Introducing nonnative metal ions or metal-containing prosthetic groups into a protein can dramatically expand the repertoire of its functionalities and thus its range of applications. Particularly challenging is the control of substrate-binding and thus reaction selectivity such as enantioselectivity. To meet this challenge, both non-covalent and single-point attachments of metal complexes have been demonstrated previously. Since the protein template did not evolve to bind artificial metal complexes tightly in a single conformation, efforts to restrict conformational freedom by modifying the metal complexes and/or the protein are required to achieve high enantioselectivity using the above two strategies. Here we report a novel site-selective dual anchoring (two-point covalent attachment) strategy to introduce an achiral manganese salen complex (Mn(salen)), into apo sperm whale myoglobin (Mb) with bioconjugation yield close to 100%. The enantioselective excess increases from 0.3% for non-covalent, to 12.3% for single point, and to 51.3% for dual anchoring attachments. The dual anchoring method has the advantage of restricting the conformational freedom of the metal complex in the protein and can be generally applied to protein incorporation of other metal complexes with minimal structural modification to either the metal complex or the protein.

cytochrome oxidase ͉ protein design ͉ protein engineering ͉ biomimetic models

Mixtures of small rigid sand particles D s and large soft rubber particles D r are prepared at different volume fractions and tested to investigate their small-strain and zero-lateral strain responses (D r /D s & 10). Both data sets are simultaneously gathered in an oedometer cell instrumented with bender elements. Data are analyzed in the context of mixture theory and with the aid of numerical simulations. Results show that the sand skeleton controls the mixture response when the volume fraction of rubber particles is Vrubber 0.3, while the rubber skeleton prevails at Vrubber 0.6. The large size and incompressibility of rubber particles provides high stress-induced stiffness in the sand skeleton near the equatorial plane of rubber particles. The corresponding increase in local small-strain shear modulus Gmax results in earlier wave arrivals in mixtures with Vrubber 0.3 than in pure sand, while the quasi-static constrained modulus is highest in pure sand. The constrained modulus and shear wave velocity are power functions of the applied effective stress in all mixtures. Results from this study (Dr /Ds & 10) and from a previous complementary study with small rubber particles (Dr /Ds = 0.25) show that the development of internal fabric, particle level processes, and the associated macroscale response of sand-rubber mixtures depend on the relative size between the soft rubber chips and the stiff sand particles Dr /Ds and their volume fractions.Résumé : Des mélanges de petites particules rigides de sable D s et de larges particules molles de caoutchouc D r ont été préparés à différentes fractions de volume et testés pour étudier leur réaction à de petites contraintes et à déformation laté-rale nulle (D r /D s &100). Les deux ensembles de données ont été simultanément regroupées dans une cellule oedométrique instrumentée avec des languettes piézocéramiques. Les données ont été analysées dans le contexte de la théorie du mé-lange et avec l'aide de simulations numériques. Les résultats montrent que le squelette de sable contrôle la réaction du mé-lange lorsque la fraction du volume de particules de caoutchouc est V rubber 0,3, alors que le squelette de caoutchouc domine à V rubber 0,6. La grande dimension et l'incompressibilité des particules de caoutchouc fournit une forte rigidité induite par la contrainte dans le squelette de sable près du plan équatorial des particules de caoutchouc. L'accroissement correspondant du G max local résulte en des arrivées plus hâtives des ondes dans les mélanges avec V rubber 0,3 que dans le sable pur, alors que le module quasi-statique sous contrainte est le plus élevé dans le sable pur. Le module sous contrainte et la vélocité des ondes de cisaillement sont des fonctions de puissance de la contrainte effective appliquée dans tous les mélanges. Les résultats de cette étude (Dr /DS & 10) et à partir d'une étude complémentaire antérieure avec de petites particules de caoutchouc (Dr /Ds = 0,25) montrent que le développement d'une fabrique interne, que les processus de niveau de particules...

An unanticipated wind shift led to the advection of plumes from two prescribed burning sites that impacted Atlanta, GA, producing a heavy smoke event late in the afternoon on February 28, 2007. Observed PM2.5 concentrations increased to over 140 microg/m3 and O3 concentrations up to 30 ppb in a couple of hours, despite the late hour in February when photochemistry is less vigorous. A detailed investigation of PM2.5 chemical composition and source apportionment analysis showed that the increase in PM2.5 mass was driven mainly by organic carbon (OC). However, both results from source apportionment and an observed nonlinear relationship between OC and PM2.5 potassium (K) indicate that the increased OC was not due solely to primary emissions. Most of the OC was water-soluble organic carbon (WSOC) and was dominated by hydrophobic compounds. The data are consistent with large enhancements in isoprenoid (isoprene and monoterpenes) and other volatile organic compounds emitted from prescribed burning that led to both significant O3 and secondary organic aerosol (SOA) production. Formation of oligomers from oxidation products of isoprenoid compounds or condensation of volatile organic compounds (VOCs) with multiple functional groups emitted during prescribed burning appears to be a major component of the secondary organic contributor of the SOA. The results from this study imply that enhanced emissions due to the fire itself and elevated temperature in the burning region should be considered in air quality models (e.g., receptor and emission-based models) to assess impacts of prescribed burning emissions on ambient air quality.

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Abstract. Aged smoke from a prescribed fire (dominated by conifers) impacted Atlanta, GA on 28 February 2007 and dramatically increased hourly ambient concentrations of PM2.5 and organic carbon (OC) up to 140 and 72 μg m−3, respectively. It was estimated that over 1 million residents were exposed to the smoky air lasting from the late afternoon to midnight. To better understand the processes impacting the aging of fire plumes, a detailed chemical speciation of carbonaceous aerosols was conducted by gas chromatography/mass spectrometry (GC/MS) analysis. Ambient concentrations of many organic species (levoglucosan, resin acids, retene, n-alkanes and n-alkanoic acids) associated with wood burning emission were significantly elevated on the event day. Levoglucosan increased by a factor of 10, while hopanes, steranes, cholesterol and major polycyclic aromatic hydrocarbons (PAHs) did not show obvious increases. Strong odd over even carbon number predominance was found for n-alkanes versus even over odd predominance for n-alkanoic acids. Alteration of resin acids during transport from burning sites to monitors is suggested by the observations. Our study also suggests that large quantities of biogenic volatile organic compounds (VOCs) and semivolatile organic compounds (SVOCs) were released both as products of combustion and unburned vegetation heated by the fire. Higher leaf temperature can stimulate biogenic VOC and SVOC emissions, which enhanced formation of secondary organic aerosols (SOA) in the atmosphere. This is supported by elevated ambient concentrations of secondary organic tracers (dicarboxylic acids, 2-methyltetrols, pinonic acid and pinic acid). An approximate source profile was built for the aged fire plume to help better understand evolution of wood smoke emission and for use in source impact assessment.

Abstract. Plant functional type (PFT) distributions affect the results of biogenic emission modeling as well as O3 and particulate matter (PM) simulations using chemistry-transport models (CTMs). This paper analyzes the variations of both surface biogenic volatile organic compound (BVOC) emissions and O3 concentrations due to changes in the PFT distributions in the Seoul Metropolitan Areas, Korea. The Fifth-Generation NCAR/Pennsylvania State Meso-scale Model (MM5)/the Model of Emissions of Gases and Aerosols from Nature (MEGAN)/the Sparse Matrix Operator Kernel Emissions (SMOKE)/the Community Multiscale Air Quality (CMAQ) model simulations were implemented over the Seoul Metropolitan Areas in Korea to predict surface O3 concentrations for the period of 1 May to 31 June 2008. Starting from a performance check of CTM predictions, we consecutively assessed the effects of PFT area deviations on the MEGAN BVOC and CTM O3 predictions, and we further considered the basis of geospatial and statistical analyses. The three PFT data sets considered were (1) the Korean PFT, developed with Korea-specific vegetation database; (2) the CDP PFT, adopted from the community data portal (CDP) of US National Center for Atmospheric Research in the United States (NCAR); (3) MODIS PFT, reclassified from the NASA Terra and Aqua combined land cover products. Although the CMAQ performance check reveals that all of the three different PFT data sets are applicable choices for regulatory modeling practice, noticeable primary data (i.e., PFT and Leaf Area Index (LAI)) was observed to be missing in many geographic locations. Based on the assessed effect of such missing data on CMAQ O3 predictions, we found that this missing data can cause spatially increased bias in CMAQ O3. Thus, it must be resolved in the near future to obtain more accurate biogenic emission and chemistry transport modeling results. Comparisons of MEGAN biogenic emission results with the three different PFT data showed that broadleaf trees (BTs) are the most significant contributor, followed by needleleaf trees (NTs), shrub (SB), and herbaceous plants (HBs) to the total BVOCs. In addition, isoprene from BTs and terpene from NTs were recognized as significant primary and secondary BVOC species in terms of BVOC emissions distributions and O3-forming potentials in the study domain. A geographically weighted regression analysis with locally compensated ridge (LCR-GWR) with the different PFT data (δO3 vs. δPFTs) suggests that addition of BT, SB, and NT areas can contribute to O3 increase, whereas addition of an HB area contributes to O3 decrease in the domain. Assessment results of the simulated spatial and temporal changes of O3 distributions with the different PFT scenarios reveal that hourly and local impacts from the different PFT distributions on occasional inter-deviations of O3 are quite noticeable, reaching up to 13 ppb. The simulated maximum 1 h O3 inter-deviations between different PFT scenarios have an asymmetric diurnal distribution pattern (low in the early morning, rising during the day, peaking at 05:00 p.m., and decreasing during the night) in the study domain. Exponentially diverging hourly BVOC emissions and O3 concentrations with increasing ambient temperature suggest that the use of different PFT distribution data requires much caution when modeling (or forecasting) O3 air quality in complicated urban atmospheric conditions in terms of whether uncertainties in O3 prediction results are expected to be mild or severe.