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Solving world problems with pyrrole: 65th birthday tribute to Prof. Jonathan L. Sessler

2022; Elsevier BV; Volume: 8; Issue: 3 Linguagem: Inglês

10.1016/j.chempr.2022.02.005

2451-9308

Calvin V. Chau, Sajal Sen, Adam C. Sedgwick, Philip A. Gale, G. Dan Pantoş, Sung Kuk Kim, Jung Su Park, Elisa Tomat, Jonathan F. Arambula, Anne E. V. Gorden, Hiroyuki Furuta,

Magnetism in coordination complexes

To celebrate Prof. Jonathan Sessler’s 65th birthday, this Backstory on his life and career follows his path to success. We begin with his early days as an independent researcher and then show how his Texas-sized chemistry has molded over the years with the help of the “Crown and Anchor approach.” We hope this article will inspire readers to pursue their own academic endeavors and remember Jonathan’s guiding motto: “people first, science second, money third.” To celebrate Prof. Jonathan Sessler’s 65th birthday, this Backstory on his life and career follows his path to success. We begin with his early days as an independent researcher and then show how his Texas-sized chemistry has molded over the years with the help of the “Crown and Anchor approach.” We hope this article will inspire readers to pursue their own academic endeavors and remember Jonathan’s guiding motto: “people first, science second, money third.” “People first, science second, money third.”"The best postdocs have fun and often ignore my intellectual input." Born in the cold, windy city of Urbana, IL, Jonathan L. Sessler was welcomed into a family full of intellectuals. Jonathan’s father, Andrew M. Sessler, was a world-famous American physicist at the Lawrence Berkeley National Laboratory in California and was recognized with the Enrico Fermi Award (2014), a presidential award (awarded by President Barack Obama) honoring scientists for lifetime achievements. Jonathan’s father made sure that Jonathan, at a very young age, knew how to think critically. Family dinners consisted of discussions on either how to solve some problem or how to gather opinions on whether a view expressed in a journal article made sense. Thus, the Sessler household was the perfect environment for Jonathan to grow into the person he is today. However, unlike his father, Jonathan found physics in high school (Berkeley High School) to be a disaster. Thankfully, a truly gifted chemistry teacher in high school, Mr. Choulet, identified his passion and gift for the subject and gave him the tools he needed to succeed. Of course, this influence led Jonathan to pursue chemistry as an undergraduate at the University of California, Berkeley (UCB), where he was taught and inspired by the likes of Leo Brewer, Andrew Streitwieser, and Alex Pines. While in college, Jonathan spent a year at the Hebrew University of Jerusalem, where he made lifelong friends in and out of chemistry. For graduate school, Jonathan switched Bay Area allegiances and joined Stanford University to work in the lab of James P. Collman (with John Brauman as a co-mentor). Here, Jonathan was exposed to various aspects of bioinorganic and biomimetic chemistry using inorganic complexes and porphyrins. Unfortunately, during this time, he suffered a relapse of his Hodgkin’s lymphoma (he was first diagnosed and treated when he was at UCB), requiring him to undergo intense chemotherapy, which left him to suffer through severe and debilitating side effects. Luckily, several group members and friends (Roger Pettman, Penny Brothers, Dave Ware, Mark Johnson, Alan Flamberg, and undergraduate Brent Iverson) assisted him throughout this process, and so too did his family. Although this was an unfortunate time, this moment of adversity led to an important connection that helped shape his career: it made him close to his oncologist, Richard A. Miller. Current and previous Sessler group members believe that this period in his life led to this simple philosophy for Jonathan’s academic career: “people first, science second, money third.” After completing his PhD, Jonathan moved to Strasbourg, France, as an NSF-NATO and NSF-CNRS postdoctoral research fellow in the lab of Nobel Laureate Jean-Marie Lehn. Inspired by Lehn’s creativity, Jonathan soon wanted to become a supramolecular chemist as well as a porphyrin chemist and attempted to merge both areas together. Like many young researchers today who fear that they might not succeed in obtaining a suitable academic position and thus delay the start of their independent careers, Jonathan took a second postdoc: he moved to Kyoto, Japan, to join the lab of the late Iwao Tabushi. There, he was exposed to the concepts of electron transfer within synthetic systems. One goal along these lines in the Tabushi group involved the development of synthetic wires designed to facilitate electron transfer over long distances. Jonathan’s postdoctoral stay in Kyoto led to his connection with the late Marye Ann Fox, who helped facilitate Jonathan’s arrival at the University of Texas at Austin. Fascinated by the “pigments of life” tetrapyrrolic porphyrins in terms of their aromaticity, rich metal coordination properties, and biological applications, Jonathan first set out to develop so-called “expanded porphyrins.” Expanded porphyrins are porphyrin analogs (1) that go beyond the traditional four pyrrolic subunits (>4 heterocycles and aromatics with a larger internal cavity).1Sessler J.L. Seidel D. Synthetic expanded porphyrin chemistry.Angew. Chem. Int. Ed. 2003; 42: 5134-5175Google Scholar The key attraction to their development was both practical and theoretical. Because of their resemblance to porphyrins, it was hoped that they would display an extensive coordination chemistry and overcome the limits of porphyrin-based metal complexes (i.e., serve as new ligands for lanthanides and actinides). Jonathan also wanted to explore the limits to which the classic Hückel definition of aromaticity (4n + 2 π-electrons) holds true and to understand what factors endow a fully conjugated macrocycle with characteristics that can be considered aromatic or antiaromatic (4n-π-electrons). This is a challenging objective still being pursued in today’s chemistry world by Harry Anderson, Dongho Kim, Atsuhiro Osuka, Lechosław Latos-Grażyński, Hirose Shinokubo, Jishan Wu, and many others. Another factor driving the development of expanded porphyrins was the idea that an increase in π-conjugation results in a significant red shift in absorption relative to the spectral features of porphyrin. These properties are desirable for use in photodynamic therapy (PDT), photothermal therapy, and optical imaging applications because the longer wavelengths allow for deeper tissue penetration. Before the term “expanded porphyrins” was introduced by Jonathan in 1988, the first example of a macrocycle fitting the definition dated back to R.B. Woodward and his research group. During their synthetic efforts to synthesize vitamin B12, they serendipitously discovered 22-π-electron sapphyrin (2), a pentapyrrolic macrocycle.1Sessler J.L. Seidel D. Synthetic expanded porphyrin chemistry.Angew. Chem. Int. Ed. 2003; 42: 5134-5175Google Scholar Although structurally unique, this was not of interest to the Woodward group and was only introduced briefly in a formal oral presentation and reported posthumously.2Bauer V.J. Clive D.L.J. Dolphin D. Paine J.B. Harris F.L. King M.M. Loder J. Wang S.W.C. Woodward R.B. Sapphyrins - Novel aromatic pentapyrrolic macrocycles.J. Am. Chem. Soc. 1983; 105: 6429-6436Google Scholar It was not until Jonathan and his team developed a streamlined synthetic route that in-depth studies became possible. As predicted, the absorption of sapphyrin was considerably red shifted in comparison to that of porphyrins.1Sessler J.L. Seidel D. Synthetic expanded porphyrin chemistry.Angew. Chem. Int. Ed. 2003; 42: 5134-5175Google Scholar Continued efforts from the Sessler group led to the isolation of 26-π-electron aromatic rubyrin (3). Not only did these studies demonstrate that Hückel’s rule still applied beyond 18-π-electron porphyrin, but these expanded porphyrins demonstrated the ability to bind to negatively charged anions, such as fluoride and phosphate ions. This initial observation was seen during the analysis of the sapphyrin crystal structure, in which a fluoride ion was found in the diprotonated core.3Král V. Furuta H. Shreder K. Lynch V. Sessler J.L. Protonated sapphyrins. Highly effective phosphate receptors.J. Am. Chem. Soc. 1996; 118: 1595-1607Google Scholar As a funny sidenote, at the time (ca. 1990), Jonathan’s graduate student, John Sibert, accidentally sniffed the sapphyrin crystal under the twin influences of excitement and allergies, which led this compound to be called suffyrin by some Sessler group members. On a more serious level, the observation that sapphyrin and rubyrin would form complexes with anions changed the way we think about pyrrolic systems. Prior to this discovery, porphyrin and its known analogs were known as ligands for positively charged metal cations. Once anion recognition was recognized as a possible feature of pyrrolic macrocycles, it inspired the development of much larger and more exotic oligopyrrole systems that can now be seen in the literature (i.e., turcasarin [4]).1Sessler J.L. Seidel D. Synthetic expanded porphyrin chemistry.Angew. Chem. Int. Ed. 2003; 42: 5134-5175Google Scholar During this time, Jonathan also focused on exploring hydrogen-bonding base pairing (DNA, nucleoside derivatives, etc.) for various new and exciting applications.4Sessler J.L. Magda D. Furuta H. Synthesis and binding-properties of monomeric and dimeric guanine and cytosine amine derivatives.J. Org. Chem. 1992; 57: 818-826Google Scholar These efforts were aided by a handful of students and postdocs, including Darren Magda, Hiroyuki Furuta, Yuji Kubo, and Janarthanan Jayawickramarajah. Jonathan’s contributions to expanded porphyrin chemistry date back to 1988. At that time, his first postdoc, Toshiaki Murai, with help from others, succeeded in producing a penta-aza Schiff-base macrocycle that bore a resemblance to the five-pointed star in the state flag of Texas.1Sessler J.L. Seidel D. Synthetic expanded porphyrin chemistry.Angew. Chem. Int. Ed. 2003; 42: 5134-5175Google Scholar An interview with Chemical & Engineering News allowed Jonathan to introduce his pet name for this molecule, texaphyrin, to the world. Before the discovery of texaphyrin, Jonathan was particularly anxious about whether he would have been offered tenure. To gain motivation within the group, Jonathan took his entire group on a ski trip to New Mexico. While the flight was refueling in a less-appealing west Texas town, Jonathan said that if he did not make tenure, they would be decamping from Austin to there. This clearly worked because the first texaphyrin, in the form of its cadmium complex, was subsequently isolated, and Jonathan made tenure. This significant discovery opened the door to research that is still being pursued today by Jonathan and other research groups (e.g., Gang Zheng at the University of Toronto) some 30 years on. Texaphyrin was the first expanded porphyrin to display diverse metalation properties and the first porphyrin-type system to form a 1:1 stable complex with trivalent cations of the lanthanide series. This special coordination chemistry of texaphyrin was ascribed to the fact that the inner coordination core is roughly 20% larger than that present in porphyrins and the available nitrogen donors in the deprotonated species.1Sessler J.L. Seidel D. Synthetic expanded porphyrin chemistry.Angew. Chem. Int. Ed. 2003; 42: 5134-5175Google Scholar Motivated by this finding, Sessler and his team went on to develop uranyl pentaphyrin (5), the first structurally characterized expanded porphyrin to display in-plane coordination with an actinide cation (uranyl [UO22+]).5Brewster II, J.T. Zafar H. Root H.D. Thiabaud G.D. Sessler J.L. Porphyrinoid f-element complexes.Inorg. Chem. 2020; 59: 32-47Google Scholar Since this report, Sessler and others have explored the potential of addressing environmental concerns associated with nuclear waste by employing expanded porphyrins in selective sequestration or as colorimetric indicators of actinide contaminants. With help from graduate students Daniel Seidel and Anne Gorden (née Vivian) and collaborators at the Los Alamos National Laboratory, they discovered a select example by using a hexaphyrin (shorthand for an expanded porphyrin with six pyrrolic subunits) to stabilize a neptunium complex, the first all-aza coordination complex for neptunium (6). Hexaphyrins are noteworthy because they can exist as stable 22-, 24-, or 26-π-electron systems.5Brewster II, J.T. Zafar H. Root H.D. Thiabaud G.D. Sessler J.L. Porphyrinoid f-element complexes.Inorg. Chem. 2020; 59: 32-47Google Scholar Notably, Jonathan and the Los Alamos National Laboratory have a long-standing collaborative network that has allowed investigations to proceed with expanded porphyrin coordination complexes of neptunium, plutonium, americium, and pertechnetate. As a porphyrin chemist and since his Stanford days, Jonathan was fully aware that porphyrins localize in tumors and were being used as PDT agents for cancer treatment. Thus, Jonathan believed that the arsenal of expanded porphyrins being created in his lab might prove useful for this purpose. Specifically, he postulated that a metallotexaphyrin wherein the coordinated metal cation is the paramagnetic lanthanide Gd(III) would be useful in the diagnosis of cancerous lesions by MRI, whereas its diamagnetic Lu(III) congener would be effective in PDT. Several attempts to obtain funding from the NIH for this combined imaging and treatment objective were unsuccessful. Sessler turned to his former oncologist and friend, Richard A. Millar, for his thoughts on one of the failed NIH proposals. Coincidentally, at the time, Richard was investigating the tumor-targeting ability of yttrium-90 antibody conjugates for radiation therapy. To their surprise, Richard and Jonathan discovered that the gadolinium texaphyrin localized in tumors to a greater extent than the antibody being tested at that point in time. This led to collaborative efforts for the exploration of texaphyrin with the synthetic help of Greg Hemmi, Tarak D. Mody, Mike Cyr, and other Sessler group members. It also led to the co-founding of Pharmacyclics in 1991. Under Richard’s leadership and with Jonathan as an advisor, Pharmacyclics managed to advance the Gd(III) and Lu(III) complexes of texaphyrin (known as MGd and MLu, respectively) into advanced clinical trials as adjuvants for the radiation- and light-based treatment of cancer and cardiovascular disease, respectively. Even though metallotexaphyrins displayed good biocompatibility, tumor selectivity, and signs of efficacy, in late 2005, MGd failed to receive FDA approval. This led to the halting of the texaphyrin program and corporate redirection at Pharmacyclics. The company turned its attention toward other in-license technologies. In due course, this led to the FDA approval of Imbruvica (ibrutinib). This approval resulted in the acquisition of Pharmacyclics by AbbVie in 2015 for $21 billion. Jonathan used his small scientist’s share of the money to pay for the education of his two sons, Jordan and Chanan, and to buy a lake house on Lake Travis (Austin, TX), where he regularly stays on the weekends over the summer to enjoy a cold beer, BBQ with friends, and go windsurfing. When the weather is fine, Jonathan drives out to his lake house in his 2008 Aston-Martin V8 Vantage. His daily drive is now a Tesla with the license plate “SESLA.” In 1994, Jonathan attended the NATO Science Committee Advanced Research Workshop on Transition Metals in Supramolecular Chemistry, which was held at Santa Margherita Ligure near Genoa, Italy. At that meeting, the late Carlo Floriani presented his work on metal complexes of porphyrinogens. Jonathan attended Floriani’s lecture and realized that the porphyrinogens (tetrapyrrolic macrocycles consisting of pyrrole rings linked in the 2- and 5-positions by sp3 hybridized carbon atoms) could serve as an “old yet new” class of anion receptors (having first been synthesized by Baeyer in 1886). Jonathan’s motivation was to develop easy-to-make pyrrole-based macrocycles that could act as anion receptors. The idea was to provide a complement to expanded porphyrins, the syntheses of which were often challenging (yields were sometimes as low as 1%) and which required protonation to bind anions well. Jonathan often shares comparisons on these synthetic yields with paper and grant rejections. Also, in the audience that day in Italy was a young DPhil student from Oxford, Phil Gale. Phil wished to follow his doctoral studies on calixarenes with further work in supramolecular chemistry; these motivations led him to join the Sessler group as a Fulbright Postdoctoral Fellow in October 1995. Gale prepared two known porphyrinogens formed by the acid-catalyzed condensation of pyrrole with either acetone or cyclohexanone and found that both of these neutral compounds (which could be obtained in very high yield) formed 1:1 complexes with anions (7 and 8).6Gale P.A. Sessler J.L. Král V. Lynch V. Calix[4]pyrroles: Old yet new anion-binding agents.J. Am. Chem. Soc. 1996; 118: 5140-5141Google Scholar When pyrrole was condensed with a ketone, the resultant macrocycles were not prone to undergo oxidation, and the pyrrole rings were free to rotate in solution through the annulus of the macrocycle. Gale obtained crystal structures of the free macrocycles, which showed that they adopt a 1,3-alternate conformation in the solid state with the pyrrole rings oriented alternatively up and down. Upon complexation of an anion, the crystal structure revealed that all four pyrrole groups form hydrogen bonds to the bound guest such that the macrocycle now adopts a cone conformation. The conformational similarities between the calixarenes and porphyrinogens led Sessler and Gale to rename these macrocycles calix[4]pyrroles. Since this first report in 1996 by Gale, Sessler, Král, and Lynch, the literature on calixpyrrole has expanded tremendously—more than 600 papers have been published on the topic to date. In 2002, a subsequent sabbatical visitor to the Sessler group, Chang Hee Lee, reported the syntheses of “strapped” calixpyrroles. This seminal report opened a whole new field for calixpyrroles in terms of ion-pair receptors, molecules that can bind both an anion and a cation.7He Q. Vargas-Zúñiga G.I. Kim S.H. Kim S.K. Sessler J.L. Macrocycles as ion pair receptors.Chem. Rev. 2019; 119: 9753-9835Google Scholar As seen with hexaphyrin in the context of actinide-related research (see above), another research passion for Jonathan was to utilize pyrrole chemistry to solve environmental issues. Jonathan and his team used this concept to develop new methods for the extraction of the cesium cation—the radioactive form of which is a major problem because of its long half-life (137Cs: 30.2 years). In collaboration with Bruce A. Moyer at Oak Ridge National Laboratory, Sung Kuk Kim (Jonathan’s graduate student at the time) and collaborators successfully developed the ion-pair receptor 9, which enabled the selective and reversible liquid-liquid extraction of CsNO3.8Kim S.K. Vargas-Zúñiga G.I. Hay B.P. Young N.J. Delmau L.H. Masselin C. Lee C.H. Kim J.S. Lynch V.M. Moyer B.A. Sessler J.L. Controlling cesium cation recognition via cation metathesis within an ion pair receptor.J. Am. Chem. Soc. 2012; 134: 1782-1792Google Scholar Ongoing work in the Sessler lab involves the incorporation of examples such as 9 into material-based systems for use in other real-world environmental applications, including but not limited to the use of “strapped” calixpyrroles for lithium-ion capture and anion transport for cancer therapy.7He Q. Vargas-Zúñiga G.I. Kim S.H. Kim S.K. Sessler J.L. Macrocycles as ion pair receptors.Chem. Rev. 2019; 119: 9753-9835Google Scholar Driven to expand the scope of host-guest complexes seen for calix[4]pyrroles, Jonathan collaborated with Jan Jeppesen (University of Southern Denmark) and members of his team to develop a series of tetrathiafulvalene(TTF)-calix[4]pyrroles. They found that the incorporation of electron-rich TTF onto the calix[4]pyrrole framework endowed the resulting frameworks with new and interesting binding characteristics and switching functions. The readily bound substrates ranged from electron-deficient molecules, nitro-aromatic explosives, and fullerenes derivatives to fluorophores. Among these host-guest interactions, donor-acceptor and charge-transfer interactions were observed. Excitingly, electron-transfer processes dependent on the nature of the electron-deficient partner and the conformation of the TTF-calix[4]pyrrole were demonstrated. Self-assembled structures were also obtained from discrete supramolecular assemblies. These newly identified properties were utilized as colorimetric and fluorometric sensors for explosives, 2- or 3-state charge- or electron-transfer switches, and molecular logic gates and to provide advanced cascade control over downstream reactions (e.g., anion-induced chemical communication between self-assembled constructs).9Bähring S. Root H.D. Sessler J.L. Jeppesen J.O. Tetrathiafulvalene-calix[4]pyrrole: A versatile synthetic receptor for electron-deficient planar and spherical guests.Org. Biomol. Chem. 2019; 17: 2594-2613Google Scholar Like his former mentor Iwao Tabushi, Jonathan shares a passion for electron transfer and hopes he can inspire future generations to pursue synthetic systems that exploit charge-transfer switching to enable chemical communication between disparate chemical entities. Jonathan actively encourages creativity and exploration among his students, often with Friday-evening beer buys at the local graduate bar—the Crown and Anchor. Here they often talk about their outside lives, but sometimes after a few beers, the discussions lead to our research. Often these discussions have been productive, leading to several new projects and research papers. Jonathan refers to these moments as the “Crown and Anchor approach.” (Legend has it that this is where the name “texaphyrin” was first conceived—while Jonathan was drinking the so-called national beer of Texas, Lonestar.) In the Sessler group, they are allowed to actively follow their research passions and explore any research with an open mind. As Jonathan has said to Adam Sedgwick: “The best postdocs have fun and often ignore my intellectual input.” As can be seen from the Sessler group’s webpage (https://www.sessler.cm.utexas.edu/), the research now ranges from molecular sensors, therapeutics, expanded porphyrins, and responsive polymers to supramolecular assemblies for a vast range of applications. Jonathan frequently says with glowing pride, “All this great chemistry happens in spite of me, not because of me.” Naturally, we former Sessler group members take that as the ultimate compliment. A notable recent focus for Jonathan has been the resurrection of the texaphyrin program. The tumor-localizing properties of texaphyrins have afforded several texaphyrin-based drug conjugates with greater efficacies and higher maximum tolerated doses than the corresponding chemotherapeutic. In 2008, Jonathan Arambula (postdoc at the time) and Sessler began work on preparing texaphyrin-platinum constructs. The first of these consisted of an MGd-based texaphyrin core linked to a Pt(II) center, analogous to the FDA-approved drug oxaliplatin.10Thiabaud G. He G. Sen S. Shelton K.A. Baze W.B. Segura L. Alaniz J. Munoz Macias R. Lyness G. Watts A.B. et al.Oxaliplatin Pt(IV) prodrugs conjugated to gadolinium-texaphyrin as potential antitumor agents.Proc. Natl. Acad. Sci. USA. 2020; 117: 7021-7029Google Scholar Conjugates of this general type are now referred to by the general name OxaliTEX. This class of texaphyrin derivatives is of particular interest because to this day, 50% of cancer patients with solid tumors will receive some form of platinum-based therapy. However, the clinical utility of platinum drugs remains limited by intrinsic or acquired resistance and dose-limiting toxicities. The first-generation OxaliTEX was found to be equally effective in vitro and overcame platinum-resistant cell lines. The current second-generation OxaliTEX uses a Pt(IV) analog of oxaliplatin. This system benefits from the presence of two additional ligands in the axial positions of the platinum center. These ligands are cleaved under the reducing conditions characteristic of tumor environments, leading to the release of the active Pt(II) complex, oxaliplatin. Extensive efforts by Jonathan Arambula, Grégory Thiabaud, other Sessler group members, and a number of collaborators resulted in the identification and detailed study of this lead.10Thiabaud G. He G. Sen S. Shelton K.A. Baze W.B. Segura L. Alaniz J. Munoz Macias R. Lyness G. Watts A.B. et al.Oxaliplatin Pt(IV) prodrugs conjugated to gadolinium-texaphyrin as potential antitumor agents.Proc. Natl. Acad. Sci. USA. 2020; 117: 7021-7029Google Scholar In September 2019, OxaliTEX and the entire texaphyrin patent portfolio were licensed to OncoTEX for further pre-clinical development, planned Investigational New Drug submission, and subsequent clinical evaluation. These current developmental efforts are being guided not just by OncoTEX but also by a strong collaboration among the Sessler group, Zahid Siddik at MD Anderson, and Rick Finch at the Keeling Center for Comparative Medicine. All aforementioned parties have been involved in this project since the early days of Jonathan’s texaphyrin-platinum conjugate research with the sole aim of completing Jonathan’s dream of achieving clinical success for OxaliTEX and seeing its use to treat a wide range of cancers. We hope from reading this Backstory that readers will appreciate Jonathan’s passion for chemistry and unconditional support for his students and postdocs. The personal experiences with Jonathan have spawned friendships around the world. The wide scope of research, as detailed in this article, shows that there should be no boundaries to research, and one should explore with scientific curiosity. The success of the research ideology that Jonathan embodies can be seen in the over 850 papers he has published and the hundreds of students and postdocs he has mentored. His influence in chemistry can be seen today in many research areas. These include numerous groups exploring expanded porphyrins, calixpyrroles, and chemotherapeutic development. It is an understatement to say that Jonathan has created his own “school of chemistry.” Previous PhDs and postdocs are now pursuing their own research interests in the US, Australia, the UK, France, China, Korea, Japan, Canada, Mexico, India, Poland, and Turkey, among others. To a person, these members of the “Sessler chemistry family” are pursuing their careers with enthusiasm for science and teaching in the way they were taught by Jonathan. His Web of Science h-index of 113 and recent election to the US National Academy of Sciences, among other honors, highlight his reputation in chemistry and validate his research successes. Within the Sessler alumni, it can all be agreed that working with Jonathan is a fantastic experience because, among all the struggles for grants and papers, he never forgets to focus on the fun of science and the joys of discovery and collaboration. Thus, it is important for us to reiterate in this Backstory his simple philosophy for his academic career: “people first, science second, money third.” It clearly works. J.F.A. is the CEO and executive board member of the oncology therapeutic company OncoTEX Inc., which has licensed several issued patents and patent applications involving texaphyrins from the University of Texas at Austin.