Search results for "substrate"

Epoxidation of Olefins with a Silica-Supported Peracid

2012

Anhydrous [2-percarboxyethyl] functionalized silica (2a) is an advantageous oxidant for performing the epoxidation of olefins 1. Epoxides 3 do not undergo the ring-opening reactions catalyzed by the acidic silica surface, except for particularly activated cases such as styrene oxide. The hydrophilic and acidic character of the silica surface does not interfere with the directing effects exerted by allylic H-bond acceptor substituents. The alkenes 1 carrying hydroxyl groups react with silica-supported peracid 2a faster than unsubstituted alkenes, thus reversing the trend known for reactions with soluble peracids. These results are attributed to the H-bond interactions of substrate 1 with the…

[39] Lipoperoxyl radical-scavenging activity of vitamin A and analogs in homogeneous solution

1994

Publisher Summary This chapter describes the assay method for determining the reactivity of all- trans -retinol and other natural and synthetic retinoids, with radicals generated by reaction of the lipid-soluble azo initiator 2,2 ' -azobis(2,4-dimethylvaleronitrile) (AMVN) with methyl linoleate. The chapter discusses the general principles for measuring antioxidant activity. The oxidation of linoleic acid methyl ester (LAME) is the simplest model for studying the oxidation of polyunsaturated lipids and has been widely adopted to evaluate antioxidant activity. Because linoleic acid has two double bonds, peroxidation occurs at the bisallylic hydrogens and generates conjugated diene hydroperox…

The Catalytic Effect of Fluoroalcohol Mixtures Depends on Domain Formation

2017

In the present contribution, we investigated catalytically active mixtures of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and aqueous H2O2 by molecular dynamics simulations. It is clearly observable that the HFIP molecule strongly binds to the H2O2, which is necessary for the desired catalytic reaction to occur. Upon the addition of the substrate cyclooctene to the solution, this interaction is enhanced, which suggests that the catalytic activity is increased by the presence of the hydrocarbon. We could clearly observe the microheterogeneous structure of the mixture, which is the result of the separation of the hydroxyl groups, water, and H2O2 from the fluorinated alkyl moiety in the form of l…

Synthesis of gold nanotubes with variable wall thicknesses

2013

We report the synthesis of gold nanotubes with variable wall thicknesses that is accomplished by the deposition of sacrificial hydrophobic polymer cores followed by gold shells within an anodic aluminum oxide template. We demonstrate that by varying polymer core hydrophobicity, the resulting gold shell thickness can be varied. There are two requirements for gold shell formation: (1) the polymer core must be able to be electrodeposited into a tubular (as opposed to wire-like) structure, and (2) the polymer must be hydrophobic, such that it collapses upon exposure to an aqueous solution. An array of gold nanotubes has variable plasmonic properties and can function as a surface enhanced Raman …

Polymer−Surfactant Interactions. A Quantitative Approach to the Enthalpy of Transfer of Poly(Ethylene Glycol)s from Water to the Aqueous Sodium Perfl…

2000

The enthalpy of transfer (ΔHt) of nonionic polymers at a fixed concentration from water to aqueous substrate solutions as a function of the substrate concentration (fSmS) was determined. The substrates studied are sodium perfluorobutanoate to sodium perfluorooctanoate, and the polymers are poly(ethyleneglycol)s with molecular weights of 400 and 35 000. For the PEG 400-sodium perfluoroheptanoate−water systems, measurements were also performed at some polymer compositions. As a general feature, the enthalpy of transfer steeply changes with fSmS, reaching a maximum beyond which it decreases, tending to level off. A qualitative analysis of the enthalpy data assigned the steep increase of ΔHt to…

Membrane Transport of l-Arginine and Cationic Amino Acid Analogs

2000

Publisher Summary This chapter reviews the current knowledge of the mechanisms and regulation of cationic amino acids (CAA) carrier proteins and discusses the potential involvement of each transporter in supplying L-arginine for nitric oxide biosynthesis. The CAA L-arginine, the substrate for nitric oxide synthases (NOSs), is considered a semi-essential amino acid in most mammals. Consequently, mammalian cells must be capable of exchanging CAA with the environment. The bilayer of the plasma membrane is impermeable to polar molecules, and thus, specialized carrier proteins with distinct substrate specificity transport hydrophilic solutes such as amino acids. L-arginine shares the same transp…

1983

Poly(ethylene glycol)s grated onto suitably functionalized, crosslinked polystyrenes were introduced as a new class of multidetachably immobilized hydrophilic macromolecular supports for the synthesis of peptides. This new polymeric carrier system facilitates both the homogeneous solvation of the reaction site and the insolubilization of the substrate, which are prerequisites for an efficient multistep synthesis using polymeric supports. In these support systems, a strongly solvated hydrophilic linear chain molecule, poly(ethylene glycol) (PEG)1 , is attached to an insoluble, crosslinked polystyrene through suitable anchoring linkages. At the free chain end of this supported PEG, amino acid…

Degradation of Acetylenic Triacylglyceroles and the Inactivation of Membrane Preparations from Moss Protonema Cells

1997

Protonema cells of the moss Ceratodon purpureus accumulate triacylglycerols with two acetylenic fatty acids, 9,12-octadecadien-6-ynoic acid (18:2A) and 9,12,15-octadeca-trein-6-ynoic acid (18:3A), as main components. By following the incorporation of the [14C]-precursors acetate, linoleate, α-linolenate, γ-linolenate, stearidonate and 18:2A, into 18:3A in triacylglycerol accumulating cells, the pathway for acetylenic acids could be established. 18:2A and 18:3A could be synthesized by a second desaturation of the Δ6 double bond of γ-linolenate and stearidonate, respectively. However the major pathway for 18:3A synthesis was via a Δ15 desaturation of 18:2A. Since 18:2A was found exclusively i…

Solution and fluorous phase synthesis of β,β-difluorinated 1-amino-1-cyclopentane carboxylic acid derivatives

2008

An efficient protocol for the preparation of β,β-difluorinated 1-amino-1-cyclopentane carboxylic acid derivatives was developed. 2,2-Difluro-4-phenyl-3-butenoic acid 6 was used as substrate for the preparation of the starting vinyl difluoro imino esters 8. The key steps of this methodology rely on the chemo- and diastereoselective addition of allylzinc bromides over the iminic functionality of 8 and subsequent RCM reaction. This synthetic sequence was successfully applied to fluorous synthesis.

Thermodynamic Properties of Sodium n-Alkanecarboxylates in Water and in Water + Cyclodextrins Mixtures

1998

Densities and heat capacities of water−substrate, water−cyclodextrin, and water−substrate−cyclodextrin systems were determined at 298 K. The substrates studied are sodium n-alkanecarboxylates (CnCOONa) (from sodium acetate to sodium decanoate) and the cyclodextrins are hydroxypropyl-α-cyclodextrin (HP-α-CD), hydroxypropyl-β-cyclodextrin, (HP-β-CD), hydroxypropyl-γ-cyclodextrin (HP-γ-CD) and β-cyclodextrin (β-CD). The apparent molar volumes and heat capacities of CnCOONa in water were calculated as functions of concentration. The standard partial molar properties agree with those obtained by using the additivity rule. HP-β-CD essentially does not affect the thermodynamic properties of C1COON…