Deliverables Documents, reports (15) 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 Websites, patent fillings, videos etc. (1) Website and project logo Website and project logo Open Research Data Pilot (1) Data management plan Preparation of data management plan Publications Peer reviewed articles (27) 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 Searching for OpenAIRE data... There was an error trying to search data from OpenAIRE No results available
