A perturbed pK(a) at the binding site of the nicotinic acetylcholine receptor: implications for nicotine binding

A series of tethered quaternary ammonium derivatives of Tyr have been incorporated into the binding site of the nicotinic acetylcholine receptor (nAChR) using the in vivo nonsense suppression method, producing constitutively active (self-gating) receptors. We have incorporated primary, secondary, and tertiary amine tethered agonists to give receptors whose constitutive activity can be modulated by pH. Lowering the pH protonates the tethered amine, giving it a positive charge and allowing it to reversibly activate the receptor. Tertiary and secondary tethered amines, TyrO3T and TyrO3S, have been successfully incorporated at alpha149 in the nAChR. Constitutive currents at pH 5.5 are 6 times those at pH 9.0. The pKa of TyrO3T in the binding site appears to be 6 or lower, differing substantially from its pKa in solution ( approximately 9.3). This local pKa perturbation has substantial implications for pharmacological research on the nAChR: of the tertiary agonists considered, noracetylcholine experiences this pKa perturbation, while nicotine does not.     

Intrinsic fiber Fabry-Perot temperature sensor with fiber Bragg grating mirrors

A fiber Fabry-Perot interferometer (FFPI) sensor is formed with broadband (~3 nm, 3-dB bandwidth) fiber Bragg grating (FBG) mirrors. Repetitively modulating a distributed-feedback laser produces chirping that modulates the reflectance of the FFPI. Because the reflectance of the FBG mirrors varies with optical frequency, the fringes in the sensor reflectance modulation are distinguishable, making it possible to extend the sensor dynamic range versus that of a FFPI sensor with conventional wavelength-dependent mirrors. An ambient temperature is determined in the range from 25 to 170 degrees C with a resolution of 0.005 degrees C.     

Helium and point defect accumulation: (i) microstructure and mechanical behaviour

Ferritic/martensitic (F/M) steels are good candidate structural materials for the future fusion reactors and spallation sources. However, irradiation of steels is known to produce hardening, loss of ductility, shift in ductile to brittle transition temperature (DBTT) and reduction of fracture toughness and creep resistance starting at low doses. Helium (He), produced by transmutation during the irradiation, also impacts mechanical properties. Numerous experimental and theoretical studies on the evolution of the microstructure of steels under irradiation have been conducted until now. We review the effect of irradiation-induced point defects and in particular of He on the mechanical properties of F/M steels. To cite this article: R. Schäublin et al., C. R. Physique 9 (2008).     

6,7‐diaza‐1‐methoxy‐ 5‐methyl‐2, 8‐dioxabicyclo[3.2.1]oct‐6‐ene. An unstable bicyclic precursor of a dioxa carbonyl ylide and carbenes by ylide ring opening

Synthesis of a bicyclic 2,2‐dioxa oxadiazoline (6,7‐diaza‐1‐methoxy‐5‐methyl‐2,8‐dioxabicyclo[3.2.1]oct‐6‐ene) is reported. Its thermolysis at 27°C is about 200 times as fast as the thermolysis of a monocyclic oxadiazoline model system. Presumably, a cyclic dioxa carbonyl ylide is formed initially and the ylide then undergoes a bond scission to afford either a dioxacarbene or a dialkylcarbene or it cyclizes to an oxirane. A small fraction of a dialkylcarbene was trapped as the product of addition to dimethyl acetylenedicarboxylate (DMAD). Computations of the barriers to the loss of N₂ from the oxadiazolines and to the formation of the carbenes from the carbonyl ylide resulting from thermolysis of the bicyclic oxadiazoline are compared to corresponding barriers for a similar monocyclic oxadiazoline. The rate acceleration is accounted for in terms of geometric factors. The complex products from the decomposition of the bicyclic oxadiazoline were not studied. Copyright © 2007 John Wiley & Sons, Ltd.     

Electrochemical determination of reduction potentials in glass-forming melts

Square-wave voltammetry (SWV) has been used to determine the reduction potentials of several multivalent elements in situ in an alkali borosilicate melt. Such reduction potentials measured at melt temperature were found to be proportional to the relative reduction potentials obtained from analyses of the quenched glasses. Accordingly, the redox state of the glass typically reflects the redox state of the melt. Although SWV is a sensitive tool for monitoring the total concentration of specific multivalent elements in the melt, the method does not directly monitor the redox state of the melt.     

Limitation of Auger electron spectroscopy in the determination of the metal-on-oxide growth mode: Pd on MgO(100)

A discussion on the use of Auger electron spectroscopy as a quantitative tool to determine the growth mode of metals on single crystal oxide surfaces is presented. In the case of Pd grown epitaxially on MgO(100), the three-dimensional character of the growth is easily seen at coverage above one monolayer. However, in the submonolayer regime, and mainly at low substrate temperatures, the AES results are ambiguous. The combination of AES with the more sensitive helium-atom diffraction method allows us to demonstrate that the growth is three-dimensional from the early stages, the particles becoming flatter when the substrate temperature decreases. We compare our results with other growth studies on different metal/oxide systems. At low temperature, the ideal growth modes are not always observed, the final morphology of the films being determined mainly by kinetic effects. Thus a pseudo-Stranski-Krastanov growth mode is often obtained with formation of 2D islands followed by 3D clustering from a critical submonolayer coverage.     

Two-phase pressure drop with twisted-tape swirl generators

An experimental study has been conducted to determine the effect of twisted-tape swirl generators on adiabatic and diabatic two-phase flow pressure drops in vertical straight tubes. Tape-twist ratios (length for 180° twist/inside tube diameter) of 3.94, 8.94, and 13.92 were tested with R-113 over a range of pressures, mass velocities, qualities, and heat fluxes. Empty tube refcrence data were successfully predicted with a correlation from the literature. The twisted tape data were successfully correlated by using the hydraulic diameter and a single-phase swirl flow friction factor in the empty tube correlation. Data from the literature also were predicted well with this correlation.     

Measurement and interpretation of the 1-0 band of 14N16O at 1900 cm−1

The wavenumbers of the vibration rotation band lines of ¹⁴N¹⁶O are reported for the ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{-}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ subbands of the 1-0 transition in the infrared. The full set of spectroscopic constants for this band has been determined by direct approach using the analysis of Zare, Schmeltekopf, Harrop, and Albritton. In addition to the band origin ν₀ and the B, D, H constants for the lower and upper vibrational levels, the following spin-orbit coupling constants have been derived: $\text{A}\text{?}{}_0\text{= 123.02772 ± 0.00011}$ and $\text{A}\text{?}{}_1\text{= 122.78248 ± 0.00011}$ (in cm^?1). Apparent centrifugal corrections to these constants have been determined and the values obtained for them are $\text{A}\text{?}{}_{\mathrm{<mtext>D</mtext><mtext>0</mtext>}}\text{= (0.347573 ± 0.00051) × 10}{}^{\mathrm{?3}}$ and $\text{A}\text{?}{}_{\mathrm{<mtext>D</mtext><mtext>1</mtext>}}\text{= (0.337135 ± 0.00050) × 10}{}^{\mathrm{?3}}\text{cm}{}^{\mathrm{?1}}$. Λ-Type doubling constants evaluated by using both grating and tunable laser data are also reported.