Search results for "Macro"

3D Conformations of Thick Synthetic Polymer Chains Observed by Cryogenic Electron Microscopy.

2019

The backbone conformations of individual, unperturbed synthetic macromolecules have so far not been observed directly in spite of their fundamental importance to polymer physics. Here we report the dilute solution conformations of two types of linear dendronized polymers, obtained by cryogenic transmission electron stereography and tomography. The three-dimensional trajectories show that the wormlike chain model fails to adequately describe the scaling of these thick macromolecules already beyond a few nanometers in chain length, in spite of large apparent persistence lengths and long before a signature of self-avoidance appears. This insight is essential for understanding the limitations o…

Polymer droplets on substrates with striped surface domains: molecular dynamics simulations of equilibrium structure and liquid bridge rupture

2005

The structure of a polymer nanodroplet adsorbed on a flat lyophobic substrate chemically decorated with a lyophilic stripe of width 2RD is studied by molecular dynamics simulation of a coarse-grained bead–spring model of short macromolecules (containing N = 20 effective monomers). Varying the stripe width, the strength of the monomer–wall attraction and the temperature, the equilibrium morphology of the resulting droplets is studied and discussed in terms of current phenomenological theories. In the second part, the behaviour of a liquid bridge connecting two such lyophilic stripes a distance L apart is analysed. It is shown that for large enough L such free-standing films are unstable and …

Radiolabeling of DOTATOC with the long-lived positron emitter 44Sc.

2010

Abstract The positron-emitting radionuclide 44 Sc with a half-life of 3.97 h and a β + branching of 94.3% is of potential interest for clinical PET. As so far it is available from a 44 Ti/ 44 Sc generator in Mainz, where long-lived 44 Ti decays to no-carrier-added (nca) 44 Sc. The 44 Sc is a trivalent metal cation and should be suitable for complexation with many well established bifunctional chelators conjugated to peptides or other molecular targeting vectors. Thus, the aim of this work was to investigate the potential of 44 Sc for labeling of DOTA-conjugated peptides. DOTA-D-Phe 1 -Tyr 3 -octreotide (DOTATOC) was used as a model molecule to study and optimize labeling procedure. Reaction…

Can one detach a fully adsorbed flexible polymer chain by an ultra-small external force?

2013

Full adsorption of flexible chains onto typical solid substrates occurs at a surface interaction energy of (5–10) kBT. The corresponding detachment force is in the range 10–50 pN. In contrast to “bare” solid substrates common to non-living materials, surfaces coated with brush-like polymer layers are very common in biological soft matter. We employ a simple mean-field approach to describe the effects of weak attraction between a floating long macromolecule and the brush. We show that even for a moderately thick brush a very small effective attraction is enough to produce complete binding of the long chain. The detachment force scales as , where W is the brush thickness. Hence the force coul…

Crystal structure and morphology of polymers from solid-state reactions

1975

Some solid-state reactions which give rise to the formation of polymer crystals are discussed and the observation of the nascent polymer morphology is used as a guide-line to learn about the reaction mechanism of solid-state polymerizations. Examples for the following three different mechanisms are treated in detail: (a) crystallization succeeding polymerization, (b) simultaneous polymerization and crystallization, and (c) polymerization in solid solution. The nascent morphology of poly(alkylene)s obtained by Ziegler-Natta catalysis is taken as an example for crystallization succeeding polymerization. Another example is the cationic polymerization of 1,3,5-trioxane from solution. In this ca…

2015

The rationale of the study was two-fold: (i) develop a functional synthetic model of the Cytochrome c oxidase (CcO) active site, (ii) use it as a convenient tool to understand or predict the outcome of the reaction of CcO with ligands (physiologically relevant gases and other ligands). At physiological pH and potential, the model catalyzes the 4-electron reduction of oxygen. This model was immobilized on self-assembled-monolayer (SAM) modified electrode. During catalytic oxygen reduction, electron delivery through SAMs is rate limiting, similar to the situation in CcO. This model contains all three redox-active components in CcO's active site, which are required to minimize the production o…

Cyclodextrins in Polymer Synthesis:  Free Radical Polymerization of a N-Methacryloyl-11-aminoundecanoic Acid/β-Cyclodextrin Pseudorotaxane in an Aque…

1999

The relatively hydrophobic monomer N-methacryloyl-11-aminoundecanoic acid (1) was incorporated as a guest into the cavity of β-cyclodextrin (β-CD) as a host, yielding the water-soluble monomer N-me...

Ferrocenyl-functionalized long chain branched polydienes

2009

A convenient two-step approach for the synthesis of ferrocenyl-functionalized long chain branched polydienes, based on both butadiene and isoprene, respectively, is presented. Classical living anionic polymerization was used to synthesize different AB n type poly(diene) macromonomers with moderate molecular weights between 1700 and 3200 g/mol and narrow polydispersity. Quantitative end-capping with chlorodimethylsilane resulted in the desired AB n macromonomer structures. In the ensuing Pt-catalyzed hydrosilylation polyaddition, branched, functionalized polydienes were obtained by a concurrent AB n + AR type of copolymerization with mono-and difunctional ferrocenyl silanes (fcSiMe 2 H or fc…

Polymer-induced phase separation in suspensions of bacteria

2010

We study phase separation in suspensions of two unrelated species of rod-like bacteria, Escherichia coli and Sinorhizobium meliloti, induced by the addition of two different anionic polyelectrolytes, sodium polystyrene sulfonate or succinoglycan, the former being synthetic and the latter of natural origin. Comparison with the known behaviour of synthetic colloid-polymer mixtures and with simulations show that "depletion" (or, equivalently, "macromolecular crowding") is the dominant mechanism: exclusion of the non-adsorbing polymer from the region between two neighbouring bacteria creates an unbalanced osmotic force pushing them together. The implications of our results for understanding phe…

The synthesis of nareielasie aldehyde and related lsocarbostyrils

1977

The synthesis of several isoearboslyrils is reported, including lorrnyl derivatives at (1-4, like nareiclasie aldehyde (I) and the homologous aldehyde (XV).