Reversible Diffusion-Limited Reactions: "Chemical Equilibrium" State and the Law of Mass Action Revisited

The validity of two fundamental concepts of classical chemical kinetics - the notion of "Chemical Equilibrium" and the "Law of Mass Action" - are re-examined for reversible \textit{diffusion-limited} reactions (DLR), as exemplified here by association/dissociation $A+A \rightleftharpoons B$ reactions. We consider a general model of long-ranged reactions, such that any pair of $A$ particles, separated by distance $\mu$, may react with probability $\omega_+(\mu)$, and any $B$ may dissociate with probability $\omega_-(\lambda)$ into a geminate pair of $A$s separated by distance $\lambda$. Within an exact analytical approach, we show that the asymptotic state attained by reversible DLR at $t = \infty$ is generally \textit{not a true thermodynamic equilibrium}, but rather a non-equilibrium steady-state, and that the Law of Mass Action is invalid. The classical picture holds \text{only} in physically unrealistic case when $\omega_+(\mu) \equiv \omega_-(\mu)$ for any value of $\mu$.Comment: 4 page

Monitoring the salt marsh vegetation and flora of the Baixo Vouga Lagunar (Ria of Aveiro, Portugal)

El carácter transicional de la Ría de Aveiro le confiere una riqueza florística singular, integrando comunidades vegetales típicas de las regiones Eurosiberiana y Mediterránea. La implantación del Proyecto Desenvolvimento Agrícola do Vouga (PDAV) va a provocar una modificación de las tasas de encharcamiento y una reducción gradual de la salinidad, factores ecológicos determinantes para muchas de las comunidades halófilas y helofíticas. El presente trabajo pretende contribuir a un mejor conocimiento de la tipología de la vegetación local, que sirva como base para desarrollar un programa de monitorización adecuado que detecte las alteraciones en los patrones espacio- temporales de la vegetación de los sistemas húmedos. Teniendo como objetivo seleccionar los puntos de muestreo donde instalar las parcelas permanentes de monitorización, se realizó una caracterización de la flora y la vegetación a través de trece transectos utilizando una aproximación simplificada al método de Braun- Blanquet. Una vez identificados los tipos de vegetación - en función de su composición florística, corología y ecología - fueron seleccionados al azar inventarios representativos de cada tipo, en los que han sido instaladas dichas parcelas.The transitional biogeographic character of the Ria de Aveiro lagoon area confers it a singular floristic richness, integrating plant communities typical for the Eurosiberian as well as Mediterranean Region. The implementation of the Agricultural Development Plan of the Lower Vouga area (PDAV) in the near future is expected to result in noticeable changes in the tidal submersion regime and a gradual reduction of salinity levels, which are determining ecological factors for many of the halophytic and helophytic plant communities. The present work pretends to contribute to a better knowledge of the local vegetation types and, thereby, to the implementation of an adequate monitoring programme for detecting changes in the spatio-temporal vegetation patterns of the wetlands. With the objective to select the locations for the installation of permanent quadrats, the vegetation of the wetlands was described along 13 transects using a simplified Braun-Blanquet approach. A total of 24 local vegetation types were recognised, 23 of which were selected for the current monitoring programme

Excess portal venous long-chain fatty acids induce syndrome X via HPA axis and sympathetic activation

We tested the hypothesis that excessive portal venous supply of long-chain fatty acids to the liver contributes to the development of insulin resistance via activation of the hypothalamus-pituitary-adrenal axis (HPA axis) and sympathetic system. Rats received an intraportal infusion of the long-chain fatty acid oleate (150 nmol/min, 24 h), the medium-chain fatty acid caprylate, or the solvent. Corticosterone (Cort) and norepinephrine (NE) were measured as indexes for HPA axis and sympathetic activity, respectively. Insulin sensitivity was assessed by means of an intravenous glucose tolerance test (IVGTT). Oleate infusion induced increases in plasma Cort (Δ = 13.5 ± 3.6 µg/dl; P < 0.05) and NE (Δ = 235 ± 76 ng/l; P < 0.05), whereas caprylate and solvent had no effect. The area under the insulin response curve to the IVGTT was larger in the oleate-treated group than in the caprylate and solvent groups (area = 220 ± 35 vs. 112 ± 13 and 106 ± 8, respectively, P < 0.05). The area under the glucose response curves was comparable [area = 121 ± 13 (oleate) vs. 135 ± 20 (caprylate) and 96 ± 11 (solvent)]. The results are consistent with the concept that increased portal free fatty acid is involved in the induction of visceral obesity-related insulin resistance via activation of the HPA axis and sympathetic system.

Magnetic Field Effects on Neutron Diffraction in the Antiferromagnetic Phase of UPt3UPt_3

We discuss possible magnetic structures in UPt$_3$ based on our analysis of elastic neutron-scattering experiments in high magnetic fields at temperatures $T<T_N$. The existing experimental data can be explained by a single-{\bf q} antiferromagnetic structure with three independent domains. For modest in-plane spin-orbit interactions, the Zeeman coupling between the antiferromagnetic order parameter and the magnetic field induces a rotation of the magnetic moments, but not an adjustment of the propagation vector of the magnetic order. A triple-{\bf q} magnetic structure is also consistent with neutron experiments, but in general leads to a non-uniform magnetization in the crystal. New experiments could decide between these structures.Comment: 5 figures included in the tex

Possible experiment to check the reality of a nonequilibrium temperature

An experiment is proposed to check the physical reality of a nonequilibrium absolute temperature previously proposed from theoretical grounds in the framework of extended irreversible thermodynamics

Steady State Thermodynamics of Langevin Systems

We study Langevin dynamics describing nonequilibirum steady states. Employing the phenomenological framework of steady state thermodynamics constructed by Oono and Paniconi [Prog. Theor. Phys. Suppl. {\bf130}, 29 (1998)], we find that the extended form of the second law which they proposed holds for transitions between steady states and that the Shannon entropy difference is related to the excess heat produced in an infinitely slow operation. A generalized version of the Jarzynski work relation plays an important role in our theory.Comment: 4 page

Awake craniotomy versus craniotomy under general anesthesia for the surgical treatment of insular glioma: choices and outcomes

Objective: To investigate differences in outcomes in patients who underwent surgery for insular glioma using an awake craniotomy (AC) vs. a craniotomy under general anesthesia (GA). Methods: Data from patients treated at our hospital between 2005 and 2015 were analyzed retrospectively. The preoperative, intraoperative, postoperative, and longer term follow-up characteristics and outcomes of patients who underwent surgery for primary insular glioma using either an AC or GA were compared. Results: Of the 52 identified patients, 24 had surgery using an AC and 28 had surgery under GA. The extent of resection was similar for the two anesthesia techniques: the median extent of resection was 61.4% (IQR: 37.8–74.3%) in the WHO grade <4 AC group vs. 50.5% (IQR: 35.0–71.2%) in the grade <4 GA group and 73.4

General Non-equilibrium Theory of Colloid Dynamics

A non-equilibrium extension of Onsager's canonical theory of thermal fluctuations is employed to derive a self-consistent theory for the description of the statistical properties of the instantaneous local concentration profile n(r,t) of a colloidal liquid in terms of the coupled time evolution equations of its mean value n(r,t) and of the covariance {\sigma}(r,r';t) \equiv of its fluctuations {\delta}n(r, t) = n(r, t) - n(r, t). These two coarse-grained equations involve a local mobility function b(r, t) which, in its turn, is written in terms of the memory function of the two-time correlation function C(r, r' ; t, t') \equiv <{\delta}n(r, t){\delta}n(r',t')>. For given effective interactions between colloidal particles and applied external fields, the resulting self-consistent theory is aimed at describing the evolution of a strongly correlated colloidal liquid from an initial state with arbitrary mean and covariance n^0(r) and {\sigma}^0(r,r') towards its equilibrium state characterized by the equilibrium local concentration profile n^(eq)(r) and equilibrium covariance {\sigma}^(eq)(r,r'). This theory also provides a general theoretical framework to describe irreversible processes associated with dynamic arrest transitions, such as aging, and the effects of spatial heterogeneities

Some thoughts about nonequilibrium temperature

The main objective of this paper is to show that, within the present framework of the kinetic theoretical approach to irreversible thermodynamics, there is no evidence that provides a basis to modify the ordinary Fourier equation relating the heat flux in a non-equilibrium steady state to the gradient of the local equilibrium temperature. This fact is supported, among other arguments, through the kinetic foundations of generalized hydrodynamics. Some attempts have been recently proposed asserting that, in the presence of non-linearities of the state variables, such a temperature should be replaced by the non-equilibrium temperature as defined in Extended Irreversible Thermodynamics. In the approximations used for such a temperature there is so far no evidence that sustains this proposal.Comment: 13 pages, TeX, no figures, to appear in Mol. Phy

Superconductivity in heavy-fermion U(Pt,Pd)3 and its interplay with magnetism

The effect of Pd doping on the superconducting phase diagram of the unconventional superconductor UPt3 has been measured by (magneto)resistance, specific heat, thermal expansion and magnetostriction. Experiments on single- and polycrystalline U(Pt1-xPdx)3 for x<= 0.006 show that the superconducting transition temperatures of the A phase, Tc+, and of the B phase, Tc-, both decrease, while the splitting DTc increases at a rate of 0.30(2)K/at.%Pd. We find that DTc(x) correlates with an increase of the weak magnetic moment m(x) upon Pd doping. This provides further evidence for Ginzburg-Landau scenarios with magnetism as the symmetry breaking field, i.e. the 2D E representation and the 1D odd parity model. Only for small splittings DTc is proportional to m^2(Tc+) (DTc<= 0.05 K) as predicted. The results at larger splittings call for Ginzburg-Landau expansions beyond 4th order. The tetracritical point in the B-T plane persists till at least x= 0.002 for B perpendicular to c, while it is rapidly suppressed for B||c. Upon alloying the A and B phases gain stability at the expense of the C phase.Comment: 25 pages text (PS), 8 pages with 14 figures (PS), submitted to Phys.Rev.