Rates and Equilibria for a Photoisomerizable Antagonist at the Acetylcholine Receptor of Electrophorus Electroplaques

Voltage-jump and light-flash experiments have been performed on isolated Electrophorus electroplaques exposed simultaneously to nicotinic agonists and to the photoisomerizable compound 2,2'-bis-[α-(trimethylammonium)methyl]-azobenzene (2BQ). Dose-response curves are shifted to the right in a nearly parallel fashion by 2BQ, which suggests competitive antagonism; dose-ratio analyses show apparent dissociation constants of 0.3 and 1 µM for the cis and trans isomers, respectively. Flash-induced trans → cis concentration jumps produce the expected decrease in agonist-induced conductance; the time constant is several tens of milliseconds. From the concentration dependence of these rates, we conclude that the association and dissociation rate constants for the cis-2BQ-receptor binding are approximately ~ 10^8 M^(-1) s^(-1) and 60 s^(-1) at 20ºC; the Q_(10) is 3. Flash-induced cis → trans photoisomerizations produce molecular rearrangements of the ligand-receptor complex, but the resulting relaxations probably reflect the kinetics of buffered diffusion rather than of the interaction between trans-2BQ and the receptor. Antagonists seem to bind about an order of magnitude more slowly than agonists at nicotinic receptors

A covalently bound photoisomerizable agonist. Comparison with reversibly bound agonists at electrophorus electroplaques

After disulphide bonds are reduced with dithiothreitol, trans-3-(alpha-bromomethyl)-3’-[alpha-(trimethylammonium)methyl]azobenzene (trans-QBr) alkylates a sulfhydryl group on receptors. The membrane conductance induced by this “tethered agonist” shares many properties with that induced by reversible agonists. Equilibrium conductance increases as the membrane potential is made more negative; the voltage sensitivity resembles that seen with 50 [mu]M carbachol. Voltage- jump relaxations follow an exponential time-course; the rate constants are about twice as large as those seen with 50 mu M carbachol and have the same voltage and temperature sensitivity. With reversible agonists, the rate of channel opening increases with the frequency of agonist-receptor collisions: with tethered trans-Qbr, this rate depends only on intramolecular events. In comparison to the conductance induced by reversible agonists, the QBr-induced conductance is at least 10-fold less sensitive to competitive blockade by tubocurarine and roughly as sensitive to “open-channel blockade” bu QX-222. Light-flash experiments with tethered QBr resemble those with the reversible photoisomerizable agonist, 3,3’,bis-[alpha-(trimethylammonium)methyl]azobenzene (Bis-Q): the conductance is increased by cis {arrow} trans photoisomerizations and decreased by trans {arrow} cis photoisomerizations. As with Bis-Q, ligh-flash relaxations have the same rate constant as voltage-jump relaxations. Receptors with tethered trans isomer. By comparing the agonist-induced conductance with the cis/tans ratio, we conclude that each channel’s activation is determined by the configuration of a single tethered QBr molecule. The QBr-induced conductance shows slow decreases (time constant, several hundred milliseconds), which can be partially reversed by flashes. The similarities suggest that the same rate-limiting step governs the opening and closing of channels for both reversible and tethered agonists. Therefore, this step is probably not the initial encounter between agonist and receptor molecules

Lattice dynamics and structural stability of ordered Fe3Ni, Fe3Pd and Fe3Pt alloys

We investigate the binding surface along the Bain path and phonon dispersion relations for the cubic phase of the ferromagnetic binary alloys Fe3X (X = Ni, Pd, Pt) for L12 and DO22 ordered phases from first principles by means of density functional theory. The phonon dispersion relations exhibit a softening of the transverse acoustic mode at the M-point in the L12-phase in accordance with experiments for ordered Fe3Pt. This instability can be associated with a rotational movement of the Fe-atoms around the Ni-group element in the neighboring layers and is accompanied by an extensive reconstruction of the Fermi surface. In addition, we find an incomplete softening in [111] direction which is strongest for Fe3 Ni. We conclude that besides the valence electron density also the specific Fe-content and the masses of the alloying partners should be considered as parameters for the design of Fe-based functional magnetic materials.Comment: Revised version, accepted for publication in Physical Review

Association Between Long-Term Cognitive Decline in Vietnam Veterans With TBI and Caregiver Attachment Style.

OBJECTIVE: To examine whether a caregiver's attachment style is associated with patient cognitive trajectory after traumatic brain injury (TBI). SETTING: National Institute of Neurological Disorders and Stroke, National Institutes of Health, Bethesda, Maryland. PARTICIPANTS: Forty Vietnam War veterans with TBI and their caregivers. MAIN OUTCOME MEASURE: Cognitive performance, measured by the Armed Forces Qualification Test percentile score, completed at 2 time points: preinjury and 40 years postinjury. DESIGN: On the basis of caregivers' attachment style (secure, fearful, preoccupied, dismissing), participants with TBI were grouped into a high or low group. To examine the association between cognitive trajectory of participants with TBI and caregivers' attachment style, we ran four 2 × 2 analysis of covariance on cognitive performances. RESULTS: After controlling for other factors, cognitive decline was more pronounced in participants with TBI with a high fearful caregiver than among those with a low fearful caregiver. Other attachment styles were not associated with decline. CONCLUSION AND IMPLICATION: Caregiver fearful attachment style is associated with a significant decline in cognitive status after TBI. We interpret this result in the context of the neural plasticity and cognitive reserve literatures. Finally, we discuss its impact on patient demand for healthcare services and potential interventions

Magnetoelastic effects in Jahn-Teller distorted CrF2_2 and CuF2_2 studied by neutron powder diffraction

We have studied the temperature dependence of crystal and magnetic structures of the Jahn-Teller distorted transition metal difluorides CrF$_2$ and CuF$_2$ by neutron powder diffraction in the temperature range 2-280 K. The lattice parameters and the unit cell volume show magnetoelastic effects below the N\'eel temperature. The lattice strain due to the magnetostriction effect couples with the square of the order parameter of the antiferromagnetic phase transition. We also investigated the temperature dependence of the Jahn-Teller distortion which does not show any significant effect at the antiferromagnetic phase transition but increases linearly with increasing temperature for CrF$_2$ and remains almost independent of temperature in CuF$_2$. The magnitude of magnetovolume effect seems to increase with the low temperature saturated magnetic moment of the transition metal ions but the correlation is not at all perfect

The influence of brazilian soils properties in Americium sorption.

Although some radioecological studies have been accomplished in Brazilian soils supplying useful information to optimization of emergency planning actions in rural areas and to the management of soils contaminated by 137Cs, 60Co and 90Sr, few studies were made with transuranic elements in tropical agricultural areas. The different scenarios found in Brazilian agricultural environments enhance the importance of studying the biogeochemical behavior of radionuclides in representative soils. The objective of this work was to determine the mobility of 241Am in 3 different Brazilian agricultural soils evaluating migration with depth and Kd values for 241Am and the effect of organic amendments on this behavior. A strong effect of organic amendments on mobility of americium could be observed. The values of Kd obtained in all studied tropical soils were however smaller than those found in European soils and from those recommended by IAEA to be used as default values in the absence of regional data. This result reinforces the vulnerability of some tropical soils to a contamination, emphasizing the need to use of regional values

Evolution and stability of a magnetic vortex in small cylindrical ferromagnetic particle under applied field

The energy of a displaced magnetic vortex in a cylindrical particle made of isotropic ferromagnetic material (magnetic dot) is calculated taking into account the magnetic dipolar and the exchange interactions. Under the simplifying assumption of small dot thickness the closed-form expressions for the dot energy is written in a non-perturbative way as a function of the coordinate of the vortex center. Then, the process of losing the stability of the vortex under the influence of the externally applied magnetic field is considered. The field destabilizing the vortex as well as the field when the vortex energy is equal to the energy of a uniformly magnetized state are calculated and presented as a function of dot geometry. The results (containing no adjustable parameters) are compared to the recent experiment and are in good agreement.Comment: 4 pages, 2 figures, RevTe

Building block libraries and structural considerations in the self-assembly of polyoxometalate and polyoxothiometalate systems

Inorganic metal-oxide clusters form a class of compounds that are unique in their topological and electronic versatility and are becoming increasingly more important in a variety of applications. Namely, Polyoxometalates (POMs) have shown an unmatched range of physical properties and the ability to form structures that can bridge several length scales. The formation of these molecular clusters is often ambiguous and is governed by self-assembly processes that limit our ability to rationally design such molecules. However, recent years have shown that by considering new building block principles the design and discovery of novel complex clusters is aiding our understanding of this process. Now with current progress in thiometalate chemistry, specifically polyoxothiometalates (POTM), the field of inorganic molecular clusters has further diversified allowing for the targeted development of molecules with specific functionality. This chapter discusses the main differences between POM and POTM systems and how this affects synthetic methodologies and reactivities. We will illustrate how careful structural considerations can lead to the generation of novel building blocks and further deepen our understanding of complex systems

From conformal embeddings to quantum symmetries: an exceptional SU(4) example

We briefly discuss several algebraic tools that are used to describe the quantum symmetries of Boundary Conformal Field Theories on a torus. The starting point is a fusion category, together with an action on another category described by a quantum graph. For known examples, the corresponding modular invariant partition function, which is sometimes associated with a conformal embedding, provides enough information to recover the whole structure. We illustrate these notions with the example of the conformal embedding of SU(4) at level 4 into Spin(15) at level 1, leading to the exceptional quantum graph E4(SU(4)).Comment: 22 pages, 3 color figures. Version 2: We changed the color of figures (ps files) in such a way that they are still understood when converted to gray levels. Version 3: Several references have been adde