Nondigestible oligosaccharides as dietary fiber

An overview is presented of the most important oligosaccharides that are classified as dietary fiber. Their occurrence and structures as well as their various physiological effects are described. The scientific evidence for health effects, associated with these physiological effects, along with the applications in the food industry, are also discussed.     

Covalent Adaptable Networks with Tunable Exchange Rates Based on Reversible Thiol–yne Cross‐Linking

The design of covalent adaptable networks (CANs) relies on the ability to trigger the rearrangement of bonds within a polymer network. Simple activated alkynes are now used as versatile reversible cross‐linkers for thiols. The click‐like thiol–yne cross‐linking reaction readily enables network synthesis from polythiols through a double Michael addition with a reversible and tunable second addition step. The resulting thioacetal cross‐linking moieties are robust but dynamic linkages. A series of different activated alkynes have been synthesized and systematically probed for their ability to produce dynamic thioacetal linkages, both in kinetic studies of small molecule models, as well as in stress relaxation and creep measurements on thiol–yne‐based CANs. The results are further rationalized by DFT calculations, showing that the bond exchange rates can be significantly influenced by the choice of the activated alkyne cross‐linker.     

Fluid phase equilibrium studies on model substances for supercritical fluid extraction with CO2 up to 100 MPa

Abstract

Multicomponent fluid phase equilibrium data are of increasing interest for applications in Supercritical Fluid Extraction (SFE) where compressed supercritical gases are used for the extraction of low-volatile substances (e.g. caffeine from coffee and tea, hops etc.). Sometimes so-called moderator substances have to be added in order to increase solvent power and/or selectivity. Systematic measurements on a four-component system of the type CO₂ + fatty alcohol (e.g. 1-do-decanol) + alkane (e.g. hexadecane) as a function of the amount of moderator added were performed at 393 K and at pressures from 10 to 100 MPa in an analytical high-pressure cell. Separation factors calculated from the p,T,w/,w, “data are presented and discussed.     

Frequency effects in capacitively coupled radio-frequency glowdischarges: a comparison between a 2-D fluid model and experiments

The results of a 2-D fluid model for argon radiofrequency (RF) discharges in a closed cylindrical vacuum chamber are compared with experimental data from an amorphous silicon deposition reactor operated in argon. Good agreement is obtained for the relation between the DC autobias voltage and the dissipated power in the frequency range 40-100 MHz at pressures between 10 and 60 Pa. Scaling laws are presented for the dissipated power and for the ion fluxes toward the electrodes. These quantities are expressed in the DC bias voltage, the RF excitation frequency and the background pressure. Also the uniformity of the ion fluxes is studied. The model yields a linear relation between the applied RF voltage and the DC bias voltage. This relation depends only on the geometry of the discharge chamber and shows an offset     

Photocatalysis—VII: Photochemical cyclodimerisation of cycloalkenes catalysed by copper(I) triflate. Formation and identification of two cycloheptene and five cyclooctene dimers

The photochemical cyclodimerisation of cycloheptene and cyclooctene has been studied under irradiation at 254 nm, using copper(I) triflate as catalyst. Two cycloheptene dimers cis-anti-cis- and trans-syn-trans-tricyclo [7.5.0.0^2,8] tetradecane and five cyclooctene dimers (all stereoisomeric tricyclo [8.6.0.0^2,9] hexadecanes) have been obtained. The ¹H and ¹³C NMR spectra of the cyclooctene dimers show an upfield shift (from 2.4 to 1 ppm) of the cyclobutyl hydrogens due to cyclobutane ring puckering and a downfield shift of the cyclobutyl carbon resonances. Their GC retention times decrease upon increased ring puckering.The photocatalysed dimerisation of cycloheptene is exceptional in that no trans-anti-trans or cis-trans isomers are formed as is the case for cyclohexene or cyclooctene. Thermally, the trans-cycloheptene ligand in the copper(I) triflate complex cyclotrimerizes exclusively, via R,R,R- or S,S,S-combinations.     

Covalent Adaptable Networks with Tunable Exchange Rates Based on Reversible Thiol–yne Cross-Linking

The design of covalent adaptable networks (CANs) relies on the ability to trigger the rearrangement of bonds within a polymer network. Simple activated alkynes are now used as versatile reversible cross-linkers for thiols. The click-like thiol–yne cross-linking reaction readily enables network synthesis from polythiols through a double Michael addition with a reversible and tunable second addition step. The resulting thioacetal cross-linking moieties are robust but dynamic linkages. A series of different activated alkynes have been synthesized and systematically probed for their ability to produce dynamic thioacetal linkages, both in kinetic studies of small molecule models, as well as in stress relaxation and creep measurements on thiol–yne-based CANs. The results are further rationalized by DFT calculations, showing that the bond exchange rates can be significantly influenced by the choice of the activated alkyne cross-linker.     

Selective liquid-phase semihydrogenation of functionalized acetylenes and propargylic alcohols with silica-supported bimetallic palladium-copper catalysts

Silica-supported, bimetallic palladium-copper catalysts were prepared in solution under mild conditions by reacting lithium di(4-tolyl)cuprate with palladium acetate in the presence of silica particles. Small bimetallic palladium-copper particles were deposited on the silica surface as confirmed with TEM-EDAX and EXAFS. The new material has been applied as catalyst in the liquid-phase semihydrogenation of mono- and disubstituted alkynes and showed high selectivity toward the cis-alkenes. The influence of addition of quinoline or potassium hydroxide to the semihydrogenation reaction mixture and the effects of exposure of the catalyst to air before use have been investigated.     

Strong support effects on the insulator to metal transition in supported Pt clusters as observed by X-ray absorption spectroscopy

The development of a new in situ probe of metallic character in supported metal clusters utilizing X-ray absorption spectroscopy is described. The technique is based on the extent of screening of the core-hole left in the neutral final state after the X-ray absorption. The technique allows for the clear differentiation between local interatomic charge transfer and more delocalized metallic screening. The particle size at the metal-insulator transition is found to depend strongly on the electron richness of the support oxygen atoms (i.e., ionic vs covalent oxides). Pt particles on supports with electron poor oxygen atoms (covalent) show metallic screening for sizes as small as 12 A in diameter. In contrast, on supports with electron rich oxygen atoms (ionic) the Pt particles do not show metallic behavior until around 20 A. The wide variation of previously reported estimates of the particle size at which the insulator to metal transition occurs is explained, giving a consistent picture for the onset of metallic character, and the reasons for the strong support effect.     

Ligand exchange reactions between copper(II)- and nickel(II)- chelates of different sulphur- and selenium-containing ligandsIII: Single-crystal ESR study on the mixed-ligand chelate (n-Bu4N) [63Cu(mnt) (et2dsc)] and crystal and molecular structure of (n-Bu4N) [Ni(mnt) (et2dsc)]

A single-crystal ESR study of the mixed-ligand complex tetra - n - butylammonium - (maleonitriledithiolato)(diethyl - di - selenocarbamato)cuprate(II) diamagnetically diluted by the corresponding Ni(II) complex, and the crystal and molecular structure of the host complex determined by a single-crystal X-ray diffraction study, is reported. (n-Bu₄N)[Ni(mnt)(et₂dsc)] is monoclinic, space group C2/c, with eight molecules in the unit cell; a = 19.932(9) Å, b = 9.597(3) Å, c = 37.580(13) Å and β = 101.32(3)°. Based on the structure the spin Hamiltonian parameters have been calculated from the results of extended Hückel molecular orbital calculations and compared with the experimentally obtained values. The principal axes of the g? and the metal hyperfine tensor do not coincide reflecting the large influence of the et₂dsc^? ligand for which this behaviour was found to be typical. A comparison between the ESR parameters and the Mulliken spin densities of the mixed-ligand chelate and the corresponding parent complexes shows that in the former one spin density appears to be transfered from the S atoms to the Se atoms of the et₂dsc^? part of the complex resulting in an increased CuSe covalency. Back-bonding effects were considered in discussing the bonding properties.     

Excellent organic/inorganic transparent thin film moisture barrier entirely made by hot wire CVD at 100 °C

We present a silicon nitride/polymer hybrid multilayer moisture barrier for flexible electronics made entirely by hot wire chemical vapor deposition (HWCVD) at substrate temperatures below 100 °C. Using the initiated CVD (iCVD) variant of HWCVD for the polymer layers, these can be extremely thin, while efficiently decoupling the defects in consecutive inorganic layers. Although a single layer of low temperature SiN_x is more prone to have pinholes than its state‐of‐the‐art high temperature equivalent, we have achieved a simple three‐layer structure consisting of two low‐temperature SiN_x layers with a polymer layer in between, which is pinhole free and shows a water vapor transmission rate (WVTR) as low as 5 × 10^–6 g/m²/day at a temperature of 60 °C and a relative humidity of 90%. This WVTR is low enough for organic devices. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)