Visual pigments. V. Ground and excited-state acid dissociation constants of protonated all-trans retinal schiff base and correlation with theory.

Abstract— The acid dissociation constants of protonated all-trans retinal Schiff base (SB-H⁺) in a 50% water-methanol solution at 0°C is 6–95 for the ground state and nominally 16–65 for the first excited singlet state, with a potential range of ? 12–21. These values are in qualitative agreement with the results of semiempirical MO calculations, which indicate that the total charge density on nitrogen is greater in the first excited singlet than in the ground state (Q_N* > Q_N). However, pertinent to vision, CNDO/2 calculations on all-trans and 11-cis Schiff base and SB-H⁺ indicate that, for torsional angles of approximately 80–100° around the 11–12 double bond, Q_N* < Q_N. This result suggests that it may be possible for the proton to come off the imine nitrogen during isomerization from 11 -cis SB-H⁺ to all-trans SB-H⁺. The potential consequence of this during isomerization of rhodopsin is the initiation of unfolding of the protein opsin.     

Thiol- and thioether-based bifunctional chelates for the {M(CO)3}+ core (M = Tc, Re)

By analogy to the recently described single amino acid chelate (SAAC) technology for complexation of the {M(CO)3}+ core (M = Tc, Re), a series of tridentate ligands containing thiolate and thioether groups, as well as amino and pyridyl nitrogen donors, have been prepared: (NC5H4CH2)2NCH2CH2SEt (L1); (NC5H4CH2)2NCH2CH2SH (L2); NC5H4CH2N(CH2CH2SH)2 (L3); (NC5H4CH2)N(CH2CH2SH)(CH2CO2R) [R = H (L4); R = -C2H5 (L5). The {Re(CO)3}+ core complexes of L1-L5 were prepared by the reaction of [Re(CO)3(H2O)3]Br or [NEt4]2[Re(CO)3Br3] with the appropriate ligand in methanol and characterized by infrared spectroscopy, 1H and 13C NMR spectroscopy, mass spectrometry, and in the case of [Re(CO)3(L2)] (Re-2) and [Re(CO)3(L1)Re(CO)3Br2] (Re-1a) by X-ray crystallography. The structure of Re-2 consists of discrete neutral monomers with a fac-Re(CO)3 coordination unit and the remaining coordination sites occupied by the amine, pyridyl, and thiolate donors of L2, leaving a pendant pyridyl arm. In contrast, the structure of Re-1a consists of discrete binuclear units, constructed from a {Re(CO)3(L1)}+ subunit linked to a {Re(CO)3Br2}- group through the sulfur donor of the pendant thioether arm. The series of complexes establishes that thiolate donors are effective ligands for the {M(CO)3}+ core and that a qualitative ordering of the coordination preferences of the core may be proposed: pyridyl nitrogen approximately thiolate > carboxylate > thioether sulfur > thiophene sulfur. The ligands L1 and L2 react cleanly with [99mTc(CO)3(H2O)3]+ in H2O/DMSO to give [99mTc(CO)3(L1)]+ (99m)Tc-1) and [99mTc(CO)3(L2)] (99mTc-2), respectively, in ca. 90% yield after HPLC purification. The Tc analogues 99mTc-1 and 99mTc-2 were subjected to ligand challenges by incubating each in the presence of 1000-fold excesses of both cysteine and histidine. The radiochromatograms showed greater than 95% recovery of the complexes.     

Determination of the branching ratiosΓ(K L→3π0)/Γ(K L→π+ - 0) andΓ(K L→3π0)/Γ(K L→πev)

Improved branching ratios were measured for theK _L3⁰ decay in a neutral beam at the CERN SPS with the NA31 detector:

230 and 492 GHz low noise sis waveguide receivers employing tuned Nb/AlOx/Nb tunnel junctions

We report results on two full height waveguide receivers that cover the 200–290 GHz and 380–510 GHz atmospheric windows. The receivers are part of the facility instrumentation at the Caltech Submillimeter Observatory on Mauna Kea in Hawaii. We have measured receiver noise temperatures in the range of 20K–35K DSB in the 200–290 GHz band, and 65–90K DSB in the 390–510 GHz atmospheric band. In both instances low mixer noise temperatures and very high quantum efficiency have been achieved. Conversion gain (3 dB) is possible with the 230 GHz receiver, however lowest noise and most stable operation is achieved with unity conversion gain.A 40% operating bandwidth is achieved by using a RF compensated junction mounted in a two-tuner full height waveguide mixer block. The tuned Nb/AlO _x /Nb tunnel junctions incorporate an end-loaded tuning stub with two quarter-wave transformer sections to tune out the large junction capacitance. Both 230 and 492 GHz SIS junctions are 0.49µm² in size and have current densities of 8 and 10 kA/cm² respectively.Fourier Transform Spectrometer (FTS) measurements of the 230 and 492 GHz tuned junctions show good agreement with the measured heterodyne waveguide response.     

Fission fragment angular distributions in 16O+181Ta

Time of flight and energy of fission fragments were measured using pulsed beam. Fission fragment mass and energy integrated angular distributions were extracted. Fission fragment anisotropy was explained in the framework of saddle point model.     

Bulk heating of transparent materials using a high-repetition-rate femtosecond laser

Femtosecond laser pulses can locally induce structural and chemical changes in the bulk of transparent materials, opening the door to the three-dimensional fabrication of optical devices. We review the laser and focusing parameters that have been applied to induce these changes and discuss the different physical mechanisms that play a role in forming them. We then describe a new technique for inducing refractive-index changes in bulk material using a high-repetition-rate femtosecond oscillator. The changes are caused by a localized melting of the material, which results from an accumulation of thermal energy due to nonlinear absorption of the high-repetition-rate train of laser pulses. Received: 21 November 2001 / Accepted: 9 July 2002 / Published online: 25 October 2002 RID="*" ID="*"Corresponding author. Fax: +1-858/534-7697, E-mail: cschaffer@ucsd.edu RID="**" ID="**"Current address: University of California, San Diego, Department of Physics, La Jolla, CA 92 093, USA