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Boosting Crop Growth using Natural Product and Synthesis Enabled Solar Harvesting

Deliverables

Synthesis (preliminary results)

Preliminary data pertaining to synthesis and production of a range of SM, DPP and PhyC analogues, all in >100 mg quantities (D1.1).

Toxicity studies 1

Task 43 Selected compounds will be subjected first to in silico computational analysis for possible metabolic byproducts generated by plants or microorganisms Task 42 will provide information about photochemical byproducts All resulting molecules will be screened for possible human toxicity using appropriate QSAR models readacross software and experimental approaches Endpoints addressed will comprise ADME cytotoxicity genotoxicity carcinogenicity as well as allergenic and phototoxic potential Suspected toxins will then be selected for OECD guidelinecompliant in vitro analysis for genotoxicity Ames test micronucleus assay and phototoxicity 3T3 phototoxicity assay BfR

Spectroscopy (preliminary results)

Preliminary results pertaining to the spectroscopy

Model for nonadiabatic relaxation of prototypical SMs/DPPs/PhyCs in the complex environment (water + cellulose)

Task 33 The nonadiabatic relaxation models in Task 33 will determine how the photon energy is converted into ground state vibrational energy heat and how possible chemical functionalisations will aid retention of excess vibrational energy near the cellulose wall This part of the project will require constant interaction with WP2 and WP4 AMU

Theory and computation (preliminary results)

Preliminary results pertaining to theory and computation

1D dynamical studies in the gas-phase, solution-phase and thin-films

Task 22 1D dynamics studies will capture in real time the evolving dynamics and photoprotection mechanisms operating in these molecules on an ultrafast timescale Gasphase femtosecond laser spectroscopic studies will unravel the photon conversion dynamics of accessible excited states of isolated SMsDPPsPhyCs and oligomers UW Solutionphase studies using femtosecond transient electronic and transient vibrational absorption spectroscopy will investigate in detail how the solvent influences the evolution of the excited state and the quantum yield for heat generation UB UW Thinfilm TF studies on SMDPPPhyC solutions sprayed onto thin transparent membranes will mimic as close to realistic conditions as possible We will then repeat the protocol used for the solutionphase studies to investigate how the excited state dynamics are affected by incorporating the molecules on a thinfilm UB UW but also employ UV pumpTHz probe studies to elucidate how the solid interface perturbs both the excited and ground state dynamics UW

Frequency resolved measurements

Task 21 Frequency resolved laser spectroscopic studies on isolated and solvent clustered photon converters will be assessed against the different functionalities to establish spectroscopic properties structural and electronic responses and decay pathways to longlived electronic states UAHIMS Structural characterisation of photoproducts formed under gasphase ie isolated molecule conditions will be explored by IR ion spectroscopy methods thereby providing the necessary insights into the fundamental photochemistry of the compounds of interest RU

Synthesis and production of a range of SM, DPP and PhyC analogues, all in >100 mg quantities

A range of synthetic procedures will be developed along with established routes to produce a library of natureinspired SM DPP analogues with functional moieties positioned at various locations along the rings see Fig 2C in addition to the synthesis of oligomeric SMs APT Likewise PhyCs synthesis bacterial expression or extraction will be utilised UASILS Particular attention will be paid to ensure that these molecules are watersoluble Results obtained from WPs24 will allow us to determine structureactivity relationships and identify the key structural features responsible for the activities eg absorptionfluorescence characteristics UW photodegradation products APT BfR UAHIMS enabling further design improvements to the most promising candidates Having identified the most active candidates which correspondingly adhere best to surfaces such as cellulose and polydimethylacrylamide PDMA we will seek to optimise their synthetic pathways to provide green and industryrelevant processes eg biocatalytic pathways

Model for internal vibrational relaxation (IVR) of candidate SMs/DPPs/PhyCs in the complex environment

Task 33 The nonadiabatic relaxation models in Task 33 will determine how the photon energy is converted into ground state vibrational energy heat and how possible chemical functionalisations will aid retention of excess vibrational energy near the cellulose wall This part of the project will require constant interaction with WP2 and WP4 AMU

Upscale production of SMs, DPPs and PhyCs (from WPs2-4) that show greatest promise.

A range of synthetic procedures will be developed along with established routes to produce a library of natureinspired SM DPP analogues with functional moieties positioned at various locations along the rings see Fig 2C in addition to the synthesis of oligomeric SMs APT Likewise PhyCs synthesis bacterial expression or extraction will be utilised UASILS Particular attention will be paid to ensure that these molecules are watersoluble Results obtained from WPs24 will allow us to determine structureactivity relationships and identify the key structural features responsible for the activities eg absorptionfluorescence characteristics UW photodegradation products APT BfR UAHIMS enabling further design improvements to the most promising candidates Having identified the most active candidates which correspondingly adhere best to surfaces such as cellulose and polydimethylacrylamide PDMA we will seek to optimise their synthetic pathways to provide green and industryrelevant processes eg biocatalytic pathways

Model for nonadiabatic relaxation of prototypical SMs/DPPs/PhyCs in the gas-phase

Task 32 Working in parallel with WP2 we will develop models for the nonadiabatic relaxation of the photon energy absorbed by the SMsDPPsPhyCs in the gasphase and in complex environments These calculations will be carried out through a twopronged strategy involving i static techniques for determining conical intersections excited state critical points and reaction pathways connecting them and ii nonadiabatic dynamics simulations AMU

2D dynamical studies in the solution-phase and thin-films

Task 23 2D dynamics studies for which the requested Dazzler ultrafast pulse shaper will be essential will provide insights into branched nonradiative relaxation dynamics Furthermore these experiments will interrogate the target moleculebath coupling which will depend on the phase that the target species is encapsulated in eg solutionthinfilms providing insights into the rate of heat dissipation UB

Analysis (preliminary results)

Preliminary results pertaining to thermal imaging photostability and toxicity

Fundamental spectroscopic signatures of SM/DPP/PhyC analogues delivered according to the needs of WP1 and WP2

Task 31 Electronic structure calculations will focus on SMsDPPsPhyCs in the gasphase and in complex environments water solution cellulosefilm These calculations will run in tandem with the experimental program specifically WP1 and WP2 and will be used to calculate characterise and predict the electronic spectra of SMDPPPhyC analogues AMU RU UAHIMS

Analytical chemistry

Task 42 Analysis of byproductstoxins using a unique combination of massspectrometry and tunable IR laser spectroscopy to assess the extent to which solar illumination can trigger byproduct release that could be toxic not just to the plant but also to the end user RU UAHIMS The ability to record IR spectra with selectivity of MS for analytical purposes is currently unique in the world and provides new opportunities to identify compounds in complex mixtures

Data management plan

Preparation of data management plan

Publications

Excited-state dynamics of isolated and (micro)solvated methyl sinapate: the bright and shady sides of a natural sunscreen

Author(s): Jiayun Fan, Wim Roeterdink, Wybren Jan Buma
Published in: Molecular Physics, Issue 119/1-2, 2021, Page(s) e1825850, ISSN 0026-8976
Publisher: Taylor & Francis
DOI: 10.1080/00268976.2020.1825850

Insight into the Photodynamics of Photostabilizer Molecules.

Author(s): Abiola, Temitope T.; Rioux, Benjamin; Sharanjit Johal; Mention, Matthieu M.; Brunissen, Fanny; Woolley, Jack M.; Allais, Florent; Stavros, Vasilios G.
Published in: J. Phys. Chem. A, Issue 126, 45, 2022, Page(s) 8388–8397, ISSN 1089-5639
Publisher: American Chemical Society
DOI: 10.1021/acs.jpca.2c05580

Modeling the heating and cooling of a chromophore after photoexcitation

Author(s): Elizete Ventura, Silmar Andrade do Monte, Mariana T. do Casal, Max Pinheiro, Jr, Josene Maria Toldo and Mario Barbatti
Published in: Physical Chemistry Chemical Physics, Issue 24, 2022, Page(s) 15604-15604, ISSN 1463-9084
Publisher: RSC
DOI: 10.1039/d2cp00686c

A systematic approach to methyl cinnamate photodynamics

Author(s): Konstantina M. Krokidi, Matthew A. P. Turner, Philip A. J. Pearcy, Vasilios G. Stavros
Published in: Molecular Physics, Issue 119/1-2, 2021, Page(s) e1811910, ISSN 0026-8976
Publisher: Taylor & Francis
DOI: 10.1080/00268976.2020.1811910

Characterization of Solar Radiation-Induced Degradation Products of the Plant Sunscreen Sinapoyl Malate

Author(s): Matthias J. A. Vink, John J. Schermer, Jonathan Martens, Wybren Jan Buma, Giel Berden, and Jos Oomens
Published in: ACS Agricultural Science & Technology, Issue 3 (2), 2023, Page(s) 171-180, ISSN 2692-1952
Publisher: American Chemical Society
DOI: 10.1021/acsagscitech.2c00279

Innovative Bio-Based Organic UV-A and Blue Light Filters from Meldrum’s Acid

Author(s): Cédric Peyrot, Matthieu M. Mention, Fanny Brunissen, Patrick Balaguer, Florent Allais
Published in: Molecules, Issue 25/9, 2020, Page(s) 2178, ISSN 1420-3049
Publisher: Multidisciplinary Digital Publishing Institute (MDPI)
DOI: 10.3390/molecules25092178

Direct structural observation of ultrafast photoisomerization dynamics in sinapate esters

Author(s): Temitope T. Abiola; Josene M. Toldo; Mariana T. do Casal; Amandine L. Flourat; Benjamin Rioux; Jack M. Woolley; Daniel Murdock; Florent Allais; Mario Barbatti; Vasilios G. Stavros
Published in: Communications Chemistry, Issue 5, 2022, Page(s) 1-9, ISSN 2399-3669
Publisher: Nature
DOI: 10.1038/s42004-022-00757-6

Probing the electronic structure and photophysics of thiophene–diketopyrrolopyrrole derivatives in solution

Author(s): Daniel W. Polak; Mariana T. do Casal; Josene M. Toldo; Xiantao Hu; Giordano Amoruso; Olivia Pomeranc; Martin Heeney; Mario Barbatti; Michael N. R. Ashfold; Thomas A. A. Oliver
Published in: Physical Chemistry Chemical Physics, Issue 24, 2022, Page(s) 20138-20151, ISSN 1463-9076
Publisher: Royal Society of Chemistry
DOI: 10.1039/d2cp03238d

Fewest switches surface hopping with Baeck-An couplings

Author(s): Mariana T. do Casal, Josene M. Toldo, Max Pinheiro Jr, Mario Barbatti
Published in: Open Research Europe, Issue 1, 2021, Page(s) 49, ISSN 2732-5121
Publisher: European Commission
DOI: 10.12688/openreseurope.13624.1

Elucidating the photoprotective properties of natural UV screening agents: ZEKE–PFI spectroscopy of methyl sinapate

Author(s): Jiayun Fan; Laura Finazzi; Wybren Jan Buma
Published in: Physical Chemistry Chemical Physics, Issue 24, 2022, Page(s) 3984-3993, ISSN 1463-9076
Publisher: Royal Society of Chemistry
DOI: 10.1039/D1CP05958K

Structural Elucidation of Agrochemicals and Related Derivatives Using Infrared Ion Spectroscopy

Author(s): Matthias J.A. Vink, Fred A.M.G. van Geenen, Giel Berden, Timothy J. C. O’Riordan, Peter W.A. Howe, Jos Oomens, Simon J. Perry, and Jonathan Martens
Published in: Environmental Science & Technology, Issue 56, 2022, Page(s) 15563-15572, ISSN 0013-936X
Publisher: American Chemical Society
DOI: 10.1021/acs.est.2c03210

Biomimetic regioselective and high-yielding Cu(I)-catalyzed dimerization of sinapate esters in green solvent CyreneTM: towards sustainable antioxidant and anti-UV ingredients

Author(s): Matthieu Mention, Amandine Lea Flourat, Cedric Peyrot, Florent Allais
Published in: Green Chemistry, 2020, ISSN 1463-9262
Publisher: Royal Society of Chemistry
DOI: 10.1039/d0gc00122h

Sustainable Synthesis of p-Hydroxycinnamic Diacids through Proline-Mediated Knoevenagel Condensation in Ethanol: An Access to Potent Phenolic UV Filters and Radical Scavengers

Author(s): Benjamin Rioux, Cédric Peyrot, Matthieu M. Mention, Fanny Brunissen, Florent Allais
Published in: Antioxidants, Issue 9/4, 2020, Page(s) 331, ISSN 2076-3921
Publisher: MDPI
DOI: 10.3390/antiox9040331

Conservation of ultrafast photoprotective mechanisms with increasing molecular complexity in sinapoyl malate derivatives

Author(s): Lewis A. Baker, Michael Staniforth, Amandine L. Flourat, Florent Allais, Vasilios G. Stavros
Published in: ChemPhysChem, 2020, ISSN 1439-4235
Publisher: John Wiley & Sons Ltd.
DOI: 10.1002/cphc.202000429

On the origin of the shift between vertical excitation and band maximum in molecular photoabsorption

Author(s): Shuming Bai, Ritam Mansour, Ljiljana Stojanović, Josene M. Toldo, Mario Barbatti
Published in: Journal of Molecular Modeling, Issue 26/5, 2020, Page(s) 107, ISSN 1610-2940
Publisher: Springer Verlag
DOI: 10.1007/s00894-020-04355-y

Exploring the Photochemistry of an Ethyl Sinapate Dimer: An Attempt Toward a Better Ultraviolet Filter

Author(s): Michael D. Horbury, Matthew A. P. Turner, Jack S. Peters, Matthieu Mention, Amandine L. Flourat, Nicholas D. M. Hine, Florent Allais, Vasilios G. Stavros
Published in: Frontiers in Chemistry, Issue 8, 2020, Page(s) 633, ISSN 2296-2646
Publisher: Frontiers
DOI: 10.3389/fchem.2020.00633

Insights into the photoprotection mechanism of the UV filter homosalate

Author(s): Emily L. Holt, Konstantina M. Krokidi, Matthew A. P. Turner, Piyush Mishra, Timothy S. Zwier, Natércia d. N. Rodrigues, Vasilios G. Stavros
Published in: Physical Chemistry Chemical Physics, Issue 22/27, 2020, Page(s) 15509-15519, ISSN 1463-9076
Publisher: Royal Society of Chemistry
DOI: 10.1039/d0cp02610g

Simulation of Excitation by Sunlight in Mixed Quantum-Classical Dynamics

Author(s): Mario Barbatti
Published in: Journal of Chemical Theory and Computation, 2020, ISSN 1549-9618
Publisher: American Chemical Society
DOI: 10.1021/acs.jctc.0c00501

Elucidating the photoprotective properties of natural UV screening agents: ZEKE-PFI spectroscopy of methyl sinapate

Author(s): Jiayun Fan; Laura Finazzi; Wybren Jan Buma
Published in: Physical Chemistry Chemical Physics, Issue 24, 2022, Page(s) 3984-3993, ISSN 1463-9084
Publisher: RSC
DOI: 10.1039/d1cp05958k

From Biomass-Derived p-Hydroxycinnamic Acids to Novel Sustainable and Non-Toxic Phenolics-Based UV-Filters: A Multidisciplinary Journey

Author(s): Benjamin Rioux, Jeanne Combes, Jack M. Woolley, Natércia d. N. Rodrigues, Matthieu M. Mention, Vasilios G. Stavros and Florent Allais
Published in: Frontiers in Chemistry, Issue 10, 2022, Page(s) 730, ISSN 2296-2646
Publisher: Frontiers Media S.A
DOI: 10.3389/fchem.2022.886367

Effects of substituent position on aminobenzoate relaxation pathways in solution

Author(s): Natércia d. N. Rodrigues, Jack M. Woolley, Konstantina M. Krokidi, Maria A. Tesa-Serrate, Matthew A. P. Turner, Nicholas D. M. Hine, Vasilios G. Stavros
Published in: Physical Chemistry Chemical Physics, Issue 23/40, 2021, Page(s) 23242-23255, ISSN 1463-9076
Publisher: Royal Society of Chemistry
DOI: 10.1039/d1cp03759e

Mechanistic Aspects of the Photophysics of UVA Filters Based on Meldrum Derivatives

Author(s): Josene M. Toldo, Mariana T. do Casal, Mario Barbatti
Published in: The Journal of Physical Chemistry A, Issue 125/25, 2021, Page(s) 5499-5508, ISSN 1089-5639
Publisher: American Chemical Society
DOI: 10.1021/acs.jpca.1c03315

Computational and experimental characterization of novel ultraviolet filters

Author(s): Jack M. Woolley, Raúl Losantos, Diego Sampedro, Vasilios G. Stavros
Published in: Physical Chemistry Chemical Physics, Issue 22/43, 2020, Page(s) 25390-25395, ISSN 1463-9076
Publisher: Royal Society of Chemistry
DOI: 10.1039/d0cp04940a

New Generation UV-A Filters: Understanding Their Photodynamics on a Human Skin Mimic

Author(s): Temitope T. Abiola, Natércia d. N. Rodrigues, Casey Ho, Daniel J. L. Coxon, Michael D. Horbury, Josene M. Toldo, Mariana T. do Casal, Benjamin Rioux, Cédric Peyrot, Matthieu M. Mention, Patrick Balaguer, Mario Barbatti, Florent Allais, Vasilios G. Stavros
Published in: The Journal of Physical Chemistry Letters, Issue 12/1, 2021, Page(s) 337-344, ISSN 1948-7185
Publisher: American Chemical Society
DOI: 10.1021/acs.jpclett.0c03004

Sinapic Acid Esters: Octinoxate Substitutes Combining Suitable UV Protection and Antioxidant Activity

Author(s): Cédric Peyrot, Matthieu M. Mention, Fanny Brunissen, Florent Allais
Published in: Antioxidants, Issue 9/9, 2020, Page(s) 782, ISSN 2076-3921
Publisher: MDPI
DOI: 10.3390/antiox9090782

Towards Developing Novel and Sustainable Molecular Light-to-Heat Converters

Author(s): Temitope T. Abiola, Florent Allais, Vasilios Stavros, Mario Barbatti, Albert Braeuning, Wybren Jan Buma, Matthieu M Mention, Cedric Peyrot, Mariana T. do Casal, Daniel J. L. Coxon, Michael N R Ashfold, Jack Matthew Woolley, Matthew Turner, Jimmy Alarcan, Benjamin Rioux, Josene M. Toldo
Published in: Chemical Science, 2021, ISSN 2041-6520
Publisher: Royal Society of Chemistry
DOI: 10.1039/d1sc05077j

Using diketopyrrolopyrroles to stabilize double excitation and control internal conversion

Author(s): Mariana Telles do Casal; Mario Barbatti; Felix Plasser; Josene M. Toldo
Published in: Physical Chemistry Chemical Physics, Issue 24, 2022, Page(s) 23279-23288, ISSN 1463-9076
Publisher: Royal Society of Chemistry
DOI: 10.1039/d2cp03533b

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