Search results for "BOND"

Hydrogen-Bonded Aggregates of Oligoaramide−Poly(ethylene glycol) Block Copolymers

2010

Rod−coil copolymers with an oligomeric rod aggregate on a nanometer length scale, which is important for many applications like e.g. organic photovoltaics. However, this aggregation behavior and the driving forces such as hydrogen bonding and π−π interactions, as well as the role of side groups, are not yet fully understood. Here, we investigated these noncovalent interactions in oligo(p-benzamide)−poly(ethylene glycol) (OPBA−PEG) copolymers using solid-state NMR supported by wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), and polarization optical microscopy (POM). It was found that longer OPBAs form layered β-sheet-like aggregates and that these are stabilized …

1995

Redoxactive liquid crystalline (LC) side group polymers were prepared by copolymerization of liquid crystalline acrylates and ferrocene-containing acrylates. The corresponding liquid crystalline ionomers were synthesized by a reversible redox reaction. The incorporation of tetra-alkylated ferrocene derivatives leads to LC polymers with reduced redox potential. These polymers can be oxidized under mild conditions to the corresponding ionomers, which are much more stable in solution than LC ionomers containing monoalkylated ferrocenium ions. Dynamic mechanical measurements and small angle X-ray scattering (SAXS) perfomed on LC ionomers prove the existence of ionic superstructures (clusters) w…

Distribution of molecularly imprinted polymer layers on macroporous silica gel particles by STEM and EDX

2005

Abstract Using transmission electron microscopy (TEM) in parallel and scanning mode (STEM) combined with energy dispersive X-ray spectroscopy (EDX) the distribution of molecularly imprinted polymer layers covalently grafted on the inner and outer surface of macroporous silica gel particles was observed. The grafting was achieved using a special initiator system ( iniferter ) and applied on a well known model system producing molecularly imprinted layers with l -phenyl alanine analide ( l -PA) as template. By staining the sample with RuO 4 before its embedment in epoxy resin and cutting ultra thin slices it was possible to identify the stained grafted polymer on the silica matrix by EDX. Bas…

Iron(II) Metallomesogens Exhibiting Coupled Spin State and Liquid Crystal Phase Transitions near Room Temperature

2008

Reaction of the ligand 2,2,2-tris(2-aza-3-((5-akloxy)(6-methyl)(2-pyridyl))prop-2-enyl)ethane (C n -tameMe) with Fe(X) 2 . sH 2 O salts afforded a series of spin crossover metallomesogens with general formula [Fe(C n -tame)](X) 2 . sH 2 O (s ≥ 0), with n = 6, 10, 12, 14, 16, 17, 18, or 20 and X =ClO 4 - or BF 4 -. Single crystal X-ray measurements have been performed on the [Fe(C 6 -tameMe)](ClO 4 ) 2 (C 6 -1) derivative at 100 K. The complex C 6 -1 crystallizes in the triclinic system and adopts the Pbca space group. The iron(II) ion is in a distorted octahedral environment shaped by three imine and three pyridine nitrogen atoms of the C n -tameMe ligand. The average Fe-N im and Fe-N py bo…

Correlations of the nonexponentiality and state dependence of mechanical relaxations with bond connectivity in Ge-As-Se supercooled liquids

1992

We have studied the mechanical responses of supercooled Ge-As-Se liquids to flexural strains and temperature steps. The departures from exponential relaxation correlate well with the variations in connectivity. The structural state dependence of the mechanical relaxation, detected in pure and weakly cross-linked Se, is suppressed completely at the rigidity percolation threshold {l angle}{ital r}{sub {ital c}}{r angle}, where the liquid fragility is a minimum. The shapes of the decay functions of samples with the same {l angle}{ital r}{sub {ital c}}{r angle} but different compositions are not universal at {ital T}{sub {ital g}} probably because of chemical effects near the binary edges of th…

Ionic iridium complex and conjugated polymer used to solution-process a bilayer white light-emitting diode.

2013

Bilayer white light-emitting devices are prepared from solution, using an ionic orange phosphorescent organometallic complex and a neutral fluorescent conjugated polymer. Because of the very different polarity of the two components, they dissolve in orthogonal solvents, allowing for the direct deposition of the blue emitter on top of the orange emitter without the need of cross-linking or special coating methodology. Fine tuning of the layer thickness of both light-emitting layers allows for the color tuning of different types of white light.

Wall mannoproteins of the yeast and mycelial cells of Candida albicans: nature of the glycosidic bonds and polydispersity of their mannan moieties.

1988

SUMMARY: Zymolyase released between 20 and 25% of the total protein from purified walls of yeast (Y) and mycelial (M) cells of Candida albicans. The material released contained 92% carbohydrate (86% mannose and 6% glucose) and 7:< protein. Over 85% of the carbohydrate was N-glycosidically linked to the protein and the rest (less than 15%) was linked O-glycosidically. Highly polydisperse, high molecular mass mannoproteins, resolved by electrophoresis as four defined bands in Y cells and two bands in M cells, had both types of sugar chains. A 34 kDa species found in both types of cells had a single 2.5 kDa N-glycosidically linked sugar chain and a 3 1.5 kDa protein moiety. Polydispersity in t…

Five-to-Six Membered Ring-rearrangements in the Reaction of 5-Perfluoroalkyl-1,2,4-oxadiazoles with Hydrazine and Methylhydrazine

2006

The hydrazinolysis reaction of 5-perfluoroalkyl-1,2,4-oxadiazoles with hydrazine or methylhydrazine as bidentate nucleophiles has been investigated. The reaction occurred through the addition of the bidentate nucleophile to the C(5)-N(4) double bond of the 1,2,4-oxadiazole followed by ring-opening and ring-closure (ANRORC) involving the second nucleophilic site of the reagent. This ring-closure step could involve either the original C(3) of the 1,2,4-oxadiazole (giving a five-to-five membered ring rearrangement) or an additional electrophilic center linked to it (exploiting a five-to-six membered ring rearrangement). An alternative initial nucleophilic attack may involve the additional elec…

Conformational properties of N-acetyl-N-methyl-alpha,beta-dehydroalanine N'-methylamide.

2006

The conformational properties of Ac-Delta(Me)Ala-NHMe (N-acetyl-N-methyl-alpha,beta-dehydroalanine N'-methylamide), as the simplest model of N-methyl-alpha,beta-dehydroamino acids, was examined with theoretical methods and in comparison with Ac-DeltaAla-NHMe and Ac-DeltaAla-NMe(2). The N-terminal amide of the Delta(Me)Ala residue easily adopts the configuration cis and the torsion angles phi, psi are highly flexible. The Delta(Me)Ala residue is a conformational flexibilizer as compared to the parent DeltaAla, which is a conformational stiffener. This seems to be the reason why Delta(Me)Ala is found in small natural cyclic peptides, where it ensures the conformational flexibility necessary f…

Dominance of Chain Entanglement over Transient Sticking on Chain Dynamics in Hydrogen-Bonded Supramolecular Polymer Networks in the Melt

2018

The chain dynamics in supramolecular polymer networks is determined by the interplay of the kinetics of transient interchain association and relaxation of the network chains themselves. This interplay can be addressed by studying model supramolecular polymer networks in which the number of associative side groups and the molar mass of the covalently jointed backbone polymers are both varied systematically. To realize this idea, we use precursor chains with three different molar masses, which comes along with different extents of entanglement in the melt state. For each molar mass, the precursor polymers are functionalized with three different relative contents of associative side groups, gi…