Photochemistry of a retinal protonated schiff-base analogue mimicking the opsin shift of bacteriorhodopsin

A retinal Schiff base analogue which artificially mimics the protein-induced red shifting of absorption in bacteriorhodopsin (BR) has been investigated with femtosecond multichannel pump probe spectroscopy. The objective is to determine if the catalysis of retinal internal conversion in the native protein BR, which absorbs at 570 nm, is directly correlated with the protein-induced Stokes shifting of this absorption band otherwise known as the "opsin shift". Results demonstrate that the red shift afforded in the model system does not hasten internal conversion relative to that taking place in a free retinal-protonated Schiff base (RPSB) in methanol solution, and stimulated emission takes place with biexponential kinetics and characteristic timescales of approximately 2 and 10.5 ps. This shows that interactions between the prosthetic group and the protein that lead to the opsin shift in BR are not directly involved in reducing the excited-state lifetime by nearly an order of magnitude. A sub-picosecond phase of spectral evolution, analogues of which are detected in photoexcited retinal proteins and RPSBs in solution, is observed after excitation anywhere within the intense visible absorption band. It consists of a large and discontinuous spectral shift in excited-state absorption and is assigned to electronic relaxation between excited states, a scenario which might also be relevant to those systems as well. Finally, a transient excess bleach component that tunes with the excitation wavelength is detected in the data and tentatively assigned to inhomogeneous broadening in the ground state absorption band. Possible sources of such inhomogeneity and its relevance to native RPSB photochemistry are discussed.     

Application of microwave superheating for the synthesis of TiO2 rods

A simple microwave irradiation method for the large-scale synthesis of submicrometer-sized TiO2 rods at normal atmospheric pressure and the boiling temperature of the solvent is demonstrated. It is emphasized that only 1-3 min of microwave irradiation is adequate to react tetra-isopropyl orthotitanate with ethylene glycol to produce rods of titanium glycolate [TG] with diameters of approximately 0.4 microm and lengths up to 5 microm. The as-formed TG rods, followed by calcination under air for 2 h, fabricated anatase (500 degrees C) and rutile (900 degrees C) titania without changing their rod-shaped morphology. The crystallinity, structure, morphology, and thermal analysis are carried out by several techniques. A mechanism based on microwave superheating phenomena is presented with the support of previous reports and several control experiments.     

Thin stationary sets and disjoint club sequences

We describe two opposing combinatorial properties related to adding clubs to : the existence of a thin stationary subset of and the existence of a disjoint club sequence on . A special Aronszajn tree on implies there exists a thin stationary set. If there exists a disjoint club sequence, then there is no thin stationary set, and moreover there is a fat stationary subset of which cannot acquire a club subset by any forcing poset which preserves and . We prove that the existence of a disjoint club sequence follows from Martin's Maximum and is equiconsistent with a Mahlo cardinal.

     

Search for a bound trineutron with the 3He(π−pgr;+)nnn reaction

A search for the production of a bound trineutron state has been performed using the reaction ³He(π⁻,π⁺)nnn at incident pion energies of 65, 75, and 120 MeV. No evidence for the existence of the ³n was found, and an upper limit for the production cross section of approximately 30 nb/sr (2σ confidence level) was obtained. Received: 22 October 1998     

Changes in vocal intensity in Parkinson's disease following pallidotomy surgery

The present study was designed to examine changes in vocal intensity following unilateral posteroventral pallidotomy (PVP) in a large sample of speakers with Parkinson's disease (PD) that exhibited a range of hypokinetic dysarthria. Twenty-five persons with PD were recorded using a variety of speech tasks, once prior to and once following PVP. The pre-PVP vocal SPL was subtracted from the post-PVP vocal SPL to derive a relative change in vocal SPL. Mildly dysarthric participants had significantly greater relative increases in vocal SPL following PVP than either moderately or severely dysarthric participants who had reduced vocal SPL following PVP. If future results follow those observed in the present data, mildly dysarthric Parkinson's patients may benefit most from unilateral PVP perhaps due to less overall destruction of the basal ganglia sensorimotor control circuits involved in oral facial functions, thus increasing the chances to observe improvements postsurgery.     

Scaling units via the canonical correlation analysis in the DEA context

This paper deals with the evaluation of decision making units which have multiple inputs and outputs. A new method (CCA/DEA) is developed where the Canonical Correlation Analysis (CCA) is utilized to provide a full rank scaling for all the units rather than a categorical classification (for efficient and inefficient units) as done by the Data Envelopment Analysis (DEA). The CCA/DEA approach is an attempt to bridge the gap between the frontier approach of DEA and the average tendencies of statistics (econometrics). Nonparametric statistical tests are employed to validate the consistency between the classification from the DEA and the postclassification that was generated by the CCA/DEA.     

An Improved Method to Determine Particle Dispersion Width for Efficient Modeling of Turbulent Two‐Phase Flows

An improved approach is presented for the hybrid Eulerian‐Lagrangian modeling of turbulent two‐phase flows. The hybrid model consists of a nonlinear k–ε model for the fluid flow and an efficient Lagrangian trajectory model for the particulate flow. The improved approach avoids an empirical correlation required to determine the dispersion width for the existing Stochastic‐Probabilistic Efficiency Enhanced Dispersion (SPEED) model. The improved SPEED model is validated using experimental data for a poly‐dispersed water spray interacting with a turbulent annular air jet behind a bluff‐body. Numerical results for the number‐mean and Sauter‐mean droplet diameters, as well as mean and fluctuating droplet velocities are compared with the experimental data and with the predictions of other dispersion models. It is demonstrated that higher computational efficiency and smoother profiles of Sauter‐mean diameter can be obtained with the improved stochastic‐probabilistic model than with the eddy‐interaction model.     

The action of a few permutations on r-tuples is quickly transitive

We prove that for every r and d≥2 there is a C such that for most choices of d permutations π₁, π₂,…,π_d of S_n, the following holds: for any two r-tuples of distinct elements in {1,…,n}, there is a product of less than C log n of the π_is which map the first r-tuple to the second. Although we came across this problem while studying a rather unrelated cryptographic problem, it belongs to a general context of which random Cayley graph quotients of S_n are good expanders. © 1998 John Wiley & Sons, Inc. Random Struct. Alg., 12: 335–350, 1998     

Evaluation of matrix-assisted laser desorption ionization mass spectrometry for polymer characterization

A protocol for the preparation of polymeric samples for time-of-flight matrix-assisted laser desorption ionization mass spectrometry (TOF-MALDI-MS) analysis was developed. Dithranol was identified as a good matrix for polystyrene (PS), and the addition of silver for cationization of molecules was determined to be necessary. Based on this preparative method, low molecular weight samples of other polymers [polyisoprene, polybutadiene, poly(ethylene oxide), poly(methyl methacrylate), and polydimethylsiloxane] were analyzed with molecular weights up to 49 ku. The effects of laser intensity were determined to influence the molecular weight distribution of intact oligomers, most significantly for low molecular weight polymers. Linear and reflectron modes of analysis were evaluated; better signal intensity and resolution were obtained in the reflectron mode. The TOF-MALDI-MS measurements are compared with time-of-flight secondary ion mass spectrometry (TOF-SIMS) and gel permeation chromatography (GPC) for the same polymers. The M _n values calculated by TOF-MALDI-MS consistently are higher than values calculated by TOF-SIMS for all classes of polymers with molecular weights up to 8 ku. The molecular weights of the PS calculated from TOF-MALDI-MS are in good agreement with GPC (±10%). The composition of the terminal group on a polymer chain may affect the ion yields. The ion yields of intact oligomers were evaluated as a function of end group composition for both TOF-MALDI-MS and TOF-SIMS. The slight disparity of results between TOF-SIMS and TOF-MALDI-MS for the perfluoroalkyl-terminated PS suggests that the oligomers are desorbed preferentially from the surface in the TOF-SIMS analysis, rather than having an increased ionization probability.