Hole Hopping Across a Protein-Protein Interface.

We have investigated photoinduced hole hopping in a Pseudomonas aeruginosa azurin mutant Re126WWCuI, where two adjacent tryptophan residues (W124 and W122) are inserted between the CuI center and a Re photosensitizer coordinated to a H126 imidazole (Re = ReI(H126)(CO)3(dmp)+, dmp = 4,7-dimethyl-1,10-phenanthroline). Optical excitation of this mutant in aqueous media (//(CuII)' back ET that occurs over 12 Å, in contrast to the 23 Å, 120 us step in Re126WWCuI. Importantly, dimerization makes Re126FWCuI photoreactive and, in the case of {Re126WWCuI}2, channels the photoproduced "hole" to the molecule that was not initially photoexcited, thereby shortening the lifetime of ReI(H126)(CO)3(dmp•-)//CuII. Whereas two adjacent W124 and W122 indoles dramatically enhance CuI->*Re intramolecular multistep ET, the tryptophan quadruplex in {Re126WWCuI}2 does not accelerate intermolecular electron transport; instead, it acts as a hole storage and crossover unit between inter- and intramolecular ET pathways. Irradiation of {Re126WWCuII}2 or {Re126FWCuII}2 also triggers intermolecular *Re////(W122•+)' intermolecular charge recombination. Our findings shed light on the factors that control interfacial hole/electron hopping in protein complexes and on the role of aromatic amino acids in accelerating long-range electron transport

Diagnostic relevance of spatial orientation for vascular dementia: A case study

Background: Spatial orientation is emerging as an early and reliable cognitive biomarker of Alzheimer’s disease (AD) pathophysiology. However, no evidence exists as to whether spatial orientation is also affected in vascular dementia (VaD). Objective: To examine allocentric (map-based) and egocentric (viewpoint-based) spatial orientation in an early stage VaD case. Methods: A spatial test battery was administered following clinical and neuropsychological cognitive evaluation. Results: Despite the patient’s complaints, little evidence of episodic memory deficits were detected when cueing was provided to overcome executive dysfunction. Similarly, medial temporal lobe-mediated allocentric orientation was intact. By contrast, medial parietal-mediated egocentric orientation was impaired, despite normal performance on standard visuospatial tasks. Conclusion: To our knowledge, this is the first in-depth investigation of spatial orientation deficits in VaD. Isolated egocentric deficits were observed. This differs from AD orientation deficits which encompass both allocentric and egocentric orientation deficits. A combination of egocentric orientation and executive function tests could serve as a promising cognitive marker for VaD pathophysiology

Two Tryptophans Are Better Than One in Accelerating Electron Flow through a Protein

We have constructed and structurally characterized a <i>Pseudomonas aeruginosa</i> azurin mutant <b>Re126WWCu^I</b>, where two adjacent tryptophan residues (W124 and W122, indole separation 3.6–4.1 Å) are inserted between the Cu^I center and a Re photosensitizer coordinated to the imidazole of H126 (Re^I(H126)­(CO)₃(4,7-dimethyl-1,10-phenanthroline)⁺). Cu^I oxidation by the photoexcited Re label (*Re) 22.9 Å away proceeds with a ∼70 ns time constant, similar to that of a single-tryptophan mutant (∼40 ns) with a 19.4 Å Re–Cu distance. Time-resolved spectroscopy (luminescence, visible and IR absorption) revealed two rapid reversible electron transfer steps, W124 → *Re (400–475 ps, <i>K</i>₁ ≅ 3.5–4) and W122 → W124^•+ (7–9 ns, <i>K</i>₂ ≅ 0.55–0.75), followed by a rate-determining (70–90 ns) Cu^I oxidation by W122^•+ ca. 11 Å away. The photocycle is completed by 120 μs recombination. No photochemical Cu^I oxidation was observed in <b>Re126FWCu^I</b>, whereas in <b>Re126WFCu^I</b>, the photocycle is restricted to the ReH126W124 unit and Cu^I remains isolated. QM/MM/MD simulations of <b>Re126WWCu^I</b> indicate that indole solvation changes through the hopping process and W124 → *Re electron transfer is accompanied by water fluctuations that tighten W124 solvation. Our finding that multistep tunneling (hopping) confers a ∼9000-fold advantage over single-step tunneling in the double-tryptophan protein supports the proposal that hole-hopping through tryptophan/tyrosine chains protects enzymes from oxidative damage

Heterostructures for Optical Devices

Contains research objectives and reports on eight research projects.Joint Services Electronics Program (Contract DAAL03-86-K-0002)Joint Services Electronics Program (Contract DAALO3-89-C-0001)National Science Foundation (Grant EET 87-03404)Charles Stark Draper Laboratory (Contract DL-H-315251)Xerox Corporation FellowshipMIT Fund

Heterostructures for High Performance Devices

Contains an introduction, reports on thirteen research projects and a list of publications.Charles S. Draper Laboratory Contract DL-H-418483DARPA/NCIPT Subcontract 542383Joint Services Electronics Program Contract DAAL03-89-C-0001IBM Corporation FellowshipNational Science Foundation FellowshipVitesse SemiconductorAT&T Bell LaboratoriesHertz Foundation FellowshipNational Science FoundationTRWBelgian American Education Foundation (BAEF) FellowshipNational Science Foundation Grant ECS 90-08485Harvard University. Division of Applied PhysicsAT&T Bell Laboratories FellowshipNational Science Foundation Grant ECS 90-0774

Heterostructures for High Performance Devices

Contains an introduction and reports on ten research projects.Charles S. Draper Laboratory, Contract DL-H-315251Joint Services Electronics Program, Contract DAAL03-89-C-0001National Science Foundation Grant, Grant EET 87-03404MIT FundsInternational Business Machines CorporationNational Science Foundation Grant ECS 84-1317

Heterostructures for High Performance Devices

Contains table of contents for Part I, table of contents for Section 1, an introduction, reports on eighteen research projects and a list of publications.Charles S. Draper Laboratories Contract DL-H-418483DARPA/NCIPTJoint Services Electronics Program Contract DAAL03-89-C-0001Joint Services Electronics Program Contract DAAL03-92-C-0001IBM Corporation FellowshipNational Science Foundation FellowshipVitesse SemiconductorGTE LaboratoriesCharles S. Draper LaboratoriesElectronics and Telecommunications Research Institute (ETRI) FellowshipNational Science Foundation/Northeastern UniversityTRW SystemsU.S. Army Research OfficeNational Science FoundationAT&T Bell Laboratories FellowshipNational Science Foundation Grant ECS 90-0774

Comparison of rhenium–porphyrin dyads for CO₂ photoreduction: photocatalytic studies and charge separation dynamics studied by time-resolved IR spectroscopy

We report a study of the photocatalytic reduction of CO₂ to CO by zinc porphyrins covalently linked to [ReI(2,2′-bipyridine)(CO)₃L]⁺/⁰ moieties with visible light of wavelength >520 nm. Dyad 1 contains an amide C₆H₄NHC(O) link from porphyrin to bipyridine (Bpy), Dyad 2 contains an additional methoxybenzamide within the bridge C₆H₄NHC(O)C₆H₃(OMe)NHC(O), while Dyad 3 has a saturated bridge C₆H₄NHC(O)CH₂; each dyad is studied with either L = Br or 3-picoline. The syntheses, spectroscopic characterisation and cyclic voltammetry of Dyad 3 Br and [Dyad 3 pic]OTf are described. The photocatalytic performance of [Dyad 3 pic]OTf in DMF/triethanolamine (5 : 1) is approximately an order of magnitude better than [Dyad 1 pic]PF₆ or [Dyad 2 pic]OTf in turnover frequency and turnover number, reaching a turnover number of 360. The performance of the dyads with Re–Br units is very similar to that of the dyads with [Re–pic]⁺ units in spite of the adverse free energy of electron transfer. The dyads undergo reactions during photocatalysis: hydrogenation of the porphyrin to form chlorin and isobacteriochlorin units is detected by visible absorption spectroscopy, while IR spectroscopy reveals replacement of the axial ligand by a triethanolaminato group and insertion of CO₂into the latter to form a carbonate. Time-resolved IR spectra of [Dyad 2 pic]OTf and [Dyad 3 pic]OTf (560 nm excitation in CH₂Cl₂) demonstrated electron transfer from porphyrin to Re(Bpy) units resulting in a shift of ν(CO) bands to low wavenumbers. The rise time of the charge-separated species for [Dyad 3 pic]OTf is longest at 8 (±1) ps and its lifetime is also the longest at 320 (±15) ps. The TRIR spectra of Dyad 1 Br and Dyad 2 Br are quite different showing a mixture of 3MLCT, IL and charge-separated excited states. In the case of Dyad 3 Br, the charge-separated state is absent altogether. The TRIR spectra emphasize the very different excited states of the bromide complexes and the picoline complexes. Thus, the similarity of the photocatalytic data for bromide and picoline dyads suggests that they share common intermediates. Most likely, these involve hydrogenation of the porphyrin and substitution of the axial ligand at rhenium