· To develop novel biosynthetic procedures for producing environment-friendly UV sunscreens
· To characterise UV sunscreens with state-of-the-art analytical (laser based) techniques
· To correlate structure-dynamics-function of sunscreens using theory and computation
Cases of cosmeceuticals interfering with marine life are now widespread. This is largely due to increasing societal trends towards exposure to ultraviolet radiation (UVR) from sunlight. Sunscreens provide UVR-protection; however, this often comes at a cost as the desired sun protection factor (SPF) is achieved with high concentrations of UVR filters within a blend. This can lead to serious environmental issues. For example, some sunscreens are known to be damaging to marine life [1,2]; indeed Hawaii, will ban the use of certain UVR filters (e.g. oxybenzone) in sunscreen blends due to coral bleaching . It is therefore key to develop next generation, safer sunscreens which preserve the quality of aquatic life.
The proposed CENTA2 project seeks to answer the overarching question: Can microorganism (e.g. algae, cyanobacteria etc.)-based UVR filters be chemically modified for human use, that combine the resilience to UVR exposure and, importantly to the ethos of NERC, are much safer to the environment? Three researchers within the University of Warwick (UoW) spanning Chemistry, Life Sciences and Centre for Scientific Computing, along with Lubrizol, a leading skin-care industry, propose to apply their complementary skills in experiment and theory to train a highly talented early career researcher to confront the multi-facetted challenges imposed by this question.
The proposed programme offers a potentially transformative contribution to the photophysically fascinating, and marine (and health)-care vital, field of sunscreen science. The present CENTA2 is an ideal platform to support this research, given the closely aligned links between NERC Research Areas including: (1) Pollution, Waste and Resources (closely aligned); (2) Marine Environments; and (3) Environmental Microbiology, as well as being intimately aligned with one of the Sciences Themes of CENTA2, that of Climate and Environmental Sustainability. Lastly, the present project provides an ideal opportunity to link with Lubrizol’s division of Skin Care, led by Professor Laurent Blasco, Honorary Professor at the University of Warwick and Lubrizol’s global skin care manager.
Theory and computation: steady-state calculations will employ TD-DFT [4,5]/CASPT2 [6,7] to yield details of molecular structure of UVR filters, while dynamics simulations will use trajectory surface hopping methods and solvation models to compute photorelaxation dynamics in solution/condensed-phases.
Biosynthesis: The UVR filters will involve bacterial expression, purification and characterisation. Bacterial production of these nature-derived systems will be based on well established procedures as discussed in REFS  and .
Spectroscopy: Transient absorption spectroscopy  will be used to track energy flow in these molecules following absorption of UVR. These techniques are crucial in enabling us to build molecular-movies of energy flow over the time window of 10-15–10-3 s.
Analytical chemistry: The most promising UVR filters will be converted to a sunscreen blend (UVR-filter/moisturizer) and deposited on skin model VITRO-SKIN® . Following UVR exposure, the blend will be washed off in water and contents analysed for potential photogenerated/phototoxic products.
Training and skills:
The excellent Early-Career Researcher (ECR) will be trained to perform a diverse range of experiments (at Warwick and Lubrizol (Analytical chemistry-see above)), complemented by high-level calculations. Their contribution will be paramount to the success of this CENTA2 project. The ECR will benefit from exposure to state-of-the-art experiment and theory and computation capabilities, set in a much wider interdisciplinary context, which strives to address an important question relating to preserving the quality of aquatic life. No doubt this environment will offer wonderful opportunities to enhance their skills sets and their future employability.
Partners and collaboration:
The proposed studies will inform industry-based researchers currently utilising ‘top-down’ methodologies to develop next generation UVR filters that combine the requirements of resilience to photodegradation and acceptably low (preferably zero) adverse effects. Stavros (PI) has already taken steps to incorporate industry by linking with Lubrizol, specifically Laurent Blasco (LB), global skin care manager at Lubrizol and Honorary Professor at Warwick. LB is thrilled at the opportunity to work with the CENTA2 Team, likely at Level 1, to explore the potential use of microbial based UVR filters that are less toxic, not just to humans, but to marine life.
This funding provides full tuition fees at the Home/EU rate, pays an annual stipend in line with UK Research Councils (currently £15,009) and a research training support grant (RTSG) of £8,000
 Toxicopathological Effects of the Sunscreen UV Filter, Oxybenzone (Benzophenone-3), on Coral Planulae and Cultured Primary Cells and Its Environmental Contamination in Hawaii and the U.S. Virgin Islands, C.A. Downs, E. Kramarsky-Winter, R. Segal, J. Fauth, S. Knutson, O. Bronstein, F.R. Ciner, R. Jeger, Y. Lichtenfeld, C.M. Woodley, P. Pennington, K. Cadenas, A. Kushmaro and Y. Loya, Arch. Environ. Contam. Toxicol., 2016, 70, 265.
 Density-functional thermochemistry. III. The role of exact exchange, A.D. Becke, J. Chem. Phys. 1993, 98, 5648–5652.
 Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density, C.T. Lee, W.T. Yang and R.G. Parr, Phys. Rev. B 1988, 37, 785–789.
 Multireference perturbation theory for large restricted and selected active space reference wave functions, P. Celani and H.J. Werner, J. Chem. Phys., 2000, 112, 5546.
 Third-order multireference perturbation theory – The CASPT3 method, H.J. Werner, Mol. Phys., 1996, 89, 645.
 pH-independent charge resonance mechanism for UV protective functions of shinorine and related mycosporine-like amino acids, K. Matsuyama, J. Matsumoto, S. Yamamoto, K. Nagasaki, Y. Inoue, M. Nishijima and T. Mori, J. Phys. Chem. A, 2015, 119, 12722.
 Discovery of gene cluster for mycosporine-like amino acid biosynthesis from Actinomycetales microorganisms and production of a novel mycosporine-like amino acid by heterologous expression, K.T. Miyamoto, M. Komatsu and H. Ikeda, Appl. Environ. Biol., 2014, 80, 5028.
 A perspective on the ultrafast photochemistry of solution-phase sunscreen molecules, L.A. Baker, S.E. Greenough and V.G. Stavros, J. Phys. Chem. Lett., 2016, 7, 4655.
 In vitro evaluation of sunscreens: an update for the clinicians, M. Pelizzo, E. Zattra, P. Nicolosi, A. Peserico, D. Garoli and M. Alaibac, ISRN Dermatol., 2012, 1-4.
Additional reading regarding sunscreen science can be found at the PIs website, specifically publication page. www.go.warwick.ac.uk/teamstavros
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FTE Category A staff submitted: 12.60
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