Concentration effects on irreversible colloid cluster aggregation and gelation of silica dispersions

Effects of particle concentration on the irreversible aggregation of colloidal silica are studied using in situ destabilization via the ionic strength increase derived from the enzymatic hydrolysis of urea by urease. Aggregation is monitored by time-resolved optical density and dynamic light scattering measurements. It terminates at a gel boundary, signaled by a prominent increase of the optical density and incipient non-ergodicity. Raman scattering is used to demonstrate that the enzymatic reaction continues, well beyond gelation for the compositions studied here, until the urea is consumed. Calibration of the ionic conductivity permits for constructing stability diagrams in terms of particle and salt concentration. As with reversible gelation, the process exhibits a collective character in that lower ionic strengths are required for gelation of concentrated dispersions and vice versa. However, light scattering demonstrates that the gel boundary is preceded here by a line marking the transition from reversible to irreversible cluster formation, with the two transition boundaries tracking each other. Comparisons are made with dispersions destabilized by direct addition of salt solutions, which gel under very different conditions.     

Phase ordering after a deep quench: the stochastic Ising and hard core gas models on a tree

Consider a low temperature stochastic Ising model in the phase coexistence regime with Markov semigroup P_t. A fundamental and still largely open problem is the understanding of the long time behavior of δ_ηP_t when the initial configuration η is sampled from a highly disordered state ν (e.g. a product Bernoulli measure or a high temperature Gibbs measure). Exploiting recent progresses in the analysis of the mixing time of Monte Carlo Markov chains for discrete spin models on a regular b-ary tree , we study the above problem for the Ising and hard core gas (independent sets) models on . If ν is a biased product Bernoulli law then, under various assumptions on the bias and on the thermodynamic parameters, we prove ν-almost sure weak convergence of δ_ηP_t to an extremal Gibbs measure (pure phase) and show that the limit is approached at least as fast as a stretched exponential of the time t. In the context of randomized algorithms and if one considers the Glauber dynamics on a large, finite tree, our results prove fast local relaxation to equilibrium on time scales much smaller than the true mixing time, provided that the starting point of the chain is not taken as the worst one but it is rather sampled from a suitable distribution.     

Constraints on new physics from the quark mixing unitarity triangle

The status of the unitary triangle beyond the standard model including the most recent results on Deltam[s] on dilepton asymmetries and on width differences is presented. Even allowing for general new physics loop contributions the unitarity triangle must be very close to the standard model result. With the new measurements from the Fermilab Tevatron, we obtain for the first time a significant constraint on new physics in the Bs sector. We present the allowed ranges of new physics contributions to DeltaF=2 processes and of the time-dependent CP asymmetry in Bs-->J/psivarphi decays.     

The Spectral Gap for the Kawasaki Dynamics at Low Temperature

In this paper we analyze the convergence to equilibrium of Kawasaki dynamics for the Ising model in the phase coexistence region. First we show, in strict analogy with the nonconservative case, that in any lattice dimension, for any boundary condition and any positive temperature and particle density, the spectral gap in a box of side L does not shrink faster than a negative exponential of the surface L ^d–1. Then we prove that, in two dimensions and for free boundary condition, the spectral gap in a box of side L is smaller than a negative exponential of L provided that the temperature is below the critical one and the particle density satisfies (*_–, *₊), where *_± represents the particle density of the plus and minus phase, respectively.     

For 2-D lattice spin systems weak mixing implies strong mixing

We prove that for finite range discrete spin systems on the two dimensional latticeZ ², the (weak) mixing condition which follows, for instance, from the Dobrushin-Shlosman uniqueness condition for the Gibbs state implies a stronger mixing property of the Gibbs state, similar to the Dobrushin-Shlosman complete analyticity condition, but restricted to all squares in the lattice, or, more generally, to all sets multiple of a large enough square. The key observation leading to the proof is that a change in the boundary conditions cannot propagate either in the bulk, because of the weak mixing condition, or along the boundary because it is one dimensional. As a consequence we obtain for ferromagnetic Ising-type systems proofs that several nice properties hold arbitrarily close to the critical temperature; these properties include the existence of a convergent cluster expansion and uniform boundedness of the logarithmic Sobolev constant and rapid convergence to equilibrium of the associated Glauber dynamics on nice subsets ofZ ², including the full lattice.Work partially supported by grant SC1-CT91-0695 of the Commission of European Communities and by grant DMS 91-00725 of the American NSF.     

Polymerizable Gd(iii) building blocks for the synthesis of high relaxivity macromolecular MRI contrast agents

A new synthetic strategy for the preparation of macromolecular MRI contrast agents (CAs) is reported. Four gadolinium(iii) complexes bearing either one or two polymerizable methacrylamide groups were synthesized, serving as monomers or crosslinkers for the preparation of water-soluble, polymeric CAs using Reversible Addition–Fragmentation Chain Transfer (RAFT) polymerization. Using this approach, macromolecular CAs were synthesized with different architectures, including linear, hyperbranched polymers and gels. The relaxivities of the polymeric CAs were determined by NMR relaxometry, revealing an up to 5-fold increase in relaxivity (60 MHz, 310 K) for the linear polymers compared with the clinically used CA, Gd-DOTA. Moreover, hyperbranched polymers obtained from Gd(iii) crosslinkers, displayed even higher relaxivities up to 22.8 mM⁻¹ s⁻¹, approximately 8 times higher than that of Gd-DOTA (60 MHz, 310 K). A detailed NMRD study revealed that the enhanced relaxivities of the hyperbranched polymers were obtained by limiting the local motion of the crosslinked Gd(iii) chelate. The versatility of RAFT polymerization of Gd(iii) monomers and crosslinkers opens the doors to more advanced polymeric CAs capable of multimodal, bioresponsive or targeting properties.

A new synthetic strategy for the preparation of efficient macromolecular MRI contrast agents is reported.     

Multigrid solution of compressible turbulent flow on unstructured meshes using a two-equation model

The steady state solution of the system of equations consisting of the full Navier-Stokes equations and two turbulence equations has been obtained using a multigrid strategy on unstructured meshes. The flow equations and turbulence equations are solved in a loosely coupled manner. The flow equations are advanced in time using a multistage Runge-Kutta time-stepping scheme with a stability-bound local time step, while the turbulence equations are advanced in a point-implicit scheme with a time step which guarantees stability and positivity. Low-Reynolds-number modifications to the original two-equation model are incorporated in a manner which results in well-behaved equations for arbitrarily small wall distances. A variety of aerodynamic flows are solved, initializing all quantities with uniform freestream values. Rapid and uniform convergence rates for the flow and turbulence equations are observed.     

Computer-aided evaluation of liquid-chromatographic profiles for anthocyanins in vaccinium myrtillus fruits

The anthocyanin constituents of thirty samples of Vaccinium myrtillus fruits of various origin were examined by high-performance liquid chromatography. The data, characterized by 15 peaks for each chromatogram, were subjected to principal component analysis in order to reveal differences in the chromatograms. The vector space generated by eigenvector projection produced a clear separation between a group composed of Norwegian and Swedish berries and a group of berries of Italian or Romanian origin. Cyanidin glycosides are highly better represented in all the samples of the first group, while delphinidin glycosides are better represented in the latter.     

Clinical analysis of human urine by means of potentiometric Electronic tongue

The Electronic tongue (ET) composed of different kind of potentiometric chemical sensors has been applied for the detection of urinary system dysfunctions and creatinine levels. The creatinine contents evaluated by ET were compared with those obtained by automated Jaffe’s method and GC-MS, obtaining a satisfying agreement for both methods. Partial least square regression discriminate analysis (PLS-DA) and feed forward back-propagation neural network (FFBP NN) classified 51 urine specimens from healthy volunteers in four classes, according to the creatinine content, showing that both techniques can satisfactorily differentiate urines according to this parameter. The best accuracy result of 92.2% correct classification of unknown samples was achieved with FFBP NN. Moreover, the possibility of ET system to distinguish between urine samples of healthy patients, and those with malignant and non-malignant tumor diagnosis of bladder has been shown.