Absorption of schiff-base retinal chromophores in vacuo

The absorption spectrum of the all-trans retinal chromophore in the protonated Schiff-base form, that is, the biologically relevant form, has been measured in vacuo, and a maximum is found at 610 nm. The absorption of retinal proteins has hitherto been compared to that of protonated retinal in methanol, where the absorption maximum is at 440 nm. In contrast, the new gas-phase absorption data constitute a well-defined reference for spectral tuning in rhodopsins in an environment devoid of charges and dipoles. They replace the misleading comparison with absorption properties in solvents and lay the basis for reconsidering the molecular mechanisms of color tuning in the large family of retinal proteins. Indeed, our measurement directly shows that protein environments in rhodopsins are blue- rather than red shifting the absorption. The absorption of a retinal model chromophore with a neutral Schiff base is also studied. The data explain the significant blue shift that occurs when metharhodopsin I becomes deprotonated as well as the purple-to-blue transition of bacteriorhodopsin upon acidification.     

Oxidation of dimethyl ether: Absolute rate constants for the self reaction of CH3OCH2 radicals,the reaction of CH3OCH2 radicals with O2, and the thermal decomposition of CH3OCH2 radicals

The rate constant for the reaction of CH₃OCH₂ radicals with O₂ (reaction (1)) and the self reaction of CH₃OCH₂ radicals (reaction (5)) were measured using pulse radiolysis coupled with time resolved UV absorption spectroscopy. k₁ was studied at 296K over the pressure range 0.025–1 bar and in the temperature range 296–473K at 18 bar total pressure. Reaction (1) is known to proceed through the following mechanism: CH₃OCH₂ + O₂ ↔ CH₃OCH₂O₂^# → CH₂OCH₂O₂H^# → 2HCHO + OH (k_prod) CH₃OCH₂ + O₂ ↔ CH₃OCH₂O₂^# + M → CH₃OCH₂O₂ + M (k_RO2) k = k_RO2 + k_prod, where k_RO2 is the rate constant for peroxy radical production and k_prod is the rate constant for formaldehyde production. The k₁ values obtained at 296K together with the available literature values for k₁ determined at low pressures were fitted using a modified Lindemann mechanism and the following parameters were obtained: k_RO2,0 = (9.4 ± 4.2) × 10⁻³⁰ cm⁶ molecule⁻² s⁻¹, k_RO2,∞ = (1.14 ± 0.04) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹, and k_prod,0 = (6.0 ± 0.5) × 10⁻¹² cm³ molecule⁻¹ s⁻¹, where k_RO2,0 and k_RO2,∞ are the overall termolecular and bimolecular rate constants for formation of CH₃OCH₂O₂ radicals and k_prod,0 represents the bimolecular rate constant for the reaction of CH₃OCH₂ radicals with O₂ to yield formaldehyde in the limit of low pressure. k_RO2,∞ = (1.07 ± 0.08) × 10⁻¹¹ exp(−(46 ± 27)/T) cm³ molecule⁻¹ s⁻¹ was determined at 18 bar total pressure over the temperature range 296–473K. At 1 bar total pressure and 296K, k₅ = (4.1 ± 0.5) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ and at 18 bar total pressure over the temperature range 296–523K, k₅ = (4.7 ± 0.6) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹. As a part of this study the decay rate of CH₃OCH₂ radicals was used to study the thermal decomposition of CH₃OCH₂ radicals in the temperature range 573–666K at 18 bar total pressure. The observed decay rates of CH₃OCH₂ radicals were consistent with the literature value of k₂ = 1.6 × 10¹³exp(−12800/T)s⁻¹. The results are discussed in the context of dimethyl ether as an alternative diesel fuel. © 1997 John Wiley & Sons, Inc.     

Synthesis of linear and three-arm star tert-chlorine-telechelic polyisobutylenes by a two-step conventional laboratory process

A two-step conventional laboratory process was developed for the synthesis of mono- and difunctional linear and three-arm star tert-chlorine-telechelic polyisobutylenes (PIB) with desired molecular weights (MW) and narrow molecular weight distribution (MWD) by living carbocationic polymerization (LCCP). This polymerization method applies easy to handle operations and chemicals. LCCP of isobutylene (IB), was carried out in CH₂Cl₂ as solvent and with BCl₃ as coinitiator in the first step to obtain soluble low MW PIB prepolymer with narrow MWD. This was followed by addition of hexane, TiCl₄ and additional monomer in the second step to prepare PIBs with desired MW and narrow MWD in practically any suitable MW region. Comparison of the one-step and two-step processes is also described.     

Diophantine exponents for mildly restricted approximation

We are studying the Diophantine exponent μ _n,l defined for integers 1≤l<n and a vector α∈ℝ ⁿ by letting

Normalizers of maximal tori

Normalizers and p-normalizers of maximal tori in p-compact groups can be characterized by the Euler characteristic of the associated homogeneous spaces. Applied to centralizers of elementary abelian p-groups these criteria show that the normalizer of a maximal torus of the centralizer is given by the centralizer of a preferred homomorphism to the normalizer of the maximal torus; i.e. that “normalizer” commutes with “centralizer”. Received April 1, 1995; in final form August 11, 1997     

Implementation of parallel branch-and-bound algorithms – experiences with the graph partitioning problem

Parallel processing is one of the essential concepts in the attempts to increase the computational power available for solving continuous and discrete optimization problems. In the case where an optimization algorithm is search-based, crucial issues of parallel distributed implementations are work-load distribution and granularity, i.e. how to distribute the search space among processors and how to control the amount of processing between interprocessor communication. The present paper compares distributed implementations of two branch-and-bound algorithms for the graph partitioning problem: Given an undirected graph with an even number of edges and weights assigned to each edge, partition the vertices into two subsets of equal size such that the sum of the costs of edges connecting vertices in different subsets is as small as possible. The problem is known to be NP-complete. The two branch-and-bound methods compared differ in design strategy: One is based on time-consuming bound calculations leading to tight bounds and thus a narrow search tree with few nodes, whereas the other employs an easy bound calculation scheme leading to a larger search tree. Both have been implemented on an iPSC-hypercube with 32 processors. We investigate the influence of the design strategy on the performance of the algorithms.     

Gearing up for optical microrobotics: micromanipulation and actuation of synthetic microstructures by optical forces

Optics is usually integrated into robotics as part of intelligent vision systems. At the microscale, however, optical forces can cause significant acceleration and so optical trapping and optical manipulation can enable the noncontact actuation of microcomponents. Microbeads are ubiquitous optically actuated structures, from Ashkin's pioneering experiments with polystyrene beads to contemporary functionalized beads for biophotonics. However, micro‐ and nanofabrication technologies are yielding a host of novel synthetic structures that promise alternative functionalities and new exciting applications. Recent works on the actuation of synthetic microstructures using optical trapping and optical manipulation are examined in this review. Extending the optical actuation down to the nanoscale is also presented, which can involve either direct manipulation of nanostructures or structure‐mediated approaches where the nanostructures form part of larger structures that are suitable for interfacing with diffraction‐limited optical fields.