Microphase Separation within a Comb Copolymer with Attractive Side Chains: A Computer Simulation Study

Computer simulation modelling of a flexible comb copolymer with attractive interactions between the monomer units of the side chains is performed. The conditions for the coil-globule transition, induced by the increase of attractive interaction, ε, between side chain monomer units, are analysed for different values of the number of monomer units in the backbone, N, in the side chains, n, and between successive grafting points, m. It is shown that the coil-globule transition of such a copolymer corresponds to a first-order phase transition. The energy of attraction (ε) required for the realisation of the coil-globule transition decreases with increasing n and decreasing m. The coil-globule transition is accompanied by significant aggregation of side chain units. The resulting globule has a complex structure. In the case of a relatively short backbone (small value of N), the globule consists of a spherical core formed by side chains and an enveloping shell formed by the monomer units of the backbone. In the case of long copolymers (large value of N), the side chains form several spherical micelles while the backbone is wrapped on the surfaces of these micelles and between them.

Globule transitions of a single homopolymer: a Wang-Landau Monte Carlo study

The temperature-independent Wang-Landau Monte Carlo approach is implemented for an off-lattice model of flexible homopolymers and applied to the coil-globule and solidification transitions based on chain sizes up to N=300. An intermediate transformation from low-density liquid globule to high-density liquid globule is suggested. A scheme for identifying polymer structures representative of particular temperatures in the course of the simulation is presented and applied to illustrate intermediate states in the coil-globule transition. Transition temperatures are calculated and used to obtain a theta point of at least Θ=1.96, distinctly higher than the solid-liquid transition temperature TM=1.26

The coil-globule transition of polymers of long rigid monomers connected by flexible spacers

A simple model of a polymer with long rigid segments which interact via excluded volume repulsions and short ranged attractions is proposed. The coil-globule transition of this model polymer is strongly first order, the globule is crystalline and the coil which coexists with the globule is swollen. A virial expansion truncated at low order is shown to provide a very poor approximation to the free energy and so a cell theory is used to calculate the free energy of the globule.Comment: 9 pages, 2 figure

Globular Structures of a Helix-Coil Copolymer: Self-Consistent Treatment

A self-consistent field theory was developed in the grand-canonical ensemble formulation to study transitions in a helix-coil multiblock globule. Helical and coil parts are treated as stiff rods and self-avoiding walks of variable lengths correspondingly. The resulting field-theory takes, in addition to the conventional Zimm-Bragg (B.H. Zimm, I.K. Bragg, J. Chem. Phys. 31, 526 (1959)) parameters, also three-dimensional interaction terms into account. The appropriate differential equations which determine the self-consistent fields were solved numerically with finite element method. Three different phase states are found: open chain, amorphous globule and nematic liquid-crystalline (LC) globule. The LC-globule formation is driven by the interplay between the hydrophobic helical segments attraction and the anisotropic globule surface energy of an entropic nature. The full phase diagram of the helix-coil copolymer was calculated and thoroughly discussed. The suggested theory shows a clear interplay between secondary and tertiary structures in globular homopolypeptides.Comment: 26 pages, 30 figures, corrected some typo

Self- generated disorder and structural glass formation in homopolymer globules

We have investigated the interrelation between the spin glasses and the structural glasses. Spin glasses in this case are random magnets without reflection symmetry (e.g. $p$ - spin interaction spin glasses and Potts glasses) which contain quenched disorder, whereas the structural glasses are here exemplified by the homopolymeric globule, which can be viewed as a liquid of connected molecules on nano scales. It is argued that the homopolymeric globule problem can be mapped onto a disorder field theoretical model whose effective Hamiltonian resembles the corresponding one for the spin glass model. In this sense the disorder in the globule is self - generated (in contrast to spin glasses) and can be related with competitive interactions (virial coefficients of different signs) and the chain connectivity. The work is aimed at giving a quantitative description of this analogy. We have investigated the phase diagram of the homopolymeric globule where the transition line from the liquid to glassy globule is treated in terms of the replica symmetry breaking paradigm. The configurational entropy temperature dependence is also discussed.Comment: 22 pages, 4 figures, submitted to Phys. Rev.

Influence of Mucilage Viscosity On The Globule Structure And Stability Of Certain Starch Emulsions

A study was carried out to determine the influence of mucilage viscosity on the globule structure (i.e. size and number) of certain starch emulsions. The starches investigated were cassava, potato and maize. The emulsions were prepared by mixing the starch mucilage of a predetermined concentration 4%w/v with arachis oil in the ratio 50:50, using a silverson mixer fitted with a dispersator head. The emulsions were stored at room temperature (28±20C) for 7 days. Changes in globule size were monitored by photomicroscopy. Viscosities of the mucilage and those of resulting emulsions were determined using a capillary flow method. The viscosities of the emulsions expressed as time of flow (seconds), were 680 (cassava starch), 369 (potato starch) and 270 (Maize starch), and for the mucilage 510 (cassava), 336 (potato) and 248 (maize). The corresponding mean globule sizes of the fresh emulsions were (µm) 28±6, 42±6 and 45±5 respectively. The increase in globule size during storage (measure of globule coalescence rate) was 1.8±0.2µm day -1 (cassava), 3.5±0.2µm day -1 (potato) and 4.6±0.3µm day -1 (maize). Thus, a higher viscosity of the dispersion medium is associated with the production of finer and more stable emulsions

Hier ist wahrhaftig ein Loch im Himmel - The NGC 1999 dark globule is not a globule

The NGC 1999 reflection nebula features a dark patch with a size of ~10,000 AU, which has been interpreted as a small, dense foreground globule and possible site of imminent star formation. We present Herschel PACS far-infrared 70 and 160mum maps, which reveal a flux deficit at the location of the globule. We estimate the globule mass needed to produce such an absorption feature to be a few tenths to a few Msun. Inspired by this Herschel observation, we obtained APEX LABOCA and SABOCA submillimeter continuum maps, and Magellan PANIC near-infrared images of the region. We do not detect a submillimer source at the location of the Herschel flux decrement; furthermore our observations place an upper limit on the mass of the globule of ~2.4x10^-2 Msun. Indeed, the submillimeter maps appear to show a flux depression as well. Furthermore, the near-infrared images detect faint background stars that are less affected by extinction inside the dark patch than in its surroundings. We suggest that the dark patch is in fact a hole or cavity in the material producing the NGC 1999 reflection nebula, excavated by protostellar jets from the V 380 Ori multiple system.Comment: accepted for the A&A Herschel issue; 7 page

High Resolution CO and H2 Molecular Line Imaging of a Cometary Globule in the Helix Nebula

We report high resolution imaging of a prominent cometary globule in the Helix nebula in the CO J=1-0 (2.6 mm) and H2 v=1-0 S(1) (2.12 micron) lines. The observations confirm that globules consist of dense condensations of molecular gas embedded in the ionized nebula. The head of the globule is seen as a peak in the CO emission with an extremely narrow line width (0.5 km/s) and is outlined by a limb-brightened surface of H2 emission facing the central star and lying within the photo-ionized halo. The emission from both molecular species extends into the tail region. The presence of this extended molecular emission provides new constraints on the structure of the tails, and on the origin and evolution of the globules.Comment: 12 pages, 3 figures. To appear in The Astrophysical Journal Letter