Why do we get sunburn and how do I stop it? Prečo nás slnko spáli a ako to zastaviť? Úvod: (Slide 1) (Slide 2) Prednáška: (Slide 3)

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1 Why do we get sunburn and how do I stop it? Prečo nás slnko spáli a ako to zastaviť? Úvod: (Slide 1) I am delighted to be here today to take part in your celebration and to tell you a little bit about my research! Before I do however, I have to thank a number of people. (Slide 2) Firstly, I am extremely grateful to Professor Philipp Kukura (University of Oxford) for the very kind invitation. Some of you may be familiar with this surname.! Philipp is the son of Mr Juraj Kukura (who needs no introduction). Philipp and I met at the University of California, Berkeley (very close to San Francisco) and have been friends/colleagues ever since. Secondly, I absolutely must thank Zuzana Hajachova, for answering all my questions, providing guidance and support throughout, especially now with the translation. Thirdly (and lastly) I must thank my entire group both present and past. I cannot overstate how crucial a role they have played in what you will hear about today. Prednáška: (Slide 3) I guess the question you may be asking is, who am I and where is Warwick? I am a researcher/teacher from the University of Warwick which, from the image shown, is approximately 100 miles North of London. When preparing these slides, I wanted to show you where Warwick is relative to Bratislava, and I accidentally clicked the button (on Google maps) that gives me directions from Bratislava to Warwick! As you can see, it is approximately 1100 miles or a short 18h drive from here! Takže, určite sa pýtate kto som a kde je Warwick? Som výskumník a učiteľ na Univerzite vo Warwicku, ktorý, ako vidíte na obrázku, je asi 100 míľ severne od Londýna. Kým som si chystal sprievodné ilustrácie, omylom som klikol na Google maps navigáciu a ukázala mi, že Bratislava je od Warwicku vzdialená asi 1100 míľ ( km) alebo krátku, len 18 hodinovú jazdu autom! (Slide 4) OK so let s talk science! I begin by telling you a little about sunlight, given the title of my talk. Sunlight is energy and is a component of what we call the electromagnetic spectrum. The electromagnetic spectrum can be broken down into different components of radiation, including infrared radiation, visible radiation (normally what we refer to as light ), ultraviolet radiation etc. For reference, a size scale of each component of electromagnetic radiation is also shown. I will be focusing on ultraviolet radiation (UVR) for the rest of my talk as my research focuses on what happens to molecules (both natural and man-made) when they are bombarded with UVR. Fajn, poďme sa porozprávať o vede! Začnem tým, že Vám poviem niečo o slnečnom svetle, keďže sa ho týka aj názov prednášky. Slnečné svetlo je energia a skladá sa z niečoho, čo voláme elektromagnetické spektrum. Toto spektrum sa dá rozdeliť na veľa rôznych zložiek/druhov žiarenia ako infračervené žiarenie, viditeľné žiarenie (bežne ho nazývame svetlom), ultrafialové žiarenie (UFŽ) atď. Aby ste si to vedeli predstaviť, uvádzam mierku veľkostí každej zložky elektromagnetického žiarenia. Po zvyšok dnešnej prednášky sa budem

2 zameriavať na ultrafialové žiarenie keďže moja výskumná práca sa zameriava na to čo sa stane s molekulami (prirodzene sa vyskytujúcimi i vytvorenými človekom) keď ich začneme bombardovať ultrafialovým žiarením. (Slide 5+7) Light is composed of many different colours. I am sure that many of you have seen similar images before but when white light passes through a prism, the different components (colours) of light are clearly visible. The longer wavelengths correspond to the red components of light (lower energy) whilst the shorter wavelengths correspond to the blue components of light (higher energy). The bluest components are neighbours to UVR. UVR is both beneficial and detrimental to health and one strives to sustain a balance through moderating exposure. For example, notable positive attributions of UVR include production of vitamin D (for healthy bones) and general mental health; people are happier when it is sunny! However, negative attributions of UVR are sunburn (erythema; reddening of the skin), DNA (our genetic code) damage and ultimately skin cancer. The statistic of 131,000 new cases of skin cancer in the UK is alarming, especially given it is mostly cloudy! It is no surprise that this alarming statistic is hitting the UK tabloids, including one of our most notorious newspapers The Sun. As a side note, here is a paper I found dating back to 2000 about sun and skin cancer incidences in Slovakia. Svetlo sa skladá z rôznych farieb. Som si istý, že ste už niečo podobné videli - keď svetlo prechádza cez hranol, je jasne vidieť rôzne zložky svetla farby. Dlhšie vlnové dĺžky korešpondujú s červenými zložkami svetla (menej energie), kým kratšie vlnové dĺžky zodpovedajú za modré zložky svetla (viac energie). Najmodrejšie zložky susedia s ultrafialovým žiarením. Toto žiarenie môže byť prospešné aj škodlivé. A mali by sme sa snažiť nájsť rovnováhu v miere vystavenia sa jeho účinkom. Napríklad, kladnými vlastnosťami UFŽ sú tvorba vitamínu D (dôležitý pre zdravé kosti) a všeobecne pre zachovanie duševného zdravia; ľudia sú šťastnejší keď je slnečno! Ale medzi záporné vplyvy ultrafialového žiarenia patrí spálenie slnok, erytém začervenanie kože, poškodenie nášho genetického kódu, teda našej DNA a nakoniec aj rakovina kože. Štatistika ukazuje, že v Spojenom Kráľovstve je 131 tisíc nových prípadov rakoviny kože a to je šokujúce, najmä vzhľadom na to, že býva často pod mrakom! Nie je snáď preto prekvapivé, že aj anglické bulvárne noviny ako The Sun (slnko) uvádzajú výsledky tejto štatitiky. Len na okraj, tu je ukážka odborného článku z roku 2000, ktorý som našiel a ktorý opisuje výskyt rakoviny kože na Slovensku. (Slide 8+9) Our body has a natural defence mechanism for combatting overexposure to UVR; eumelanin, a brown pigment, is produced within skin cells to protect our DNA. The process of generating this pigment (ie., tanning) is a slow one and can take 3-5 days (typically). This is a long time and damage to DNA may have already occurred. As such, we need more immediate protection against UVR. Chemists like to come up with names for processes, and we call protection again light photoprotection. Sunscreens provide this immediate photoprotection, when you apply them to skin. Sunscreens contain many ingredients; next time you pick up a bottle, have a look at the ingredients! Broadly speaking, they contain physical scatterers, chemical absorbers and other components such as oils, moisturisers and many more components Physical scatterers, such as titanium dioxide nanoparticles, behave like very small mirrors and reflect UVR. Chemical filters on the other hand absorb the UVR (a bit like a sponge and water) and convert this potentially harmful light energy to

3 harmless heat energy. Developing better chemical filters is a very active field, especially given the growing trend in travel and tourism and more of us wanting to look good by having a nice tan. Understanding how chemical filters work, at the most detailed level, forms the main focus of my groups research. Naše telo má prirodzený obranný mechanizmus pre boj s nadmerným vystavením sa UFŽ; eumelanín, hnedý pigment, ktorý sa tvorí v kožných bunkách aby chránil našu DNA. Proces vytvárania tohoto pigmentu (samotného opálenia sa) je pomalý a môže trvať asi 3-5 dní. To je dosť dlhý čas, počas ktorého už mohlo dôjsť k porušeniu našej DNA. Potrebujeme teda viac okamžitej ochrany pred UFŽ. Chemici radi vymýšľajú nové názvy pre procesy a tak ochranu pred svetlom nazývame foto-ochrana. Opaľovacie krémy ponúkajú takúto okamžitú foto-ochranu keď si ich nanesiete na pokožku. Obsahujú veľa zložiek; nabudúce, keď vezmete fľaštičku krému na opaľovanie do rúk, pozrite sa na zloženie! Vo všeobecnosti sa dá povedať, že opaľovacie krémy obsahujú fyzické rozptyľové látky, chemické pohlcovače a iné zložky ako oleje, zvlhčovače a množstvo iných. Fyzické rozptyľovacie látky, ako kysličník titaničitý, sa správajú ako veľmi maličké zrkadielka a odrážajú UFŽ. Chemické filtre na druhej strane pohlcujú UFŽ (ako špongia vodu) a menia potenciálne škodlivú svetelnú energiu na neškodnú tepelnú energiu. V dnešnej dobe je hľadanie nových chemických filtrov veľmi aktívnou oblasťou vedeckého výskumu, predovšetkým s narastajúcim počtom turistov a cestovateľov, ktorí chcú pekne vyzerať a byť opálení. Hlavnou náplňou práce môjho výkumného tímu je snaha do detailu pochopiť ako chemické filtre fungujú. (Slide 10) To develop better chemical filters, one must understand, at a smallest level (or molecular level) what goes on in chemical filters once they absorb UVR. Consider the simple analogy: A car on a roundabout can come off at any one of the exits, each exit leading to a different destination; likewise a molecule having absorbed UVR can channel this energy along different pathways. Some pathways (viz. exits) are good, some pathways are bad. Grasping a handle on how to direct this energy flow is crucial as it then enables one to design better chemical filters. Crucially, if we can optimise the pathway that results in harmless heat production (100% of the time), then this would be an incredible result. Aby sme mohli vytvoriť lepšie chemické filtre, je potrebné pochopiť čo sa deje v chemických filtroch po pohltení UFŽ na najnižšej (molekulárnej) úrovni. Skúste si to predstaviť pomocou tohoto prirovnania: Auto ide po kruhovom objazde a môže z neho zísť niekoľkými východmi/cestami, z ktorých každý smeruje inam; takisto molekula po pohltení UFŽ môže nasmerovať prijatú energiu rôznymi cestami. Niektoré z týchto ciest/východov sú dobré, iné zlé. Presné pochopenie toho ako ovplyvniť tok energie je dôležitým predpokladom na vytvorenie lepších chemických filtrov. Ak by sme vedeli predurčiť najlepšiu z ciest prijatej energie na 100% po celý čas procesu pohlcovania svetla, bol by to úžasný výsledok, zmenila by sa na neškodnú tepelnú energiu! (Slide 11) As mentioned earlier, sunscreens are multicomponent, their ingredients varying somewhat depending on sunscreen type. The active ingredients listed here are chemical filters. As we can see, the chemical filters listed under ingredients are avobenzone (3%), homosalate (10%) and octyl-methoxycinnamate (7.5%). In fact, we have studied how all of these ingredients respond to UVR in my laboratory. To give

4 you an idea of what one of these chemical filters looks like, here is octylmethoxycinnamate (conveniently abbreviated EHMC). In our experiments, we typically zap this molecule with light and study its light absorbing properties (light emission, reaction, heat generation etc.) both in an isolated environment, a bit like space, and in solution, as shown. Here, the Death Star serves to depict one of our key instruments, the laser, which mimics the UVR from the Sun. The laser also enables us to visualise the different (competing) pathways; in essence we can develop a movie of what happens to a chemical filter when it absorbs UVR! We are one of the very few groups in the world that can do this. Ako som už predtým hovoril, opaľovacie krémy sú viaczložkové a ich zložky sú rôzne v závislosti od druhu opaľovacieho prípravku. Aktívne zložky, ktoré tu uvádzam, sú chemické filtre. Ako vidíte na obrázku, sú to avobenzón (3%), homosalát (10%) a oktyl-metoxycinamát (7.5%). V mojom laboratóriu sme skúmali ako všetky spomenuté filtre reagujú na UFŽ. Aby ste mali predstavu ako to vyzerá, tu je oktyl-metoxycinamát, skrátene EHMC (etylhexyl-metoxicinamát). V našich pokusoch zväčša preženieme jeho molekulu svetlom a skúmame aké má vlastnosti pohlcovania svetla (žiarenie svetla, reakcia, vytváranie tepla atď.) v izolovanom prostredí, trochu podobnom tomu vo vesmíre, a potom v roztoku, ako vidíte na obrázku. Hviezda smrti (obrovská útočná bojová loď z filmov Star Wars, poznámka prekladateľky) nám tu ukazuje jeden z kľúčových nástrojov, ktoré používame laser, ktorý napodobňuje UFŽ zo Slnka. Laser nám umožňuje predstaviť si rôzne (alternatívne) cesty vedenia energie, vlastne dokážeme vytvoriť film toho, čo sa deje, keď chemický filter pohltí UFŽ! Je len veľmi málo výskumných tímov na svete, ktoré dokážu niečo také. (Slide 12) The molecules we study are far ranging, each molecule having a different composition of hydrogen, carbon, nitrogen and oxygen atoms. Indeed, both the composition of atoms and their arrangement play a crucial role in their light absorbing properties including (and importantly) how they may convert light energy to heat energy. In fact, we (as well as others) have shown that particular regions of the molecule, composed of specific groups of atoms, are more important in a molecule s light absorbing properties than others. I have circled these for clarity. By developing some predictive tools about how such groups of atoms best control a molecules light absorbing properties, we may then be able to generate the perfect chemical filter! Študujeme široké spektrum rôznych molekúl, z ktorých každá má iné zloženie atómov vodíka, uhlíka, dusíka a kyslíka. V skutočnosti práve zloženie atómov a ich usporiadanie zohrávajú kľúčovú úlohu v ich schopnosti pohlcovať svetlo vrátane toho, čo je dôležité, ako premieňajú svetelnú energiu na tepelnú. Tak ako niektoré iné tímy, aj my sme dokázali, že isté oblasti molekúl, zložené zo špecifických atómov, sú dôležitejšie pre pohlcovanie svetla ako iné. Zakrúžkoval som ich pre Vás na obrázku. Ak by sme dokázali vytvoriť akési pomôcky či nástroje na predvídanie, ktoré skupiny atómov najlepšie riadia schopnosti molekúl pohlcovať svetlo, mohli by sme vytvoriť dokonalý chemický filter! (Slide 13) What is shown here are three different classes of chemical filter: cinnamate (left), anthranilate (middle) and benzophenone (right). For the cinnamate, once it absorbs UVR, the molecular pathway that drives the light absorbing properties is a bond-flip. This is an extremely fast process (5 billion times every blink of an eye)! For the anthranilate, upon absorbing UVR, it remains trapped in an excited state (see video

5 for illustration!). This is not good news as the anthranilate in this state is highly reactive and may break down into toxic products. Lastly for the benzophenone chemical filter, the molecular pathway that drives its light absorbing properties is also an extremely fast process. However, in addition to generating heat, it can also generate a product that that is highly toxic. Tu môžete vidieť tri rôzne skupiny/triedy chemických filtrov: cinamát (vľavo), antranilát (v strede) a benzofenón (vpravo). Keď cinamát pohltí UFŽ, jeho molekulárnou cestičkou, ktorá ovplyvňuje pohltenie svetla, je preklopená chemická väzba. Je to extrémne rýchly proces (5 miliard krát za každé mihnutie oka)! Antranilát zostáva po pohltení UFŽ uväznený v excitovanom/vzbudenom stave (pozrite si video s mačkou). To by sa nemal stať, pretože v tomto stave je antranilát veľmi reaktívny a mohol by sa zmeniť a produkovať toxické látky. Benzofenón a jeho molekulárna cesta pohltenia svetla je tiež neuveriteľne rýchla. Bohužiaľ, okrem toho, že vytvára tepelnú energiu, produkuje aj vysoko toxické/škodlivé látky. (Slide 14+15) Developing new chemical filters has never been more pressing, especially given the recent findings that oxybenzone, an FDA (Food and Drug Administration) approved chemical filter, is toxic to corals and causes coral bleaching. In fact, the state of Hawaii is now banning the use of oxybenzone. Potreba vytvárania nových chemických filtrov nikdy nebola taká naliehavá ako dnes, predovšetkým kvôli novým zisteniam, že oxybenzón, chemický filter pôvodne schválený Úradom pre kontrolu potravín a liečiv (FDA), je škodlivý a spôsobuje bielenie podmorských korálov. Štát Hawai preto nedávno zakázal používanie oxybenzónu. (Slide 16+17) There is certainly hope for sunscreens! Along with other teams of researchers across the globe, we are starting to truly get a handle on how can we modify the arrangement of atoms in a chemical filter (predictably) which in turn influences its light absorbing properties. Recent work from my group (self-dubbed Team Stavros) has shown that simple modifications to an anthranilate, such as moving two groups of atoms apart (by one atom!), can have an enormous influence on its light absorbing, including heat generating, properties. Likewise extending the complexity of a cinnamate can make it absorb more UVR. This latter results means that a sunscreen may not need to be multicomponent (cheaper and reduces potential risks to health). Nevzdávajme sa však nádeje pre opaľovacie prípravky! Spolu s inými výskumnými tímami na svete sa nám začína dariť skutočne chápať ako môžeme meniť usporiadanie atómov v chemickom filtri aby sme vedeli predvídať a ovplyvniť jeho schopnosti pohlcovať svetlo. Nedávne výsledky práce mojej výskumnej skupiny (ktorá sa sama nazvala Tím Stavros) ukazujú, že jednoduché pozmenenie antranilátu, akým je oddelenie dvoch skupín atómov (len jedným atómom) môže mať obrovský dopad na ovplyvnenie jeho schopnosti pohlcovať svetlo a vytvárať teplo. Takisto rozšírením skladby cinamátu môžeme ovplyvniť to, že pohltí viaz UFŽ. Výsledkom niečoho takého môže byť opaľovací krém s menším množstvom zložiek, čo kladne ovplyvní jeho cenu a tiež zníži riziká pre naše zdravie. (Slide 18) To summarise, sunscreens are very important, please use them! Every sunscreen molecule (in a given class) behaves differently and knowing how they channel the UVR energy is crucial in helping us design new sunscreens. Notably, this

6 work forms part of a much larger puzzle; the next step will involve building the complexity of the systems we study to include more ingredients and how these ingredients influence the properties of the chemical filter. Na záver teda zhrniem, že opaľovacie prípravky sú nesmierne dôležité, prosím, používajte ich! Každá molekula opaľovacieho krému sa v rámci svojej triedy správa odlišne a pochopenie toho, ako cez ňu bezpečne previesť UFŽ je dôležitým poznatkom pre vytváranie nových opaľovacích prípravkov. Naša výskumná práca je dielikom väčšej skladačky; nasledujúcim krokom bude vytvoriť komplexné systémy toho, čo skúmame a zapojiť do nich viac zložiek, a tiež pochopiť ako ovplyvňujú vlastnosti chemických filtrov. (Slide 19) I would like to finish by once again acknowledging my hosts, Team Stavros, the funding agencies that generously keep this research running and of course you for listening. Congratulations on your special day and thank you. Rád by som na záver ešte raz poďakoval mojim hostiteľom, výskumnému tímu Stavros, inštitúciám, ktoré náš výskum financujú a samozrejeme, najmä Vám za pozornosť. Gratulujem Vám k úspešnému absjolvovaniu tohto ročníka DUK! Ďakujem!

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