A green alternative to fragrant agarwood sesquiterpenoid production DOI Creative Commons
Sergio Gutiérrez, Sebastian Overmans, Gordon B. Wellman

et al.

bioRxiv (Cold Spring Harbor Laboratory), Journal Year: 2023, Volume and Issue: unknown

Published: Oct. 6, 2023

Abstract Certain endangered Thymelaeaceous trees are major sources of the fragrant and highly valued resinous agarwood, comprised hundreds oxygenated sesquiterpenoids (STPs). Despite growing pressure on natural agarwood sources, chemical complexity STPs severely limits synthetic production. Here, we catalogued diversity in 58 samples by two-dimensional gas chromatography–mass spectrometry partially recreated complex STP mixtures through biology. We improved yields unicellular alga Chlamydomonas reinhardtii combinatorial engineering to biosynthesise nine macrocyclic backbones found agarwood. A bioprocess following green-chemistry principles was developed that exploits ‘milking’ without cell lysis, solvent–solvent extraction, solvent–STP nanofiltration, bulk oxy-functionalisation obtain terpene like those This process occurs with total solvent recycling enables continuous Our synthetic-biology approach offers a sustainable alternative harvesting complex, fragrant, STPs.

Language: Английский

Atmospheric new particle formation from the CERN CLOUD experiment DOI
J. Kirkby, A. Amorim, Urs Baltensperger

et al.

Nature Geoscience, Journal Year: 2023, Volume and Issue: 16(11), P. 948 - 957

Published: Nov. 1, 2023

Language: Английский

Citations

29
Even cooler insights: On the power of forests to (water the Earth and) cool the planet DOI Creative Commons
David Ellison, Jan Pokorný, Martin Wild

et al.

Global Change Biology, Journal Year: 2024, Volume and Issue: 30(2)

Published: Feb. 1, 2024

Scientific innovation is overturning conventional paradigms of forest, water, and energy cycle interactions. This has implications for our understanding the principal causal pathways by which tree, vegetation cover (TFVC) influence local global warming/cooling. Many identify surface albedo carbon sequestration as TFVC affects Moving toward outer latitudes, in particular, where snow more important, effects are perceived to overpower sequestration. By raising albedo, deforestation thus predicted lead cooling, while increasing forest assumed result warming. Observational data, however, generally support opposite conclusion, suggesting poorly understood. Most accept that temperatures influenced interplay incoming shortwave (SW) radiation, partitioning remaining, post-albedo, SW radiation into latent sensible heat. However, extent avoidance heat formation first foremost mediated presence (absence) water not well both mediates availability on land drives potential production (evapotranspiration, ET). While directly linked than cooling/warming, it driven photosynthesis powers additional cloud top-of-cloud reflectivity, drive cooling. loss reduces storage, precipitation recycling, downwind rainfall potential, driving reduction ET (latent heat) formation. reducing heat, formation, precipitation, warming (sensible formation), further diminishes growth (carbon sequestration). Large-scale tree restoration could, therefore, contribute significantly temperature cooling through

Language: Английский

Citations

18
Gas-Phase Oxidation of Atmospherically Relevant Unsaturated Hydrocarbons by Acyl Peroxy Radicals DOI Creative Commons

Dominika Pasik,

Benjamin N. Frandsen, Melissa Meder

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(19), P. 13427 - 13437

Published: May 7, 2024

This study assesses the atmospheric impact of reactions between unsaturated hydrocarbons such as isoprene and monoterpenes peroxy radicals containing various functional groups. We find that alkenes acyl have reaction rates high enough to be feasible in atmosphere lead molar mass accretion products. Moreover, leads an alkyl radical, which molecular oxygen rapidly adds. finding is confirmed by both theoretical calculations experiments. The formed perester radical may either undergo further H-shift or react bimolecularly. multifunctional oxygenated compounds through + alkene are potentially important contributors particle formation growth. Thus, radical-initiated oxidation chemistry need included models.

Language: Английский

Citations

8
A synthetic biology and green bioprocess approach to recreate agarwood sesquiterpenoid mixtures DOI Creative Commons
Sergio Gutiérrez, Sebastian Overmans, Gordon B. Wellman

et al.

Green Chemistry, Journal Year: 2023, Volume and Issue: 26(5), P. 2577 - 2591

Published: Dec. 19, 2023

We show terpene diversity of endangered agarwoods, engineering a sustainable green algal host for production, and ‘milking’ bioprocess coupled to green-chemistry functionalisation produce terpenes like those found in agarwood.

Language: Английский

Citations

12
The search for sparse data in molecular datasets: Application of active learning to identify extremely low volatile organic compounds DOI Creative Commons
Vitus Besel, Milica Todorović, Theo Kurtén

et al.

Journal of Aerosol Science, Journal Year: 2024, Volume and Issue: 179, P. 106375 - 106375

Published: March 30, 2024

The formation of aerosol particles in the atmosphere is driven by gas to particle conversion extremely low volatile organic compounds (ELVOC), with a particularly saturation vapor pressure (pSat). Identifying ELVOCs and their chemical structures both experimentally theoretically challenging: Measuring very pSat difficult, computing for these often large molecules computationally costly. Moreover, are underrepresented available datasets atmospheric species, which reduces value statistical models built on such data. We propose an active learning (AL) approach efficiently identify data pool species initially unknown pSat. assess performance our AL comparing it traditional machine regression methods, as well ELVOC classification based molecular properties. proves be highly efficient method identification limitations type can identify. also show that or property-based methods adequate tools depending desired degree efficiency.

Language: Английский

Citations

5
A cluster-of-functional-groups approach for studying organic enhanced atmospheric cluster formation DOI Creative Commons
A. Pedersen, Yosef Knattrup, Jonas Elm

et al.

Aerosol Research, Journal Year: 2024, Volume and Issue: 2(1), P. 123 - 134

Published: June 4, 2024

Abstract. The role of organic compounds in atmospheric new particle formation is difficult to disentangle due the myriad potentially important oxygenated molecules (OOMs) present atmosphere. Using state-of-the-art quantum chemical methods, we here employ a novel approach, denoted “cluster-of-functional-groups” for studying involvement OOMs cluster formation. Instead usual “trial-and-error” approach testing ability experimentally identified form stable clusters with other nucleation precursors, study which, and how many, intermolecular interactions are required given OOM clusters. In this manner can reverse engineer elusive structure candidates that might be involved enhanced We calculated binding free energies all combinations donor acceptor functional groups investigate which most preferentially bind each precursors such as sulfuric acid bases (ammonia, methyl-, dimethyl- trimethylamine). find multiple carboxyl lead substantially more compared groups. Employing dynamics simulations, hypothetically composed stabilize acid–base provide recommendations potential multi-carboxylic tracer should explicitly studied future. presented generally applicable employed many applications, ion-induced elucidating structural patterns facilitate ice nucleation.

Language: Английский

Citations

5
Interactions of peroxy radicals from monoterpene and isoprene oxidation simulated in the radical volatility basis set DOI Creative Commons
Meredith Schervish, Martin Heinritzi, Dominik Stolzenburg

et al.

Environmental Science Atmospheres, Journal Year: 2024, Volume and Issue: 4(7), P. 740 - 753

Published: Jan. 1, 2024

Isoprene affects new particle formation rates in environments and experiments also containing monoterpenes.

Language: Английский

Citations

4
Indoor Emission, Oxidation, and New Particle Formation of Personal Care Product Related Volatile Organic Compounds DOI Creative Commons
Tianren Wu, Tatjana Müller, Nijing Wang

et al.

Environmental Science & Technology Letters, Journal Year: 2024, Volume and Issue: 11(10), P. 1053 - 1061

Published: Aug. 30, 2024

Personal care products (PCPs) contain diverse volatile organic compounds (VOCs) and routine use of PCPs indoors has important implications for indoor air quality human chemical exposures. This chamber study deployed aerosol instrumentation two online mass spectrometers to quantify VOC emissions from the five fragranced examined formation gas-phase oxidation particles upon ozone-initiated reactive VOCs. The tested include a perfume, roll-on deodorant, body spray, hair hand lotion. Indoor these emitted over 200 VOCs resulted in mixing ratios several parts per million. emission factors varied 2 964 mg g

Language: Английский

Citations

4
Ether and ester formation from peroxy radical recombination: a qualitative reaction channel analysis DOI Creative Commons
Lauri Franzon, M. Camredon,

Richard Valorso

et al.

Atmospheric chemistry and physics, Journal Year: 2024, Volume and Issue: 24(20), P. 11679 - 11699

Published: Oct. 21, 2024

Abstract. The least volatile organic compounds participating in atmospheric new-particle formation are very likely accretion products from self- and cross-reactions of peroxy radicals (RO2). It has long been assumed that the only possible product channel this reaction is forming a peroxide (RO2+RO2→ROOR+O2), but it recently discovered rapid alkoxy radical (RO) decomposition may precede step mechanism, slightly fragmented more stable ether (ROR) or ester (RC′(O)OR) products. In work, implications new have explored further by using modified version Generator for Explicit Chemistry Kinetics Organics Atmosphere (GECKO-A) software to generate large amount representative RO2 + reactive pairs formed oxidation typical primary hydrocarbons applying structure–activity relationships (SARs) predict potential These data analysed terms low-volatility products, discoveries presented on what types especially efficient (and which surprisingly inefficient) at findings discussed relevance these channels. As generation rests several simplifications assumptions, many open questions worthy later studies also raised.

Language: Английский

Citations

3
Reply on RC1 DOI Creative Commons

Dominika Pasik

Published: Jan. 1, 2025

Abstract. Monoterpenes are released into the atmosphere in significant quantities, where they undergo various oxidation reactions. Despite extensive studies this area, there still gaps that need to be addressed fully understand processes occurring atmosphere. Recent findings suggest reactions between alkenes and acyl peroxy radicals can competitive under atmospheric conditions. In study, we investigate of seven monoterpenes with subsequent diverse reactions, including accretion, alkyl radical rearrangements, H-shift, β-scissions The accretion reaction leads release excess energy, which is sufficient open small secondary rings structures. This most for sabinene (39 %) α-thujene (20 %). A competing O2 addition, majority undergo, subsequently leading formation radicals. These then react further, forming alkoxy β-scission Our calculations show β-pinene, camphene, sabinene, rearrangements result capable undergoing further propagation oxidative chain, while limonene, α-pinene α-thujene, scissions closed-shell products terminate chain preferred. results indicate if indeed conditions, their would lead more oxygenated compounds a higher molar mass, potentially contributing organic aerosol yields. Moreover, study highlights significance stereochemistry controlling initiated by

Language: Английский

Citations

0