Organic reactions in ionic liquids; Ionic liquid-accelerated three-component reaction: a rapid one-pot synthesis of 3-alkyl-5-[(Z)-arylmethylidene]-1,3-thiazolidine-2,4-diones

A rapid one-pot synthesis of 3-alkyl-5-[(Z)-arylme­thylidene]-1,3-thiazolidine-2,4-dionesis described that occurs in recyclable ionic liquid [bmim]PF6 (1-butyl-3-methylimidazolium hexafluorophosphate).Significant rate enhancement and good selectivity have been observed.

Conformal sulfated zirconia monolayer catalysts for the one-pot synthesis of ethyl levulinate from glucose

Here we describe a simple route to creating conformal sulphated zirconia monolayers throughout an SBA-15 architecture that confers efficient acid-catalysed one-pot conversion of glucose to ethyl levulinate.

A general one-pot strategy for the synthesis of high-performance transparent-conducting-oxide nanocrystal inks for all-solution-processed devices

For all-solution-processed (ASP) devices, transparent conducting oxide (TCO) nanocrystal (NC) inks are anticipated as the next-generation electrodes to replace both those synthesized by sputtering techniques and those consisting of rare metals, but a universal and one-pot method to prepare these inks is still lacking. A universal one-pot strategy is now described; through simply heating a mixture of metal-organic precursors a wide range of TCO NC inks, which can be assembled into high-performance electrodes for use in ASP optoelectronics, were synthesized. This method can be used for various oxide NC inks with yields as high as 10 g. The formed NCs are of high crystallinity, uniform morphology, monodispersity, and high ink stability and feature effective doping. Therefore, the inks can be readily assembled into films with a surface roughness of 1.6 nm. Typically, a sheet resistance of 110 Ω sq-1 can be achieved with a transmittance of 88%, which is the best performance for TCO NC ink-based electrodes described to date. These electrodes can thus drive a polymer light-emitting diode (PLED) with a luminance of 2200 cdm-2 at 100 mA cm-2.

Base-free, one-pot chemocatalytic conversion of glycerol to methyl lactate using supported gold catalysts

We report an efficient one-pot conversion of glycerol (GLY) to methyl lactate (MLACT) in methanol in good yields (73 % at 95 % GLY conversion) by using Au nanoparticles on commercially available ultra-stable zeolite-Y (USY) as the catalyst (160 °C, air, 47 bar pressure, 0.25 M GLY, GLY-to-Au mol ratio of 1407, 10 h). The best results were obtained with zeolite USY-600, a catalyst that has both Lewis and Brønsted sites. This methodology provides a direct chemo-catalytic route for the synthesis of MLACT from GLY. MLACT is stable under the reaction conditions, and the Au/USY catalyst was recycled without a decrease in the activity and selectivity. From glycerol to green building blocks and solvents! An efficient, base-free conversion of glycerol to methyl lactate in methanol is reported, achieving good yields (73 % at 95 % glycerol conversion) using Au/ultra-stable zeolite-Y (USY) as the catalyst and environmentally benign oxygen as the oxidant by combining two separate reaction steps efficiently in a one pot procedure. The Au/USY catalyst can be recycled without a decrease in the activity and selectivity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile synthesis of well-defined hydrophilic methacrylic macromonomers using ATRP and click chemistry

A range of well-defined hydrophilic methacrylic macromonomers has been synthesized by the judicious combination of atom transfer radical polymerization (ATRP) and copper-catalyzed 1,3-dipolar cycloaddition (azide-alkyne click chemistry). An azido a-functionalized ATRP initiator was used to produce well-defined homopolymers with terminal azide functionality via ATRP in protic media at 20 °C, with generally good control being achieved over both target molecular weight and final polydispersity (Mw/Mn = 1.10-1.35). Suitable methacrylic monomers include 2-aminoethyl methacrylate hydrochloride, 2-(diethylamino)ethyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-(methacryloyloxy)ethyl phosphorylcholine, glycerol monomethacrylate, potassium 3-sulfopropyl methacrylate, and quaternized 2-(dimethylamino)ethyl methacrylate. These homopolymer precursors were then efficiently clicked using either propargyl methacrylate or propargyl acrylate to yield near-monodisperse (meth)acrylate-capped macromonomers with either cationic, anionic, nonionic, or zwitterionic character. Moreover, this generic route to well-defined hydrophilic macromonomers is also suitable for “one-pot” syntheses, as exemplified for 2-hydroxyethyl methacrylate and glycerol monomethacrylate-based macromonomers.

Living cationic polymerization of isobutene

The polymerization of isobutene initiated by 1-chloro-1-phenylethane has been investigated, and molecular weight studies conducted using size exclusion chromatography. Polymerizations carried out in a 40/60 (v/v) mixture of dichloromethaneIcyclohexane, using titanium (IV) chloride as a catalyst in the presence of pyridine at -30 °C were found to be controlled and living. The number average molecular weights of the polymers increased linearly with monomer conversion, and the molecular weight distributions were between 1.15 and 1.20. Efficiencies of initiation were between 80 and 100%, and evidence was found to suggest that backbiting to the initiator had occurred, resulting in the formation of cyclic oligomers during the early stages of polymerization. The kinetics of polymerization can be explained in terms of active species in. equilibrium with dormant species. The effects of temperature. and dielectric constant on this equilibrium were studied and a model based upon the Fuoss equation was developed. Pyridine was found to behave as proton trap in the system, and when it was used in excess the rate of polymerization was retarded. By assuming that the catalyst and pyridine formed a one to one complex, it was possible to show that the reaction was second order with respect to the catalyst. The synthesis of low molecular weight polyisobutenes was studied. When the concentration of initiator was increased relative to that of the isobutene, such that the theoretical degree of polymerization was 20 or less, the rate of initiation was slow compared to propagation. The efficiency of initiation in these polymerizations was typically between 30 and 40 %. Optimal conditions of temperature. and.catalyst concentration were established, leading to a 60 % efficiency of initiation. A one-pot synthesis of phenol end-capped polyisobutene was attempted by adding phenol at the end of a living polymerization. Evidence to substantiate the existence of capped polymer chains in the resultant product was inconclusive. Block copolymerizations of oxetane and isobutene were conducted using 1-chloro-1phenylethane/TiCl4, but no copolymer or oxetane homopolymer could be isolated.

Quinols as novel therapeutic agents. 2.1 4-(1-arylsulfonylindol- 2-yl)-4-hydroxycyclohexa-2,5-dien-1-ones and related agents as potent and selective antitumor agents

A series of substituted 4-(1-arylsulfonylindol-2-yl)-4-hydroxycyclohexa-2, 5-dien-1-ones (indolylquinols) has been synthesized on the basis of the discovery of lead compound 1a and screened for antitumor activity. Synthesis of this novel series was accomplished via the "one-pot" addition of lithiated (arylsulfonyl)indoles to 4,4-dimethoxycyclohexa-2,5-dienone followed by deprotection under acidic conditions. Similar methodology gave rise to the related naphtho-, 1H-indole-, and benzimidazole-substituted quinols. A number of compounds in this new series were found to possess in vitro human tumor cell line activity substantially more potent than the recently reported antitumor 4-substituted 4-hydroxycyclohexa-2,5-dien-1-ones1 with similar patterns of selectivity against colon, renal, and breast cell lines. The most potent compound in the series in vitro, 4-(1-benzenesulfonyl-6-fluoro-1H-indol- 2-yl)-4-hydroxycyclohexa-2,5-dienone (1h), exhibits a mean GI50 value of 16 nM and a mean LC50 value of 2.24 μM in the NCI 60-cell-line screen, with LC50 activity in the HCT 116 human colon cancer cell line below 10 nM. The crystal structure of the unsubstituted indolylquinol 1a exhibits two independent molecules, both participating in intermolecular hydrogen bonds from quinol OH to carbonyl O, but one OH group also interacts intramolecularly with a sulfonyl O atom. This interaction, which strengthens upon ab initio optimization, may influence the chemical environment of the bioactive quinol moiety. In vivo, significant antitumor activity was recorded (day 28) in mice bearing subcutaneously implanted MDA-MB-435 xenografts, following intraperitoneal treatment of mice with compound 1a at 50 mg/kg.

Facile synthesis of hierarchical Cu2O nanocubes as visible light photocatalysts

Hierarchically structured Cu2O nanocubes have been synthesized by a facile and cost-effective one-pot, solution phase process. Self-assembly of 5 nm Cu2O nanocrystallites induced through reduction by glucose affords a mesoporous 375 nm cubic architecture with superior visible light photocatalytic performance in both methylene blue dye degradation and hydrogen production from water than conventional non-porous analogues. Hierarchical nanocubes offer improved accessible surface active sites and optical/electronic properties, which act in concert to confer 200–300% rate-enhancements for the photocatalytic decomposition of organic pollutants and solar fuels.

ICT and internet use at the household levels:a melting pot of sub-optimum decision making in the case of E-Grocery shopping

Research shows that consumers are readily embracing the Internet to buy products. This paper proposes that, in the case of grocery shopping, this may lead to sub-optimal decisions at the household level. Decisions online on what, where and from who to buy are normally taken by one individual. In the case of grocery shopping, decisions, however, need to be ‘vetted’ by ‘other’ individuals within the household. The ‘household wide related’ decisions influence how information technologies and systems for commerce should be designed and managed for optimum decision making. This paper argues, unlike previous research, that e-grocery retailing is failing to grow to its full potential not solely because of the ‘classical’ hazards and perceived risks associated with doing grocery shopping online but because e-grocery retailing strategy has failed to acknowledge the micro-household level specificities that affect decision making. Our exploratory research is based on empirical evidence which were collected through telephone interviews. We offer an insight into how e-grocery ‘fits’ and is ‘disrupted’ by the reality of day to day consumption decision making at the household level. Our main finding is to advocate a more role-neutral, multi-user and multi-technology approach to e-grocery shopping which re-defines the concept of the main shopper/decision maker thereby reconceptualising the ‘shopping logic’ for grocery products.