Non-universal coarsening and universal distributions in far-from equilibrium systems

Anomalous coarsening in far-from equilibrium one-dimensional systems is investigated by simulation and analytic techniques. The minimal hard core particle (exclusion) models contain mechanisms of aggregated particle diffusion, with rates epsilon<<1, particle deposition into cluster gaps, but suppressed for the smallest gaps, and breakup of clusters which are adjacent to large gaps. Cluster breakup rates vary with the cluster length x as kx^alpha. The domain growth law x ~ (epsilon t)^z, with z=1/(2+alpha) for alpha>0, is explained by a scaling picture, as well as the scaling of the density of double vacancies (at which deposition and cluster breakup are allowed) as 1/[t(epsilon t)^z]. Numerical simulations for several values of alpha and epsilon confirm these results. An approximate factorization of the cluster configuration probability is performed within the master equation resulting from the mapping to a column picture. The equation for a one-variable scaling function explains the above results. The probability distributions of cluster lengths scale as P(x)= 1/(epsilon t)^z g(y), with y=x/(epsilon t)^z. However, those distributions show a universal tail with the form g(y) ~ exp(-y^{3/2}), which disagrees with the prediction of the independent cluster approximation. This result is explained by the connection of the vacancy dynamics with the problem of particle trapping in an infinite sea of traps and is confirmed by simulation.Comment: 30 pages (10 figures included), to appear in Phys. Rev.

Viscoelastic monitoring of starch-based biomaterials in simulated physiological conditions

Dynamic mechanical analysis (DMA) was used to investigate the solid-state rheological behaviour in a starch-based thermoplastic aimed to be used in different biomedical applications. The tested samples were processed by different injection moulding procedures. The dry samples were immersed in a simulated physiological solution and the relevant viscoelastic parameters were monitored against time. The decrease of stiffness due to swelling can be followed in real time, being less pronounced for the composite sample with hydroxyapatite (HA). The temperature control of the liquid bath was found to be very good. Frequency scans were also performed in wet conditions in samples previously immersed during different times, indicating that DMA is a suitable method to control in-vitro the changes on the viscoelastic properties of biomaterials during degradation

Finite-size effects in roughness distribution scaling

We study numerically finite-size corrections in scaling relations for roughness distributions of various interface growth models. The most common relation, which considers the average roughness $$as scaling factor, is not obeyed in the steady states of a group of ballistic-like models in 2+1 dimensions, even when very large system sizes are considered. On the other hand, good collapse of the same data is obtained with a scaling relation that involves the root mean square fluctuation of the roughness, which can be explained by finite-size effects on second moments of the scaling functions. We also obtain data collapse with an alternative scaling relation that accounts for the effect of the intrinsic width, which is a constant correction term previously proposed for the scaling of$$. This illustrates how finite-size corrections can be obtained from roughness distributions scaling. However, we discard the usual interpretation that the intrinsic width is a consequence of high surface steps by analyzing data of restricted solid-on-solid models with various maximal height differences between neighboring columns. We also observe that large finite-size corrections in the roughness distributions are usually accompanied by huge corrections in height distributions and average local slopes, as well as in estimates of scaling exponents. The molecular-beam epitaxy model of Das Sarma and Tamborenea in 1+1 dimensions is a case example in which none of the proposed scaling relations works properly, while the other measured quantities do not converge to the expected asymptotic values. Thus, although roughness distributions are clearly better than other quantities to determine the universality class of a growing system, it is not the final solution for this task.Comment: 25 pages, including 9 figures and 1 tabl

Chemistry and applications of phosphorylated chitin and chitosan

Chitin and chitosan are natural based non-toxic, biodegradable and biocompatible polymers and have been used in biomedical areas in the form of sutures, wound healing materials and artificial skin, and for the sustained release of drugs as well as in various industrial applications. However, practical use of these polymers has been mainly confined to the unmodified forms. Recently, there has been a growing interest in chemical modification of chitin and chitosan to improve their solubility and widen their applications. Among them, phosphorylated chitin and chitosan have attracted considerable interest because of their various advantages: anti-inflammatory property, ability to form metal complexes, blood compatibility and formation of anionic polyelectrolyte hydrogels. The purpose of this review is to take a closer look of different synthetic methods of phosphorylated chitin and chitosan and their potential applications in environmental, food, fuel cell, and biomedical fields. Based on current research and existing products, some new and futuristic approaches in this context area are discussed.R. Jayakumar acknowledges the Portuguese Foundation for Science and Technology for providing him a Post-Doc scholarship (SFRH/BPD/14670/2003). This work was partially supported by FCT Foundation for Science and Technology, through funds from the POCTI and/or FEDER program. This work was partially supported by the European Union funded STREP Project HIPPOCRATES (NMP3-CT-2003-505758)

Synthesis and characterization of N-methylenephenyl phosphonic chitosan

Chitosan is a natural based polymer obtained by alkaline deacetylation of chitin, exhibiting excellent properties such as non‐toxicity, biocompatibility and biodegradability. N‐Methylenephenyl phosphonic chitosan (NMPPC) is synthesized from chitosan by reacting with phenyl phosphonic acid using formaldehyde. The NMPPC was characterized by FTIR, 31P‐NMR, X‐ray diffraction, scanning electron microscopy, thermogravimeteric analysis and solubility studies. A significant decrease of molecular weight was observed in the NMPPC. The TGA studies suggested that NMPPC has less thermal stability than chitosan. The X‐ray diffraction analysis showed that NMPPC was amorphous in nature. The solubility property of the polymer was improved after the incorporation of a phenyl phosphonic grou

Broad Iron Emission from Gravitationally Lensed Quasars Observed by Chandra

Recent work has demonstrated the potential of gravitationally lensed quasars to extend measurements of black hole spin out to high-redshift with the current generation of X-ray observatories. Here we present an analysis of a large sample of 27 lensed quasars in the redshift range 1.0<z<4.5 observed with Chandra, utilizing over 1.6 Ms of total observing time, focusing on the rest-frame iron K emission from these sources. Although the X-ray signal-to-noise (S/N) currently available does not permit the detection of iron emission from the inner accretion disk in individual cases in our sample, we find significant structure in the stacked residuals. In addition to the narrow core, seen almost ubiquitously in local AGN, we find evidence for an additional underlying broad component from the inner accretion disk, with a clear red wing to the emission profile. Based on simulations, we find the detection of this broader component to be significant at greater than the 3-sigma level. This implies that iron emission from the inner disk is relatively common in the population of lensed quasars, and in turn further demonstrates that, with additional observations, this population represents an opportunity to significantly extend the sample of AGN spin measurements out to high-redshift.Comment: 5 pages, 2 figures, accepted for publication in Ap

Study of the fosfosal controlled permeation through glutaraldehyde crosslinked chitosan membranes

Advanced material forum III : proceedings of the III International Materials Symposium, Aveiro, 2005Fosfosal, a phosphate derivative of salicylic acid, which presents both analgesic and antiinflammatory properties, was used as a model drug to study the potential of recently developed chitosan membranes (with different crosslinking degrees) to be used as drug release rate-controlling membranes. The fosfosal permeation across these membranes was studied using an in-house built developed diffusion cell with online automatic monitoring. Experiments were performed using phosphate buffer saline (PBS) solution at 37ºC. Different flow properties of the detection set up were determined in order to estimate the errors introduced by the automatic online monitoring system. For increasing crosslinking degrees the permeability initially decreased, and then increased, likely as a consequence of the crosslinking influence on a variety of properties like crystallinity and hydrophilicity that have opposite influence on permeability. In summary, it was possible to control the drug release profile by means of changing the degree of crosslinking of chitosan membranes and to follow the respective release kinetics by means of using the developed diffusion cell(undefined

Surface properties of extracts from cork black condensate

The insulation corkboard production generates black condensate (BC), a paste-like solid waste. It is hydrophobic and has the potential to be used as protective coating. To evaluate this potential, coatings were prepared from BC extracts and their surface behavior was evaluated by contact angle (CA) measurements. The CA dynamics were recorded as a function of time; advancing CAs were also registered; the approaches were applied according to Fowkes, Owens- Wendt-Rabel-Kaelble (OWRK), and Van Oss to determine the surface energy (SE) for each coating. Depending on the liquid probe, three phenomena were observed: water evaporation, diiodomethane diffusion into the coating, and rearrangement of the chemical groups on the coating surface, when glycerol was dropped onto the surface. Based on the results from the CA dynamics, the applicability of the coatings against hydrophobic environments was limited owing to its affinity to apolar compounds. The results show that the coating prepared by the toluene BC extract was the best coating. The key data were: water CA of 99.38, total SE (between 37.4 mN m-1 and 40.1 mN m-1), SE polar component (0.1 mN m-1), and the acidic and basic characters were negligible. It can be concluded that the BC extracts have potential for coatings.R.P. acknowledges a post-doc research grant BPD/39333/2007 from the Portuguese Foundation for Science and Technology (FCT). We gratefully acknowledge Amorim Isolamentos S.A. for the supply of black condensate