bifunctional Cubic Silsesquioxanes and Their Application in Targeted Bioimaging

A general procedure for the assembly of hetero‐bifunctional cubic silsesquioxanes with diverse functionality and a perfectly controlled distribution of functional groups on the inorganic framework has been developed. The method is based on a two‐step sequence of mono‐ and hepta‐functionalization through the ligand‐accelerated copper(I)‐catalyzed azide–alkyne cycloaddition of a readily available octaazido cubic silsesquioxane. The stoichiometry of the reactants and the law of binomial distribution essentially determine the selectivity of the key monofunctionalization reaction when a copper catalyst with strong donor ligands is used. The methodology has been applied to the preparation of a set of bifunctional nano‐building‐blocks with orthogonal reactivity for the controlled assembly of precisely defined hybrid nanomaterials and a fluorescent multivalent probe for application in targeted cell‐imaging. The inorganic cage provides an improved photostability to the covalently attached dye as well as a convenient framework for the 3D multivalent display of the pendant epitopes. Thus, fluorescent bioprobes based on well‐defined cubic silsesquioxanes offer interesting advantages over more conventional fully organic analogues and ill‐defined hybrid nanoparticles and promise to become powerful tools for the study of cell biology and for biomedical applications.     

Finished-vehicle transporter routing problem solved by loading pattern discovery

This work addresses a new transportation problem in outbound logistics in the automobile industry: the finished-vehicle transporter routing problem (FVTRP). The FVTRP is a practical routing problem with loading constraints, and it assumes that dealers have deterministic demands for finished vehicles that have three-dimensional irregular shapes. The problem solution will identify optimal routes while satisfying demands. In terms of complex packing, finished vehicles are not directly loaded into the spaces of transporters; instead, loading patterns matching finished vehicles with transporters are identified first by mining successful loading records through virtual and manual loading test procedures, such that the packing problem is practically solved with the help of a procedure to discover loading patterns. This work proposes a mixed-integer linear programming (MILP) model for the FVTRP considering loading patterns. As a special class of routing models, the FVTRP is typically difficult to solve within a manageable computing time. Thus, an evolutionary algorithm is designed to solve the FVTRP. Comparisons of the proposed algorithm and a commercial MILP solver demonstrate that the proposed algorithm is more effective in solving medium- and large-scale problems. The proposed scheme for addressing the FVTRP is illustrated with an example and tested with benchmark instances that are derived from well-studied vehicle routing datasets.     

Chinese regional energy efficiency change and its determinants analysis: Malmquist index and Tobit model

China becomes the largest energy consumer in 2010 but its energy productivity is well below the world average. To meet China’s fast growing energy using, energy efficiency should be especially emphasized under China’s energy policy. This paper focuses on the regional level of energy efficiency change in China. And we analyze total factor energy efficiency for 30 Chinese provinces over the period 1998–2009 using Malmquist index method and Tobit analysis. The Malmquist estimation results suggest there is a dropping change trend of energy productivity growth. Chinese energy efficiency still faces with huge regional disparity, but the energy technical efficiency reflects convergence in the nationwide and west region. As a result of Tobit regression, we find that industrial structure, energy consumption structure and institutional factor have different influences on energy efficiency.     

Almost Sure Approximation of the Superposition of the Random Processes

This article presents sufficient conditions, which provide almost sure (a.s.) approximation of the superposition of the random processes S(N(t)), when càd-làg random processes S(t) and N(t) themselves admit a.s. approximation by a Wiener or stable Lévy processes. Such results serve as a source of numerous strong limit theorems for the random sums under various assumptions on counting process N(t) and summands. As a consequence we obtain a number of results concerning the a.s. approximation of the Kesten–Spitzer random walk, accumulated workload input into queuing system, risk processes in the classical and renewal risk models with small and large claims and use such results for investigation the growth rate and fluctuations of the mentioned processes.