There are several drawbacks with the current commercially available ultraviolet (UV) filters used in sunscreen formulations, namely deleterious human and ecotoxic effects. As a result of the drawbacks, a current research interest is in identifying and designing new UV filters. One approach that has been explored in recent years is to use nature as inspiration, which is the focus of this review. Both plants and microorganisms have adapted to synthesize their own photoprotective molecules to guard their DNA from potentially harmful UV radiation. The relaxation mechanism of a molecule after it has been photoexcited can be unravelled by several techniques, the ones of most interest for this review being ultrafast spectroscopy and computational methods. Within the literature, both techniques have been implemented on plant-, and microbial-inspired UV filters to better understand their photoprotective roles in nature. This review aims to explore these findings for both families of nature-inspired UV filters in the hope of guiding the future design of sunscreens.

Light-to-heat conversion materials generate great interest due to their widespread applications, notable exemplars being solar energy harvesting and photoprotection. Another more recently identified potential application for such materials is in molecular heaters for agriculture, whose function is to protect crops from extreme cold weather and extend both the growing season and the geographic areas capable of supporting growth, all of which could help reduce food security challenges. To address this demand, a new series of phenolic-based barbituric absorbers of ultraviolet (UV) radiation has been designed and synthesised in a sustainable manner. The photophysics of these molecules has been studied in solution using femtosecond transient electronic and vibrational absorption spectroscopies, allied with computational simulations and their potential toxicity assessed by in silico studies. Following photoexcitation to the lowest singlet excited state, these barbituric absorbers repopulate the electronic ground state with high fidelity on an ultrafast time scale (within a few picoseconds). The energy relaxation pathway includes a twisted intramolecular charge-transfer state as the system evolves out of the Franck–Condon region, internal conversion to the ground electronic state, and subsequent vibrational cooling. These barbituric absorbers display promising light-to-heat conversion capabilities, are predicted to be non-toxic, and demand further study within neighbouring application-based fields.

Given the negative impacts of overexposure to ultraviolet radiation (UVR) on humans, sunscreens have become a widely used product. Certain ingredients within sunscreens are responsible for photoprotection and these are known, collectively herein, as ultraviolet (UV) filters. Generally speaking, organic UV filters work by absorbing the potentially harmful UVR and dissipating this energy as harmless heat. This process happens on picosecond time scales and so femtosecond pump–probe spectroscopy (FPPS) is an ideal technique for tracking this energy conversion in real time. Coupling FPPS with complementary techniques, including steady-state spectroscopy and computational methods, can provide a detailed mechanistic picture of how UV filters provide photoprotection. As such, FPPS is crucial in aiding the future design of UV filters. This Perspective sheds light on the advancements made over the past two years on both approved and nature-inspired UV filters. Moreover, we suggest where FPPS can be further utilized within sunscreen applications for future considerations.

Sinapoyl malate, naturally present in plants, has proved to be an exceptional UV filter and molecular heater for plants. Although there are nowadays industrially relevant sustainable synthetic routes to sinapoyl malate, its incorporation into certain cosmetic formulations, as well as its adsorption on plant leaves, is limited by its hydrophilicity. To overcome these obstacles, it is important to find a way to effectively control the hydrophilic–lipophilic balance of sinapoyl malate to make it readily compatible with the cosmetic formulations and stick on the waxy cuticle of leaves. To this end, herein, we describe a highly regioselective chemo-enzymatic synthesis of sinapoyl malate analogues possessing fatty aliphatic chains of variable length, enabling the lipophilicity of the compounds to be modulated. The potential toxicity (i.e., mutagenicity, carcinogenicity, endocrine disruption, acute and repeated-dose toxicity), bioaccumulation, persistence and biodegradability potential of these new analogues were evaluated in silico, along with the study of their transient absorption spectroscopy, their photostability as well as their photodegradation products.

The recent ban of some organic UV-filters – such as oxybenzone or octinoxate – considered toxic for coral reef, has heightened the need for eco-friendly alternatives, especially those synthesized using green approaches that reduce the carbon footprint. In this context, several thiobarbituric acid derivatives were synthetized from bio-based p-hydroxybenzaldehydes (e.g. vanillin, syringaldehyde) through a high-yielding sustainable Knoevenagel condensation, and their UV-filtering activity, stability and antiradical properties were investigated. The results showed promising UVA and blue light coverage over time, as well as competitive EC₅₀ values in comparison to commercial antioxidants (i.e. BHA and BHT). In order to evaluate the potential of these molecules as substitutes to current petroleum-based UV-filters, the potential toxicity and fate in environment of these new compounds were evaluated in silico. This screening did not show a critical potential for toxicity, making them promising candidates for further in vitro and in vivo assessment. GRAPHICAL ABSTRACT

Sinapate esters have been extensively studied for their potential application in ‘nature-inspired’ photoprotection. There is general consensus that the relaxation mechanism of sinapate esters following photoexcitation with ultraviolet radiation is mediated by geometric isomerization. This has been largely inferred through indirect studies involving transient electronic absorption spectroscopy in conjunction with steady-state spectroscopies. However, to-date, there is no direct experimental evidence tracking the formation of the photoisomer in real-time. Using transient vibrational absorption spectroscopy, we report on the direct structural changes that occur upon photoexcitation, resulting in the photoisomer formation. Our mechanistic analysis predicts that, from the photoprepared ππ* state, internal conversion takes place through a conical intersection (CI) near the geometry of the initial isomer. Our calculations suggest that different CI topographies at relevant points on the seam of intersection may influence the isomerization yield. Altogether, we provide compelling evidence suggesting that a sinapate ester’s geometric isomerization can be a more complex dynamical process than originally thought.