Selective hydroxylation of small alkanes by the particulate methane monooxygenase

The particulate methane monooxygenase (pMMO) catalyzes the oxidation of methane to methanol under ambient temperatures and pressures. Other small alkanes and alkenes are also substrates of this enzyme. We measured and compared the initial rate constants of oxidation of small alkanes (C1 to C5) catalyzed by pMMO. Both primary and secondary alcohols were formed from oxidation of n-butane and n-pentane. The alcohols produced from alkane oxidation can be further oxidized, probably by pMMO, to aldehydes and ketones. The apparent regioselectivity for n-butane and n-pentane is 100% 2-alcohols because the formation of primary alcohols is slower than further oxidation of these alcohols. The hydroxylation at the secondary carbons is highly stereoselective: (R)-alcohols are preferentially formed. The enantiomeric excess increases slightly with decreasing reaction temperature. The steric course of hydroxylation on primary carbons was also studied by using isotopically substituted ethane: (S)- or (R)-CH_3-CHDT, and (S)- or (R)-CD_3- CHDT and the reactions were found to proceed with 100% retention of configuration. A primary isotopic effect of k_H/k_D=5.0 was observed in these experiments.

Succinate:ubiquinone oxidoreductase from Paracoccus denitrificans and particulate methane monooxygenase from Methylococcus capsulatus (Bath): experimental and theoretical EPR studies of the metal cofactors

This thesis summarizes the application of conventional and modern electron paramagnetic resonance (EPR) techniques to establish proximity relationships between paramagnetic metal centers in metalloproteins and between metal centers and magnetic ligand nuclei in two important and timely membrane proteins: succinate:ubiquinone oxidoreductase (SQR) from Paracoccus denitrificans and particulate methane monooxygenase (pMMO) from Methylococcus capsulatus. Such proximity relationships are thought to be critical to the biological function and the associated biochemistry mediated by the metal centers in these proteins. A mechanistic understanding of biological function relies heavily on structure-function relationships and the knowledge of how molecular structure and electronic properties of the metal centers influence the reactivity in metalloenzymes. EPR spectroscopy has proven to be one of the most powerful techniques towards obtaining information about interactions between metal centers as well as defining ligand structures. SQR is an electron transport enzyme wherein the substrates, organic and metallic cofactors are held relatively far apart. Here, the proximity relationships of the metallic cofactors were studied through their weak spin-spin interactions by means of EPR power saturation and electron spin-lattice (T_1) measurements, when the enzyme was poised at designated reduction levels. Analysis of the electron T_1 measurements for the S-3 center when the b-heme is paramagnetic led to a detailed analysis of the dipolar interactions and distance determination between two interacting metal centers. Studies of ligand environment of the metal centers by electron spin echo envelope modulation (ESEEM) spectroscopy resulted in the identication of peptide nitrogens as coupled nuclei in the environment of the S-1 and S-3 centers.

Finally, an EPR model was developed to describe the ferromagnetically coupled trinuclear copper clusters in pMMO when the enzyme is oxidized. The Cu(II) ions in these clusters appear to be strongly exchange coupled, and the EPR is consistent with equilateral triangular arrangements of type 2 copper ions. These results offer the first glimpse of the magneto-structural correlations for a trinuclear copper cluster of this type, which, until the work on pMMO, has had no precedent in the metalloprotein literature. Such trinuclear copper clusters are even rare in synthetic models.

Infrared luminescence properties of bismuth-doped barium silicate glasses

Infrared (IR) luminescence covering 1.1 to similar to 1.6 mu m wavelength region was observed from bismuth-doped barium silicate glasses, excited by a laser diode at 808 nm wavelength region, at room temperature. The peak of the IR luminescence appears at 1325 nm. A full width half-maximum (FWHM) and the lifetime of the fluorescence is more than 200 nm and 400 mu s, respectively. The fluorescence intensity increases with Al2O3 content, but decreases with BaO content. We suggest that the IR luminescence should be ascribed to the low valence state of bismuth Bi2+ or Bi+, and Al3+ ions play an indirect dispersing role for the infrared luminescent centers.

Infrared-to-visible upconversion fluorescence of Er3+-doped novel lithium-barium-lead-bismuth glass

Er3+-doped lithium-barium-lead-bismuth glass for developing upconversion lasers has been fabricated and characterized. The Judd-Ofelt intensity parameters Omega(t) (t = 2, 4, 6), calculated based on the experimental absorption spectrum and Judd-Ofelt theory, were found to be Omega(2) = 3.05 x 10(-20) cm(2), Omega(4) = 0.95 x 10(-20) cm(2), and Omega(6) = 0.39 x 10(-20) cm(2). Under 975 nm excitation, intense green and red emissions centered at 525, 546, and 657 nm, corresponding to the transitions H-2(11/2) -> I-4(15/2), S-4(3/2) -> I-4(15/2), and F-4(9/2) -> I-4(15/2), respectively, were observed at room temperature. The upconversion mechanisms are discussed based on the energy matching and quadratic dependence on excitation power, and the dominant mechanisms are excited state absorption and energy transfer upconversion for the green and red emissions. The long-lived I-4(11/2) level is supposed to serve as the intermediate state responsible for the intense upconversion processes. The intense upconversion luminescence of Er3+-doped lithium-barium-lead-bismuth glass may be a potentially useful material for developing upconversion optical devices. (c) 2004 Elsevier B.V. All rights reserved.

Intense frequency upconversion fluorescence of Er3+/Yb3+-codoped novel potassium-barium-strontium-lead-bismuth glasses

Er3+/Yb3+-codoped potassium-barium-strontium-lead-bismuth glasses for developing potential upconversion lasers have been fabricated and characterized. Based on the results of energy transfer efficiency, the optimal Yb3+/Er3+ concentration ratio is found to be 5:1. Intense green and red emissions centered at 525, 546, and 657 run, corresponding to the transitions H-2(11/2) -> I-4(15/2), S-4(3/2) -> I-4(15/2), and F-4(9/2) -> I-4(15/2), respectively, were observed. The quadratic dependence of the 525, 546, and 657 nm emissions on excitation power indicates that a two-photon absorption process occurs under 975 nm excitation. The long-lived I-4(11/2) level is supposed to serve as the intermediate state responsible for the upconversion processes. (c) 2004 Elsevier B.V. All rights reserved.

Novel lithium-barium-lead-bismuth glasses

New lithium-barium-lead-bismuth glasses with low OH- concentration have been obtained. The role of the different components in the glass formation has been explored from the thermal, density, and refractive index measurements. The T-g, T-x, and T-x-T-g values of these glasses are in the range of 358-400, 453-575, and 87-197 degreesC, respectively. The densities (p) and refractive indices of these glasses are mainly affected by Bi2O3 and PbO contents. A wide transmitting window from visible to infrared (IR) regions for some compositions of these glasses has been observed, which makes them appealing candidates for different optical applications such as upconverting phosphors, new laser materials, optical waveguides, and crystal-free fibre drawing. (C) 2004 Elsevier B.V. All rights reserved.

Growth of beta barium borate (beta-BaB2O4) thin films on alpha barium borate (alpha-BaB2O4) substrates

Crystalline beta-BBO thin films have been successfully prepared on (001)-oriented Sr2+-doped alpha-BBO substrates using liquid phase epitaxy and pulsed laser deposition techniques. The films were characterized by X-ray diffraction and X-ray rocking curve (XRC). The present results manifest that the beta-BBO thin films grown on Sr2+-doped alpha-BBO substrates have larger degree of orientation f-value and smaller XRC FWHM than the ones grown on other reported substrates. Compared with other substrates, alpha-BBO has the same UV cutoff and the similar structure to beta-BBO. These results reveal that alpha-BBO single crystal may be a promising substrate proper to the growth of beta-BBO films. (c) 2005 Elsevier B.V. All rights reserved.

Infrared broadband emission of bismuth-doped barium-aluminum-borate glasses

We report near infrared broadband emission of bismuth-doped barium-aluminum-borate glasses. The broadband emission covers 1.3 mum window in optical telecommunication systems. And it possesses wide full width at half maximum (FWHM) of similar to 200nm and long lifetime as long as 350 mus. The luminescent properties are quite sensitive to glass compositions and excitation wavelengths. Based on energy matching conditions, we suggest that the infrared emission may be ascribed to P-3(1) --> P-3(0) transition of Bi+. The broad infrared emission characteristics of this material indicate that it might be a promising candidate for broadband optical fiber amplifiers and tunable lasers. (C) 2005 Optical Society of America.