Calculation of exchange couplings in the electronically excited state of molecular three-spin systems

Photogenerated molecular three-spin systems, composed of a chromophore and a covalently bound stable radical, are promising candidates for applications in the field of molecular spintronics. Through excitation with light, an excited doublet state and a quartet state are generated, whereby their energy difference depends on the exchange interaction JTR between the chromophore triplet state (T) and the stable radical (R). In order to establish design rules for new materials to be used in molecular spintronics devices, it is of great importance to gain knowledge on the magnitude of JTR as well as the factors influencing JTR on a molecular level. Here, we present a robust and reliable computational method to determine excited state exchange couplings in three-electron-three-centre systems based on a CASSCF/QD-NEVPT2 approach. The methodology is benchmarked and then applied to a series of molecules composed of a perylene chromophore covalently linked to various stable radicals. We calculate the phenomenological exchange interaction JTR between chromophore and radical, which can be compared directly to the experiment, but also illustrate how the individual exchange interactions Jij can be extracted using an effective Hamiltonian that corresponds to the Heisenberg–Dirac–Van-Vleck Hamiltonian. The latter procedure enables a more detailed analysis of the contributions to the exchange interaction JTR and yields additional insight that will be invaluable for future design optimisation

Mean-field glass transition in a model liquid

We investigate the liquid-glass phase transition in a system of point-like particles interacting via a finite-range attractive potential in D-dimensional space. The phase transition is driven by an `entropy crisis' where the available phase space volume collapses dramatically at the transition. We describe the general strategy underlying the first-principles replica calculation for this type of transition; its application to our model system then allows for an analytic description of the liquid-glass phase transition within a mean-field approximation, provided the parameters are chosen suitably. We find a transition exhibiting all the features associated with an `entropy crisis', including the characteristic finite jump of the order parameter at the transition while the free energy and its first derivative remain continuous.Comment: 12 pages, 6 figure

Localization Properties of Two Interacting Electrons in a Disordered Quasi One-Dimensional Potential

We study the transport properties of two electrons in a quasi one-dimensional disordered wire. The electrons are subject to both, a disorder potential and a short range two-body interaction. Using the approach developed by Iida et al. [ Ann. Phys. (N.Y.) 200 (1990) 219 ], the supersymmetry technique, and a suitable truncation of Hilbert space, we work out the two-point correlation function in the framework of a non-linear sigma model. We study the loop corrections to arbitrary order. We obtain a remarkably simple and physically transparent expression for the change of the localization length caused by the two-body interaction.Comment: 10 page

Following microscopic motion in a two dimensional glass-forming binary fluid

The dynamics of a binary mixture of large and small discs are studied at temperatures approaching the glass transition using an analysis based on the topology of the Voronoi polygon surrounding each atom. At higher temperatures we find that dynamics is dominated by fluid-like motion that involves particles entering and exiting the nearest-neighbour shells of nearby particles. As the temperature is lowered, the rate of topological moves decreases and motion becomes localised to regions of mixed pentagons and heptagons. In addition we find that in the low temperature state particles may translate significant distances without undergoing changes in their nearest neig hbour shell. These results have implications for dynamical heterogeneities in glass forming liquids.Comment: 12 pages, 7 figure

Analysis of chronic rejection and obliterative arteriopathy: Possible contributions of donor antigen-presenting cells and lymphatic disruption

Sequential analysis of changes that lead to chronic rejection was undertaken in an animal model of chronic rejection and obliterative arteriopathy. Brown Norway rats are pretreated with a Lewis bone marrow infusion or a Lewis orthotopic liver allograft and a short course of immunosuppression. They are challenged 100 days later with a Lewis heterotopic heart graft without immunosuppression. The heart grafts in both groups undergo a transient acute rejection, but all rats are operationally tolerant; the heart grafts are accepted and remain beating for more than 100 days. Early arterial remodeling, marked by arterial bromodeoxyuridine incorporation, occurred in both groups between 5 and 30 days during the transient acute rejection. It coincided with the presence of interstitial (but not arterial intimal) inflammation and lymphatic disruption and resulted in mild intimal thickening. Significant arterial narrowing occurred only in the bone-marrow-pretreated rats between 60 and 100 days. It was associated with T lymphocyte and macrophage inflammation of the heart graft that accumulated in the endocardium and arterial intima and adventitia near draining lymphatics. There also was loss of passenger leukocytes from the heart graft, up-regulation of cytokine mRNA and major histocompatibility class II on the endothelium, and focal disruption of lymphatics. In contrast, long-surviving heart grafts from the Lewis orthotopic liver allograft pretreated group are near normal and freedom from chronic rejection in this group was associated with persistence of donor major histocompatibility class-II-positive hematolymphoid cells, including OX62+ donor dendritic cells. This study offers insights into two different aspects of chronic rejection: 1) possible mechanisms underlying the persistent immunological injury and 2) the association between immunological injury and the development of obliterative arteriopathy. Based on the findings, it is not unreasonable to raise the testable hypothesis that direct presentation of alloantigen by donor antigen-presenting cells is required for long-term, chronic-rejection-free allograft acceptance. In addition, chronic intermittent lymphatic disruption is implicated as a possible mechanism for the association between chronic interstitial allograft inflammation and the development of obliterative arteriopathy

Mitochondrial proteomics: analysis of a whole mitochondrial extract with two-dimensional electrophoresis

Mitochondria are complex organelles, and their proteomics analysis requires a combination of techniques. The emphasis in this chapter is made first on mitochondria preparation from cultured mammalian cells, then on the separation of the mitochondrial proteins with two-dimensional electrophoresis (2DE), showing some adjustment over the classical techniques to improve resolution of the mitochondrial proteins. This covers both the protein solubilization, the electrophoretic part per se, and the protein detection on the gels, which makes the interface with the protein identification part relying on mass spectrometry

Experimental search for dynamic heterogeneities in molecular glass formers

We have measured the linear dielectric susceptibility of two molecular glass formers close to Tg in order to estimate the size of the dynamically correlated clusters of molecules which are expected to govern the physics of glass formation. This size has been shown to be related to the dynamic dielectric susceptibility dEps(w)/dT (Eps : dielectric susceptibility, T : temperature, w&#61472;: frequency). To allow for an accurate determination of the T derivative, we scanned the interval 192 < T < 232 K every 1 K for glycerol and 159 < T < 179 K every 0.5 K for propylene carbonate. The resolution on T variations was about 1 mK. The result for glycerol is that the number of correlated molecules increases by a factor 3 when T goes from 226 to 195 K. It has been shown that the non-linear susceptibility provides a direct measurement of dynamic correlations. To measure it, we used a standard Lockin technique yielding the third harmonic of the current flowing out of a capacitor. We obtained only an upper limit on the ratio of the third to the first harmonic, due to the non-linear response of standard electronics.Comment: 7 page

Growth and Reproductive Development of Male Piglets Are More Vulnerable to Midgestation Maternal Stress Than That of Female Piglets

In many mammalian species, prenatal stress masculinizes female and feminizes male offspring impairing their reproductive capacity. Regrouping gestating sows is a common, stressful production practice, but its impact on the developing pigs of the sow is not fully known. This study examined the effects of regrouping gestating sows and the administration of exogenous glucocorticoids on the growth and external reproductive morphology of pigs. At 37.2 ± 0.26 d of gestation, 6 cohorts of 18 sows (N = 108) were placed in 1 of 3 treatments: socially stable (Stable), hydrocortisone acetate (HCA), or mixed (Mixed). The HCA sows were administered 70 mg HCA, a synthetic glucocorticoid, twice daily during the 21 d experimental period. Each Mixed sow was penned with 2 companion sows (Companion) and regrouped on d 7 and 14 with 2 different Companion sows in a new pen. Stable and HCA sows were penned in treatment groups of 3 sows. Sow social rank was assessed weekly during feeding. After the 21 d experimental period, all sows were housed in gestation stalls for the duration of pregnancy. During the 21 d, Companion sows gained more weight than HCA and Mixed sows (P \u3c 0.05) with Stable sows intermediate. High ranked sows gained more weight than middle and low ranked sows (P \u3c 0.05). Mixed sows had greater head lesion scores than Stable and HCA sows (P \u3c 0.05) with Companion sows intermediate. Head lesions increased with lower social rank (P \u3c 0.001). Sow treatment did not affect farrowing rate, litter size, or sex ratio (P \u3e 0.10). Social rank also had no effect on farrowing rate (P \u3e 0.10), but affected total litter size (P = 0.03). High ranked sows bore and weaned more live females than low ranked sows (P \u3c 0.05), in part due to differential preweaning mortality among female pigs (P = 0.01). Only male pigs were affected by sow treatment. Preweaning mortality was higher among male pigs from HCA than from Mixed sows (P = 0.04) with other treatments intermediate. Despite no weight differences in the preweaning period, at 160 d of age males from HCA sows weighed more than males from Stable sows (P = 0.01) with other treatments intermediate. Males born to Companion sows had longer relative anogenital distances, a marker of fetal testosterone exposure, than males from Mixed sows (P = 0.03) with other treatments intermediate. The prenatal environment affected the pigs in a sex-specific manner altering the growth and reproductive morphology of the males more than that of the females