Development of tyrosinase labile protecting groups for amines

The development of two novel protecting groups for amines is described. Thus, a range of amines have been converted to ureas, and the deprotection of these upon exposure to mushroom tyrosinase (E.C. 1.14.18.1) has been demonstrated.

Macrocyclic amines as structure-directing agents for the synthesis of three-dimensional antimony-sulfide frameworks

A new family of antimony sulfides, incorporating the macrocyclic tetramine 1,4,8,11-tetraazacyclotetradecane ( cyclam), has been prepared by a hydrothermal method. [C10N4H26][Sb4S7] (1), [Ni(C10N4H24)][Sb4S7] (2), and [Co(C10N4H24)](x)[C10N4H26](1-x)[Sb4S7] (0.08 <= x <= 0.74) (3) have been characterized by single-crystal X-ray diffraction, elemental analysis, thermogravimetry, and analytical electron microscopy. All three materials possess the same novel three-dimensional Sb4S72- framework, constructed from layers of parallel arrays of Sb4S84- chains stacked at 90 to one another. In 1, doubly protonated macrocyclic cations reside in the channel structure of the antimonysulfide framework. In 2 and 3, the cyclam acts as a ligand, chelating the divalent transition- metal cation. Analytical and X-ray diffraction data indicate that the level of metal incorporation in 2 is effectively complete, whereas in 3, both metalated and nonmetalated forms of the macrocycle coexist within the structure.

Asymmetric synthesis of cyclic β-amino acids and cyclic amines via sequential diastereoselective conjugate addition and ring closing metathesis

Diastereoselective conjugate addition of lithium (S)-N-allyl-N-alpha-methylbenzylamide to a range of alpha,beta-unsaturated esters followed by ring closing metathesis is used to afford efficiently a range of substituted cyclic beta-amino esters in high d.e. Alternatively, conjugate addition to alpha,beta-unsaturated Weinreb amides, functional group conversion and ring closing metathesis affords cyclic amines in high d.e. The further application of this methodology to the synthesis of a range of carbocyclic beta-amino esters via conjugate addition, enolate alkylation and ring closing metathesis is also described. Application of this methodology affords, after deprotection, (S)-homoproline, (S)-homopipecolic acid, (S)-coniine and (1S,2S)-trans-pentacin.

Sensitivity of biogenic isoprene emissions to past, present and future environmental conditions and implications for atmospheric chemistry.

[1] We have implemented a process-based isoprene emission model in the HadGEM2 Earth-system model with coupled atmospheric chemistry in order to examine the feedback between isoprene emission and climate. Isoprene emissions and their impact on atmospheric chemistry and climate are estimated for preindustrial (1860–1869), present-day (2000–2009), and future (2100–2109) climate conditions. The estimate of 460 TgC/yr for present-day global total isoprene emission is consistent with previous estimates. Preindustrial isoprene emissions are estimated to be 26% higher than present-day. Future isoprene emissions using the RCP8.5 scenario are similar to present-day because increased emissions resulting from climate warming are countered by CO2 inhibition of isoprene emissions. The impact of biogenic isoprene emissions on the global O3 burden and CH4 lifetime is small but locally significant, and the impact of changes in isoprene emissions on atmospheric chemistry depends strongly on the state of climate and chemistry.

Evaluation of a photosynthesis-based biogenic isoprene emission scheme in JULES and simulation of isoprene emissions under present-day climate conditions

We have incorporated a semi-mechanistic isoprene emission module into the JULES land-surface scheme, as a first step towards a modelling tool that can be applied for studies of vegetation – atmospheric chemistry interactions, including chemistry-climate feedbacks. Here, we evaluate the coupled model against local above-canopy isoprene emission flux measurements from six flux tower sites as well as satellite-derived estimates of isoprene emission over tropical South America and east and south Asia. The model simulates diurnal variability well: correlation coefficients are significant (at the 95 % level) for all flux tower sites. The model reproduces day-to-day variability with significant correlations (at the 95 % confidence level) at four of the six flux tower sites. At the UMBS site, a complete set of seasonal observations is available for two years (2000 and 2002). The model reproduces the seasonal pattern of emission during 2002, but does less well in the year 2000. The model overestimates observed emissions at all sites, which is partially because it does not include isoprene loss through the canopy. Comparison with the satellite-derived isoprene-emission estimates suggests that the model simulates the main spatial patterns, seasonal and inter-annual variability over tropical regions. The model yields a global annual isoprene emission of 535 ± 9 TgC yr−1 during the 1990s, 78 % of which from forested areas.

Flow synthesis of organic azides and the multistep synthesis of imines and amines using a new monolithic triphenylphosphine reagent

Here we describe general flow processes for the synthesis of alkyl and aryl azides, and the development of a new monolithic triphenylphosphine reagent, which provides a convenient format for the use of this versatile reagent in flow. The utility of these new tools was demonstrated by their application to a flow Staudinger aza-Wittig reaction sequence. Finally, a multistep aza-Wittig, reduction and purification flow process was designed, allowing access to amine products in an automated fashion.

Structural complexity in indium selenides prepared using bicyclic amines as structure-directing agents

The synthesis and characterization of five new indium selenides, [C9H17N2]3[In5Se8+x(Se2)1−x] (1–2), [C6H12N2]4[C6H14N2]3[In10Se15(Se2)3] (3), [C6H14N2][(C6H12N2)2NaIn5Se9] (4) and [enH2][NH4][In7Se12] (5), are described. These materials were prepared under solvothermal conditions, using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,4-diazabicyclo[2.2.2]octane (DABCO) as structure-directing agents. Compounds 1–4 represent the first examples of ribbons in indium selenides, and 4 is the first example of incorporation of an alkali metal complex. Compounds 1, 2 and 4 contain closely related [In5Se8+x(Se2)1−x]3− ribbons which differ only in their content of (Se2)2− anions. These ribbons are interspaced by organic countercations in 1 and 2, while in 4 they are linked by highly unusual [Na(DABCO)2]+ units into a three-dimensional framework. Compound 3 contains complex ribbons, with a long repeating sequence of ca. 36 Å, and 4 is a non-centrosymmetric three-dimensional framework, formed as a consequence of the decomposition of DABCO into ethylenediamine (en) and ammonia.

BAECC: a field campaign to elucidate the impact of Biogenic Aerosols on Clouds and Climate

Observations obtained during an 8-month deployment of AMF2 in a boreal environment in Hyytiälä, Finland, and the 20-year comprehensive in-situ data from SMEAR-II station enable the characterization of biogenic aerosol, clouds and precipitation, and their interactions. During “Biogenic Aerosols - Effects on Clouds and Climate (BAECC)”, the U.S. Department of Energy’s Atmospheric Radiation Measurement (ARM) Program deployed the ARM 2nd Mobile Facility (AMF2) to Hyytiälä, Finland, for an 8-month intensive measurement campaign from February to September 2014. The primary research goal is to understand the role of biogenic aerosols in cloud formation. Hyytiälä is host to SMEAR-II (Station for Measuring Forest Ecosystem-Atmosphere Relations), one of the world’s most comprehensive surface in-situ observation sites in a boreal forest environment. The station has been measuring atmospheric aerosols, biogenic emissions and an extensive suite of parameters relevant to atmosphere-biosphere interactions continuously since 1996. Combining vertical profiles from AMF2 with surface-based in-situ SMEAR-II observations allow the processes at the surface to be directly related to processes occurring throughout the entire tropospheric column. Together with the inclusion of extensive surface precipitation measurements, and intensive observation periods involving aircraft flights and novel radiosonde launches, the complementary observations provide a unique opportunity for investigating aerosol-cloud interactions, and cloud-to-precipitation processes, in a boreal environment. The BAECC dataset provides opportunities for evaluating and improving models of aerosol sources and transport, cloud microphysical processes, and boundary-layer structures. In addition, numerical models are being used to bridge the gap between surface-based and tropospheric observations.

Rainforest Aerosols as Biogenic Nuclei of Clouds and Precipitation in the Amazon

The Amazon is one of the few continental regions where atmospheric aerosol particles and their effects on climate are not dominated by anthropogenic sources. During the wet season, the ambient conditions approach those of the pristine pre-industrial era. We show that the fine submicrometer particles accounting for most cloud condensation nuclei are predominantly composed of secondary organic material formed by oxidation of gaseous biogenic precursors. Supermicrometer particles, which are relevant as ice nuclei, consist mostly of primary biological material directly released from rainforest biota. The Amazon Basin appears to be a biogeochemical reactor, in which the biosphere and atmospheric photochemistry produce nuclei for clouds and precipitation sustaining the hydrological cycle. The prevailing regime of aerosol-cloud interactions in this natural environment is distinctly different from polluted regions.

Stereochemical transfer to atmospheric aerosol particles accompanying the oxidation of biogenic volatile organic compounds

Asymmetric emission profiles of the stereoisomers of plant-derived volatile organic compounds vary with season, geography, plant type, and stress factors. After oxidation of these compounds in the atmosphere, the low-vapor pressure products ultimately contribute strongly to the particle-phase material of the atmosphere. In order to explore the possibility of stereochemical transfer to atmospheric aerosol particles during the oxidation of biogenic volatile organic compounds, second-order coherent vibrational spectra were recorded of the particle-phase organic material produced by the oxidation of different stereoisomeric mixes of alpha-pinene. The spectra show that the stereochemical configurations are not scrambled but instead are transferred from the gas-phase molecular precursors to the particle-phase molecules. The spectra also show that oligomers formed in the particle phase have a handed superstructure that depends strongly and nonlinearly on the initial stereochemical composition of the precursors. Because the stereochemical mix of the precursors for a material can influence the physical and chemical properties of that material, our findings suggest that chirality is also important for such properties of plant-derived aerosol particles. Citation: Ebben, C. J., S. R. Zorn, S.-B. Lee, P. Artaxo, S. T. Martin, and F. M. Geiger (2011), Stereochemical transfer to atmospheric aerosol particles accompanying the oxidation of biogenic volatile organic compounds, Geophys. Res. Lett., 38, L16807, doi: 10.1029/2011GL048599.

Mass spectral characterization of submicron biogenic organic particles in the Amazon Basin

Submicron atmospheric particles in the Amazon Basin were characterized by a high-resolution aerosol mass spectrometer during the wet season of 2008. Patterns in the mass spectra closely resembled those of secondary-organic-aerosol (SOA) particles formed in environmental chambers from biogenic precursor gases. In contrast, mass spectral indicators of primary biological aerosol particles (PBAPs) were insignificant, suggesting that PBAPs contributed negligibly to the submicron fraction of particles during the period of study. For 40% of the measurement periods, the mass spectra indicate that in-Basin biogenic SOA production was the dominant source of the submicron mass fraction, contrasted to other periods (30%) during which out-of-Basin organic-carbon sources were significant on top of the baseline in-Basin processes. The in-Basin periods had an average organic-particle loading of 0.6 mu g m(-3) and an average elemental oxygen-to-carbon (O:C) ratio of 0.42, compared to 0.9 mu g m(-3) and 0.49, respectively, during periods of out-of-Basin influence. On the basis of the data, we conclude that most of the organic material composing submicron particles over the Basin derived from biogenic SOA production, a finding that is consistent with microscopy observations made in a concurrent study. This source was augmented during some periods by aged organic material delivered by long-range transport. Citation: Chen, Q., et al. (2009), Mass spectral characterization of submicron biogenic organic particles in the Amazon Basin, Geophys. Res. Lett., 36, L20806, doi: 10.1029/2009GL039880.

Relative roles of biogenic emissions and Saharan dust as ice nuclei in the Amazon basin

Some aerosol particles, known as ice nuclei, can initiate ice formation in clouds, thereby influencing precipitation, cloud dynamics and the amount of incoming and outgoing solar radiation. In the absence of biomass burning, aerosol mass concentrations in the Amazon basin are low(1). Tropical forests emit primary biological particles directly into the atmosphere; secondary organic aerosols form from the emission and oxidation of biogenic gases(2). In addition, particles derived from biomass burning in central Africa, marine aerosols, and windblown dust from North Africa(3-5) often reach the central part of the Amazon basin during the wet season. The contribution of these aerosol sources to ice nucleation in the region is uncertain. Here we present observations of the concentration and elemental composition of ice nuclei in the Amazon basin during the wet season. Using transmission electron microscopy combined with energy-dispersive X-ray spectroscopy, we show that ice nuclei are primarily composed of carbonaceous material and dust. We show that biological particles dominate the carbonaceous fraction, whereas import of Saharan dust explains the intermittent appearance of dust-containing nuclei. We conclude that ice-nucleus concentration and abundance can be explained almost entirely by local emissions of biological particles supplemented by import of Saharan dust. Using a simple model, we tentatively suggest that the contribution of local biological particles to ice nucleation is increased at higher atmospheric temperatures, whereas the contribution of dust particles is increased at lower temperatures.

Determination of anthropogenic and biogenic compounds on atmospheric aerosol collected in urban, biomass burning and forest areas in Sao Paulo, Brazil

This study was conducted at three sites of different characteristics in Sao Paulo State Sao Paulo (SPA), Piracicaba (PRB) and Mate Atlantica Forest (MAT) PM(10), n-alkanes. pristane and phytane, PAHs, water-soluble ions and biomass burning tracers like levoglucosan and retene, were determined in quartz fiber filters. Samplings occurred on May 8th to August 8th, 2007 at the MAT site; on August 15th to 29th in 2007 and November 10th to 29th in 2008 at the PRB site and, March 13th to April 4th in 2007 and August 7th to 29th in 2008 at the SPA site Aliphatic compounds emitted biogenically were less abundant at the urban sites than at the forest site, and its distribution showed the influence of tropical vascular plants Air mass transport front biomass burning regions is likely to impact the sites with specific molecular markers The concentrations of all species were variable and dependent of seasonal changes In the most dry and polluted seasons, n-alkane and canon total concentrations were similar between the megacity and the biomass burning site PAHs and inorganic ion abundances were higher at Sao Paulo than Piracicaba, yet, the site influenced by biomass burning seems lobe the most impacted by the organic anion abundance in the atmosphere Pristane and phytane confirm the contamination by petroleum residues at urban sites, at the MAT site, biological activity and long range transport of pollutants might influence the levels of pristane (C) 2010 Elsevier B V All rights reserved

Chemoenzymatic synthesis of boron-containing chiral amines and amides

The first application of lipases as catalysts to obtain optically active boron-containing amines and amides is described. We studied several reaction conditions to achieve the kinetic resolution of boron-containing amines via enantioselective acylation mediated by Candida antarctica lipase B (CAL-B). Excellent enantioselectivity (E>200) and high enantiomeric excess (up to >99%) of both the remaining amines and amides were obtained. (C) 2010 Elsevier Ltd. All rights reserved.

First dynamic kinetic resolution of selenium-containing chiral amines catalyzed by palladium (Pd/BaSO(4)) and Candida antartica lipase (CAL-B)

An efficient method for chemoenzymatic dynamic kinetic resolution of selenium-containing chiral amines (organoselenium-1-phenylethanamines) has been developed, leading to the corresponding amides in excellent enantioselectivities and high isolated yields. This one-pot procedure employs two different types of catalysts: Pd on barium sulphate (Pd/BaSO(4)) as racemization catalyst and lipase (CAL-B) as the resolution catalyst. (C) 2009 Elsevier Ltd. All rights reserved.