Structural Studies on a Mitochondrial Glyoxalase II

Glyoxalase 2 is a β-lactamase fold-containing enzyme that appears to be involved with cellular chemical detoxification. Although the cytoplasmic isozyme has been characterized from several organisms, essentially nothing is known about the mitochondrial proteins. As a first step in understanding the structure and function of mitochondrial glyoxalase 2 enzymes, a mitochondrial isozyme (GLX2-5) from Arabidopsis thaliana was cloned, overexpressed, purified, and characterized using metal analyses, EPR and 1H NMR spectroscopies, and x-ray crystallography. The recombinant enzyme was shown to bind 1.04 ± 0.15 eq of iron and 1.31 ± 0.05 eq of Zn(II) and to exhibit kcat and Km values of 129 ± 10 s-1 and 391 ± 48 μm, respectively, when using S-d-lactoylglutathione as the substrate. EPR spectra revealed that recombinant GLX2-5 contains multiple metal centers, including a predominant Fe(III)Z-n(II) center and an anti-ferromagnetically coupled Fe(III)Fe(II) center. Unlike cytosolic glyoxalase 2 from A. thaliana, GLX2-5 does not appear to specifically bind manganese. 1H NMR spectra revealed the presence of at least eight paramagnetically shifted resonances that arise from protons in close proximity to a Fe(III)Fe(II) center. Five of these resonances arose from solvent-exchangeable protons, and four of these have been assigned to NH protons on metal-bound histidines. A 1.74-Å resolution crystal structure of the enzyme revealed that although GLX2-5 shares a number of structural features with human GLX2, several important differences exist. These data demonstrate that mitochondrial glyoxalase 2 can accommodate a number of different metal centers and that the predominant metal center is Fe(III)Zn(II)

The Final SDSS High-Redshift Quasar Sample of 52 Quasars at z>5.7

We present the discovery of nine quasars at $z\sim6$ identified in the Sloan Digital Sky Survey (SDSS) imaging data. This completes our survey of $z\sim6$ quasars in the SDSS footprint. Our final sample consists of 52 quasars at $5.7<z\le6.4$, including 29 quasars with $z_{\rm AB}\le20$ mag selected from 11,240 deg$^2$ of the SDSS single-epoch imaging survey (the main survey), 10 quasars with $20\le z_{\rm AB}\le20.5$ selected from 4223 deg$^2$ of the SDSS overlap regions (regions with two or more imaging scans), and 13 quasars down to $z_{\rm AB}\approx22$ mag from the 277 deg$^2$ in Stripe 82. They span a wide luminosity range of $-29.0\le M_{1450}\le-24.5$. This well-defined sample is used to derive the quasar luminosity function (QLF) at $z\sim6$. After combining our SDSS sample with two faint ($M_{1450}\ge-23$ mag) quasars from the literature, we obtain the parameters for a double power-law fit to the QLF. The bright-end slope $\beta$ of the QLF is well constrained to be $\beta=-2.8\pm0.2$. Due to the small number of low-luminosity quasars, the faint-end slope $\alpha$ and the characteristic magnitude $M_{1450}^{\ast}$ are less well constrained, with $\alpha=-1.90_{-0.44}^{+0.58}$ and $M^{\ast}=-25.2_{-3.8}^{+1.2}$ mag. The spatial density of luminous quasars, parametrized as $\rho(M_{1450}<-26,z)=\rho(z=6)\,10^{k(z-6)}$, drops rapidly from $z\sim5$ to 6, with $k=-0.72\pm0.11$. Based on our fitted QLF and assuming an IGM clumping factor of $C=3$, we find that the observed quasar population cannot provide enough photons to ionize the $z\sim6$ IGM at $\sim90$\% confidence. Quasars may still provide a significant fraction of the required photons, although much larger samples of faint quasars are needed for more stringent constraints on the quasar contribution to reionization.Comment: 20 pages, 12 figures, Accepted for publication in The Astrophysical Journa

Interpreting the Time-Resolved Photoluminescence of Quasi-2D Perovskites

Optical excitation of quasi-2D perovskites leads to excited-state populations of excitons, free charge carriers, or a mixture of both, depending on the type and amount of 2D spacer used. The fluence dependence of three quantities: 1) the time-resolved photoluminescence decay, 2) the photoluminescence quantum yield (PLQY) after pulsed excitation, and 3) the initial rate of photon emission, allow the mixture of excited states present to be determined. These can be described by a simple model considering noninteracting populations of excitons and charge carriers in separate subvolumes of the film. The model reproduces all unique features of the data, such as the anomalous peak of the PLQY at intermediate fluences, due to bimolecular free carrier emission gaining efficiency before exciton–exciton annihilation reduces the exciton emission efficiency. The excited state population varies from 100% excitons in films made from high concentrations of butylamine spacers to ≈7% excitons and 93% free carriers for low concentrations of 1-naphthylmethylamine spacers. The effective rates of free carrier recombination and exciton–exciton annihilation are high, often on the order of 1 × 10−9 cm3 s−1. The implications for the different excited-state populations and their dynamics in terms of device engineering are discussed

Susceptibility of the Spin 1/2 Heisenberg Antiferromagnetic Chain

Highly accurate results are presented for the susceptibility, $\chi (T)$ of the $s=1/2$ Heisenberg antiferromagnetic chain for all temperatures, using the Bethe ansatz and field theory methods. After going through a rounded peak, $\chi (T)$ approaches its asympotic zero-temperature value with infinite slope.Comment: 8 pages and 3 postscript figures appended (uuencoded), Revtex, Report #:UBCTP-94-00

Silica Aerogels Doped with Ru(II) Tris 1,l0-Phenanthro1ine)-Electron Acceptor Dyads: Improving the Dynamic Range, Sensitivity and Response Time of Sol-Gel Based Oxygen Sensors

Complexes 1 and 2 were characterized in fluid and frozen solution and as dopants of silica aerogels. The intramolecular quenching efficiency of pendant 4-benzoyl-N-methylpyridinium group (4BzPy) is solvent dependent: emission is quenched completely in acetonitrile but not in alcohols. On the other hand, N-benzyl-N'-methylviologen (BzMeV) quenches the emission in all solvents completely. The differences are traced electrochemically to a stronger solvation effect by the alcohol in the case of 1. In fiozen matrices or absorbed on the surfaces of silica aerogel, both 1 and 2 are photoluminescent. The lack of quenching has been traced to the environmental rigidity. When doped aerogels are cooled to 77K, the emission shifts to the blue and its intensity increases in analogy to what is observed with Ru(II) complexes in media undergoing fluid-to-rigid transition. The photoluminescence of 1 and 2 from the aerogel is quenched by oxygen diffusing through the pores. In the presence of oxygen, aerogels doped with 1 can modulate their emission over a wider dynamic range than aerogels doped with 2, and both are more sensitive than aerogels doped with Ru(II) tris(1,l0- phenanthroline). In contrast to frozen solutions, the luminescent moieties in the bulk of aerogels kept at 77K are still accessible, leading to more sensitive platforms for oxygen sensors than other ambient temperature configurations

Uniform patchy and hollow rectangular platelet micelles from crystallizable polymer blends

Growing patterned rectangular objects The growth of patterned objects usually requires a template to aid the positioning of multiple materials. Qiu et al. used the seeded growth of a crystallizable block copolymer and a homopolymer to produce highly uniform rectangular structures (see the Perspective by Ballauff). Chemical etching, or dissolution, of uncross-linked regions of the rectangular structures produced perforated platelet micelles. The sequential addition of different blends and cross-linking/dissolution strategies allowed the formation of well-defined hollow rectangular micelles, which can be functionalized in a variety of ways. Science , this issue p. 697 ; see also p. 656 </jats:p