492 research outputs found
Absorption/Expulsion of Oligomers and Linear Macromolecules in a Polymer Brush
The absorption of free linear chains in a polymer brush was studied with
respect to chain size and compatibility with the brush by means of
Monte Carlo (MC) simulations and Density Functional Theory (DFT) /
Self-Consistent Field Theory (SCFT) at both moderate, , and
high, , grafting densities using a bead-spring model.
Different concentrations of the free chains are
examined. Contrary to the case of when all species are almost
completely ejected by the polymer brush irrespective of their length , for
we find that the degree of absorption (absorbed amount)
undergoes a sharp crossover from weak to strong () absorption,
discriminating between oligomers, , and longer chains. For a
moderately dense brush, , the longer species, ,
populate predominantly the deep inner part of the brush whereas in a dense
brush they penetrate into the "fluffy" tail of the dense
brush only. Gyration radius and end-to-end distance of absorbed
chains thereby scale with length as free polymers in the bulk. Using both
MC and DFT/SCFT methods for brushes of different chain length , we demonstrate the existence of unique {\em critical} value of
compatibility . For the energy of free
chains attains the {\em same} value, irrespective of length whereas the
entropy of free chain displays a pronounced minimum. At all density
profiles of absorbing chains with different intersect at the same distance
from the grafting plane. The penetration/expulsion kinetics of free chains into
the polymer brush after an instantaneous change in their compatibility
displays a rather rich behavior. We find three distinct regimes of penetration
kinetics of free chains regarding the length : I (), II (), and III (), in which the time of absorption grows with
at a different rate. During the initial stages of penetration into the
brush one observes a power-law increase of with power
whereby penetration of the free chains into the
brush gets {\em slower} as their concentration rises
A COMPARATIVE STUDY OF OVARIAN FOLLICLE DYNAMICS AND IGF-I CONCENTRATION DURING AN OESTRUS CYCLE IN TWO GENOTYPES OF LACTATING HOLSTEIN-FRIESIAN COWS OFFERED PASTURE OR A TOTAL MIXED RATION
SUMMARY The objective was to characterize ovarian follicle dynamics and changes in systemic concentration of IGF-I during an oestrous cycle. The four treatment groups were New Zealand Holstein-Friesian (NZHF) Pasture (n=6) and TMR (n=10) and Overseas Holstein-Friesian (OSHF) Pasture (n=7) and TMR (n=6). From Day 17 following a synchronised oestrus, blood samples were collected and ovarian structures were monitored by ultrasound until the end of the subsequent cycle (ovulation). Every cow in the study had two waves of follicle development. NZHF cows had shorter (P<0.05) oestrous cycles than OSHF cows. Genotype or feeding system had no effect on emergence, selection, growth rate, maximum diameter or duration of dominance of the anovulatory or ovulatory follicles. Mean (±se) plasma IGF-I concentrations were higher (57.5±3.3 v 37.1±3.9 ng/mL; P<0.01) for cows offered TMR compared to pasture and also for NZHF compared to OSHF cows (56.3±3.6 v 38.3±3.6 ng/mL; P<0.01). In conclusion, this study has identified substantial differences in circulating IGF-I concentrations between dairy cow genotypes and between the feeding systems under which such cows are managed
Effects of polymer polydispersity on the phase behaviour of colloid-polymer mixtures
We study the equilibrium behaviour of a mixture of monodisperse hard sphere
colloids and polydisperse non-adsorbing polymers at their -point, using
the Asakura-Oosawa model treated within the free-volume approximation. Our
focus is the experimentally relevant scenario where the distribution of polymer
chain lengths across the system is fixed. Phase diagrams are calculated using
the moment free energy method, and we show that the mean polymer size at which gas-liquid phase separation first occurs decreases with increasing
polymer polydispersity . Correspondingly, at fixed mean polymer size,
polydispersity favours gas-liquid coexistence but delays the onset of
fluid-solid separation. On the other hand, we find that systems with different
but the same {\em mass-averaged} polymer chain length have nearly
polydispersity-independent phase diagrams. We conclude with a comparison to
previous calculations for a semi-grandcanonical scenario, where the polymer
chemical potentials are imposed, which predicted that fluid-solid coexistence
was over gas-liquid in some areas of the phase diagram. Our results show that
this somewhat counter-intuitive result arose because the actual polymer size
distribution in the system is shifted to smaller sizes relative to the polymer
reservoir distribution.Comment: Changes in v2: sketch in Figure 1 corrected, other figures improved;
added references to experimental work and discussion of mapping from polymer
chain length to effective radiu
Partially directed paths in a wedge
The enumeration of lattice paths in wedges poses unique mathematical
challenges. These models are not translationally invariant, and the absence of
this symmetry complicates both the derivation of a functional recurrence for
the generating function, and solving for it. In this paper we consider a model
of partially directed walks from the origin in the square lattice confined to
both a symmetric wedge defined by , and an asymmetric wedge defined
by the lines and Y=0, where is an integer. We prove that the
growth constant for all these models is equal to , independent of
the angle of the wedge. We derive functional recursions for both models, and
obtain explicit expressions for the generating functions when . From these
we find asymptotic formulas for the number of partially directed paths of
length in a wedge when .
The functional recurrences are solved by a variation of the kernel method,
which we call the ``iterated kernel method''. This method appears to be similar
to the obstinate kernel method used by Bousquet-Melou. This method requires us
to consider iterated compositions of the roots of the kernel. These
compositions turn out to be surprisingly tractable, and we are able to find
simple explicit expressions for them. However, in spite of this, the generating
functions turn out to be similar in form to Jacobi -functions, and have
natural boundaries on the unit circle.Comment: 26 pages, 5 figures. Submitted to JCT
Effect of BMAP-28 Antimicrobial Peptides on Leishmania major Promastigote and Amastigote Growth: Role of Leishmanolysin in Parasite Survival
Protozoan parasites are the causative agent of much disease in tropical areas of the world. Currently, the control of these diseases is dependent on outdated drug treatment, with associated high toxicity and drug resistance. There is an urgent need for novel anti-parasitic therapies. One emerging anti-parasitic therapies is Host defence peptides (HDPs). Here we test the HDP BMAP-28 as an anti-leishmanial therapy against two lifecycle stages of Leishmania major, the promastigotes (insect infective form) and the intracellular amastigote (mammalian infective form). Two stereoisomers of BMAP-28, the D-amino acid form (D-BMAP-28) and the retro-inverso form (RI-BMAP-28), were also tested for anti-leishmanial activity. The BMAP-28 form (L-form) was susceptible to degradation by GP63, the metalloproteinase that covers the promastigotes cell surface. However, the BMAP-28 isomers, the D-form and RI-form were resistant, and therefore more potent against the promastigote parasite. Though other anti-leishmanial HDP studies focus on the promastigote form of the parasite, it is the mammalian infective form, the amastigote, which causes the disease symptoms. Here we demonstrate that BMAP-28 and its isomers D-BMAP-28 and RI-BMAP-28 are effective against the amastigote form of the parasite using a macrophage infection model. These findings show that BMAP-28 has excellent potential as a novel anti-leishmanial therapeutic
Surface Grafting of Poly(L-glutamates). 3. Block Copolymerization
This paper describes for the first time the synthesis of surface-grafted AB-block copolypeptides, consisting of poly(γ-benzyl L-glutamate) (PBLG) as the A-block and poly(γ-methyl L-glutamate) (PMLG) as the B-block. Immobilized primary amine groups of (γ-aminopropyl)triethoxysilane (APS) on silicon wafers initiated the ring-opening polymerization of N-carboxyanhydrides of glutamic acid esters (NCAs). After removal of the BLG-NCA monomer solution after a certain reaction time, the amine end groups of the formed PBLG blocks acted as initiators for the second monomers. This method provides the possibility of making layered structures of surface-grafted block copolymers with tuned properties. Ellipsometry and small-angle X-ray reflection (SAXR) measurements revealed the thickness of the polypeptide layers ranging from 45-100 Å of the first block to 140-270 Å for the total block copolypeptides. The chemical composition of the blocks was determined by X-ray photoelectron spectroscopy (XPS). In addition, Fourier transform infrared transmission spectroscopy (FT-IR) revealed that the polypeptide main chains of both blocks consisted of pure R-helices. The average orientation of the helices ranging from 22-42° with respect to the substrate within the first block to 31-35° in the second block could be derived with FT-IR as well.
Self-Consistent Field study of Polyelectrolyte Brushes
We formulate a self-consistent field theory for polyelectrolyte brushes in
the presence of counterions. We numerically solve the self-consistent field
equations and study the monomer density profile, the distribution of
counterions, and the total charge distribution. We study the scaling relations
for the brush height and compare them to the prediction of other theories. We
find a weak dependence of the brush height on the grafting density.We fit the
counterion distribution outside the brush by the Gouy-Chapman solution for a
virtual charged wall. We calculate the amount of counterions outside the brush
and find that it saturates as the charge of the polyelectrolytes increases
Structure of Colloid-Polymer Suspensions
We discuss structural correlations in mixtures of free polymer and colloidal
particles based on a microscopic, 2-component liquid state integral equation
theory. Whereas in the case of polymers much smaller than the spherical
particles the relevant polymer degree of freedom is the center of mass, for
polymers larger than the (nano-) particles conformational rearrangements need
to be considered. They have the important consequence that the polymer
depletion layer exhibits two widely different length scales, one of the order
of the particle radius, the other of the order of the polymer radius or the
polymer density screening length in dilute or semidilute concentrations,
respectively. Their consequences on phase stability and structural correlations
are discussed extensively.Comment: 37 pages, 17 figures; topical feature articl
Determining the Effective Density and Stabilizer Layer Thickness of Sterically Stabilized Nanoparticles.
A series of model sterically stabilized diblock copolymer nanoparticles has been designed to aid the development of analytical protocols in order to determine two key parameters: the effective particle density and the steric stabilizer layer thickness. The former parameter is essential for high resolution particle size analysis based on analytical (ultra)centrifugation techniques (e.g., disk centrifuge photosedimentometry, DCP), whereas the latter parameter is of fundamental importance in determining the effectiveness of steric stabilization as a colloid stability mechanism. The diblock copolymer nanoparticles were prepared via polymerization-induced self-assembly (PISA) using RAFT aqueous emulsion polymerization: this approach affords relatively narrow particle size distributions and enables the mean particle diameter and the stabilizer layer thickness to be adjusted independently via systematic variation of the mean degree of polymerization of the hydrophobic and hydrophilic blocks, respectively. The hydrophobic core-forming block was poly(2,2,2-trifluoroethyl methacrylate) [PTFEMA], which was selected for its relatively high density. The hydrophilic stabilizer block was poly(glycerol monomethacrylate) [PGMA], which is a well-known non-ionic polymer that remains water-soluble over a wide range of temperatures. Four series of PGMA x -PTFEMA y nanoparticles were prepared (x = 28, 43, 63, and 98, y = 100-1400) and characterized via transmission electron microscopy (TEM), dynamic light scattering (DLS), and small-angle X-ray scattering (SAXS). It was found that the degree of polymerization of both the PGMA stabilizer and core-forming PTFEMA had a strong influence on the mean particle diameter, which ranged from 20 to 250 nm. Furthermore, SAXS was used to determine radii of gyration of 1.46 to 2.69 nm for the solvated PGMA stabilizer blocks. Thus, the mean effective density of these sterically stabilized particles was calculated and determined to lie between 1.19 g cm(-3) for the smaller particles and 1.41 g cm(-3) for the larger particles; these values are significantly lower than the solid-state density of PTFEMA (1.47 g cm(-3)). Since analytical centrifugation requires the density difference between the particles and the aqueous phase, determining the effective particle density is clearly vital for obtaining reliable particle size distributions. Furthermore, selected DCP data were recalculated by taking into account the inherent density distribution superimposed on the particle size distribution. Consequently, the true particle size distributions were found to be somewhat narrower than those calculated using an erroneous single density value, with smaller particles being particularly sensitive to this artifact
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