In the name of spontaneity - ACS Publications - American Chemical

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In the name of spontaneity Royce Murray’s long career as a scholar, teacher, and editor in chief is guided by spontaneity.

ne should always be on the lookout for something that is more intriguing and original and less understood than what one is currently doing,” wrote Royce Murray of the University of North Carolina Chapel Hill (UNC) in an autobiographical piece for his 65th birthday (J. Phys. Chem. B 2001, 105, 8642⫺8647). This philosophy has served him well throughout his career. Driven by a curiosity that is loaded with sparks of spontaneity and a deep sense of service to science, Murray has shaped several areas of analytical chemistry, the chemistry community, and AC. His name is inextricably intertwined with chemically modified electrodes and is closely linked with the field of nanoparticles. Electron-transfer reactions in monolayers and polymer melts, synthesis of materials that act as molecular rectifiers, theory for coupled electron transfersOall these scientific topics have connections to research done on Murray’s watch. He is an elected member of the National Academy of Sciences (NAS) and of the American Academy of Arts and Sciences. This journal bears the unmistakable imprint of his guiding hand as editor in chief (EIC). And it is hard to think of UNC without Murray’s presenceOhe has been a member of the faculty there for 48 years. Not bad for a man who once described himself as a “southern pumpkin” (SEAC Commun. 7[4], Nov 1989). Colleagues and former students and postdocs say Murray is so self-effacing and humble that it’s sometimes hard to equate his demeanor with his remarkable career. “Here’s a guy who has accomplished so much and has so much recognition but is still down-to-earth and approachable,” says Lowry Caudill, an adjunct professor at UNC and former president of pharmaceutical development at Cardinal Health in Research 6462

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“O

Colleagues of Murray describe him as a scholar, a teacher, and a statesman.

Triangle Park. “So many people go off and do things that are top-notch but become egotistical and arrogant jerks. That’s not him. He is just a wonderful person.”

Loose ammunition Murray grew up in Birmingham, Ala., and one could say his thirst for quantitative measurements began in his childhood. Murray’s father, Royce Leeroy, was his first inspiration for science. Murray Senior worked at the Alabama Power Co. and was a devoted home-shop tinkerer. Young Murray grew up playing with electrical meters, generators, lathes, wiring diagrams, and insulating materials and helping his father with projects in the shop. “There was a lot of unspoken communication between me and my dad,” says Murray. “I think he knew my buttons were spontaneity and curiosity.” At one point, Murray’s father, who rewound electrical motors as a side business, got a gig at a scrap-metal company and took his son along. “At the end of World War II, this scrap-metal company had a lot of airplane fuselages. I had a

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lot of fun running up and down fuselages and looking out the gun turrets,” recalls Murray. “Along the way, I picked up a lot of loose ammunition.” Murray carried the ammunition home, poured out the gunpowder, and set out to quantitate the relationship between the amount of gunpowder packed under a tin can and the distance the can shot up in the air when the gunpowder was lit. So absorbed was he in the analysis that he failed to inform his father. “He found out when he heard the explosion,” says Murray. “He wasn’t very happy with me but knew I just was curious and experimenting.” The Birmingham public schools followed a system of half-year semesters and permitted academically qualified students to skip semesters. Murray skipped two semesters and graduated early from high school. “It produced some weird outcomes because I skipped the semester where you learn long division,” he says. “I remember seeing the teacher doing this strange thing on the board and being terrified I didn’t know what she was doing and that I was going to get sent back a grade. Finally, I figured out how it worked. That was the only hiccup for me in skipping a grade.” In a similar fashion, Murray breezed through Birmingham Southern College for his bachelor’s degree in chemistry and earned his Ph.D. in 3 years from Northwestern University under the supervision of two giants of electrochemistry, Richard Bowers and Don DeFord. In 1960, he landed a faculty position at UNC after graduating with his Ph.D. Describing himself as young at 23 and wet behind the ears, Murray says, “I had tremendous luck that I had a colleague [at UNC] named Charles Reilley. He, in his patient way, helped me a great deal by teaching me the ropes on how to do

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things that I never encountered because I went by too fast.” Murray settled down into his new home and proceeded to make a name for himself.

GRCs and chemically modified electrodes Chemically modified electrodes were introduced in the 1970s by Murray and his colleagues. These are electrodes that are coated with a very thin film of a particular chemical to give the electrodes defined chemical, electrochemical, or optical properties. They are now indispensable in a wide range of electrochemical studiesOthe relationship of heterogeneous electron transfer and chemical reactivity to electrode surface chemistry, electrostatic phenomena at electrode surfaces, and electron and ion transport phenomena in polymers. They have also had an impact on the design of electrochemical devices and systems for chemical sensing, energy conversion and storage, molecular electronics, and corrosion protection. The idea for these entities grew in Murray’s mind while he attended the Gordon Research Conferences (GRCs) on electrochemistry in the late 1960s and early 1970s. Back then, there was a great deal of debate about the nature of electrochemical reactions and electrode surfaces. Electrochemists were trying to better understand reactions, but “a problem that would continuously come up was whether an electrode showed its intrinsic property or that of an unknown contaminant,” says Murray. “You would frequently hear at these conferences, ‘Well, your electrodes are just dirty. You’re looking at a contamination.’ It impressed on me that it would be nice to make electrode surfaces that behaved like chemicals whose properties you already knew.” Murray points out that he wasn’t the only one thinking along those linesOTed Kuwana at Case Western Reserve University, Fred Anson of the California Institute of Technology, and Arthur Hubbard at the University of Hawaii had been similarly inspired. But Murray’s idea “got a

really nice kick in the pants to start it when I was at a GRC in 1973,” he says. “In the middle of a session, someone came in and asked, ‘Is Murray in the room?’ I said, ‘Yes.’ He said, ‘You have a telephone call.’ You know, when something like that happens, you think the worst.” But the telephone call was from Fred Findeis at the National Science Foundation. He was calling young scholars he knew who were doing interesting work. He informed Murray that a new program was coming up that had research money to offer. “I wrote a proposal right away. With that proposal, Charlie Reilley and I were able to purchase an X-ray photoelectron spectrometer. That was really the key in making the project work,” says Murray. The X-ray photoelectron spectrometer became the workhorse for the project. The investigators used it to analyze the modified electrodes to make sure that the reactions produced the intended chemical surfaces. The idea soon caught on,..., so much so that in 1997, Murray was asked to be part of a task force under the aegis of IUPAC to recommend terminology and definitions for chemically modified electrodes to bring some order to the field (Pure Appl. Chem. 1997, 69, 1317⫺1323). “I was being spontaneous,” says Murray when asked about embarking on the project. “It was only after I saw the excitement that I realized that this maybe was a novel thought, and maybe I should stick around in this area for a while! And I did for about 10 years.” “The concept that solid electrodes could be functionalized with entities that were controlled by chemical synthesis transformed the nature of electrochemical analysis. We wouldn’t have modern glucose sensing or photovoltaic technology without that idea,” says Holden Thorp, a member of the chemistry faculty and the chancellor of UNC. “And it was Royce’s idea.”

“Let’s make the gold into little balls.” Another of Murray’s claims to fame is his research on metal nanoparticles, re-

search that is still ongoing in his laboratory. Again, the work rose from a burst of spontaneity more than a decade ago. The investigators at the time were trying to determine the electron-transfer properties of tetrathiolated porphyrins. They needed to attach the molecules to electrodes so that the molecules stood up like coffee tables, but “we were having a devil of a time determining the orientation of this porphyrin on nice flat gold surfaces,” recalls Murray. “So I had this idea out of frustrationOif we had more surface area, we could get better signals [from the porphyrin]. Let’s make the gold into little balls.” Gold colloids are an old topic, but what differentiated the nanoparticles from the colloids was their extremely small size. At about the same time that Murray and his colleagues wanted to make little gold balls, groups headed by David Schiffrin at the University of Liverpool (U.K.) and Robert Whetten at the Georgia Institute of Technology were coming up with procedures to synthesize nanoparticles and were carrying out fundamental studies on them. These gold nanoparticles were in the range of sizes where their properties changed from bulk gold to molecular. “No one knew just what those changes would look like or exactly at what dimensions the metal-to-molecule change would occur,” says Murray. “So learning to make, purify, and study properties of gold nanoparticles as a function of size was an immediate product of interest.” As the investigators delved deeper into the art and craft of making gold nanoparticles, “the porphyrin idea receded. It got put on a shelf, where it still is, because I came to realize there was so much that wasn’t known about these nanoparticles.” Now Murray and his laboratory members are engrossed in characterizing these metal nanoparticles. “When we started this topic, I had a feeling that previous nanoparticle investigations characterized [the nanoparticles] by saying how big they are in diameter,” he says. “But I want to give them formulae.”

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The rationale for formulae of nanoparticles is that if you know the number of metal atoms and the number of modifying ligands on the nanoparticle, you can predict the behavior of nanoparticles in a reaction. “It has posed a really formidable challenge to analytical chemistry,” says Murray. “Besides our traditional electrochemistry, we’ve gotten into MS, Raman spectroscopy, even Xray crystallography! It has just been a delightful path to wander down.”

Philosophy of science Jumping from one interest to another is Murray’s trademark, and spontaneity is his watchword. “There’s always some spontaneity involved by getting interested in something,” says Murray. “If you ask me if I have a plan of what I’m going to do with these nanoparticles, I would say I just want to understand them. And that, in itself, is sufficient for the time being.” “His style isn’t to go after specific application goals but to go after things because they are just plain interesting,” confirms Andy Ewing, of Go¨teborg University (Sweden) and Pennsylvania State University, who did his postdoctoral research in the Murray laboratory. “If they are novel and interesting, he feels we are going to find something exciting.” Former graduate students and postdocs say Murray pays unwavering attention to details in data. “He is constantly looking at dataOevaluating it and looking for new insight,” says Mark Wightman of UNC, one of Murray’s early graduate students. “I think that’s the thing I’ve really learned from him: watch the data very carefully because it’s going to tell you lots of things. It’s going to help you interpret the chemical system that you’re studying.” Murray wrote in his autobiographical piece that he loves to watch his students learn that “the interpretation is as important as the experiment”. Correct interpretation is not just a matter of good science. Murray feels it’s an ethical issue as well. “Scientists should challenge 6464

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Murray loves to go fishing and does so every year with former UNC colleague Jim Collman. “It’s an annual event. You can set your clock by it!” quips Wightman.

their own interpretations,” says Murray. “Sometimes, in the course of doing science, in the need to publish and move one’s program along, there’s a temptation not to step back and challenge the interpretations yet one more time.”

Imitating his style Former students and postdocs and colleagues at UNC all say that they follow Murray’s example in some shape or form. Ewing says it was after he met Murray that he realized a successful academic researcher could be both scientifically creative and organizationally disciplined. “I try to organize things the way Royce does. I think that helped me tremendously when I was department head [at Pennsylvania State University] for 5 years,” says Ewing. “Without interacting with Royce, I would never be able to do that.” Everyone remarks that Murray is extremely organized, which they believe is one of the secrets of his success. “One big thing that I’ve picked up from Dr. Murray is that you can get a lot done in small segments. Even if you have 20 dif-

ferent things that you have to accomplish, if you just spend a little time on each thing every day, you can get those things done,” says Deon Miles, who is now at Sewanee: The University of the South and was a graduate student under Murray. “I remember he used to have a little scheduler in his office, and it would have the times when he would be busy doing somethingOwhether it is grant writing or doing something with the journalOand then there were times he would have available to meet with us. I saw the scheduling and thought, ‘Man, he’s using all his time very efficiently!’” The former postdocs and students all remember the time Murray devoted to them during their tenure in his laboratory. “We would meet weekly. It was clear that when you were in his office, there was nothing more important than you and your work. It was a sense of really deep caring about what you were doing and about you as a scientist and a person. It was a fantastic feeling for graduate students, especially early on when people are insecure,” says Héctor

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Abrun ˜a, who was one of Murray’s graduate students and is now at Cornell University. “I now use the identical procedure in my lab. I meet with my students weekly, one-on-one, because I remember him being so good in terms of keeping track of what I, the student, was doing without being intrusive and getting a sense that he did care about my progress and how I was doing.” Caudill was an undergraduate student in the Murray lab during his senior year at UNC. Caudill went on to do his Ph.D. with Wightman and became a successful pharmaceutical industry executive in the Research Triangle of North Carolina. Caudill says watching Murray manage all aspects of running a successful academic research laboratory taught him lessons that he carried with him into his career. “I was watching a real pro in how to go about in conducting big-league research, how to motivate people, to set goals and visions,” says Caudill. “Looking back on the experience 30 years later, I realize he was top-notch at the business of leading a successful research team. I was very lucky to be exposed to that.” Colleagues say the way Murray conducts himself is inspiring and they try to take a leaf from his book. “His deliberative approach; his extraordinary energy; the amount of homework that he does when he works on something; and his temperament, which is always on the high roadOI think those are the great lessons for anybody,” states Thorp.

“Scientists should challenge their own interpretations,”saysMurray. Work of an EIC Murray was appointed EIC of AC in 1991, the same year he was elected to NAS. “It was Dick Zare [of Stanford University] who called me on the telephone and asked me some 20 years ago, ‘Would you consider being editor?’,” says Murray. “He was chair of the search committee, as I recall. The first thing he said to me was, ‘Now, you won’t have

to write editorials unless you want to.’ He felt that might be a sticking point!” Murray replied that he had never considered being an EIC and requested time to think about it. “I called Al Bard [at the University of Texas Austin], who was editor of JACS at the time, and asked him his advice,” says Murray. “He said, ‘You get to meet a wide range of people. Life gets more interesting and it’s fun. It’s hard work, but it’s fun.’ I took him at his word, and I think he was right.” Authors and the associate editors of AC say Murray has broadened the research fields represented in the journal and therefore broadened its audience. He has made the peer-review process more rigorous and raised the journal’s visibility and credibility. “The impact factor of the journal has gone up, it’s modernized, and it’s moved seamlessly into the online age,” says Wightman. “I think the journal’s in a lot better place because of his contributions.” “Royce has led the transition of the journal to a truly international publication, guided its transition into the age of electronic distribution and electronic manuscript flow, and guided a tremendous expansion in publication pages while maintaining its high status in the field,” says Catherine Fenselau, who is at the University of Maryland and is one of the journal’s associate editors. Murray says that working with the authors and associate editors to put together a high-quality journal is gratifying. But he notes that the job has become more challenging as the electronic age has prompted more manuscripts to be submitted that have to get processed through peer review. “You don’t have as much time to sit and enjoy a submitted manuscript that’s really neat. You would like to read it more leisurely, but you have less and less time to do that because you have more and more manuscripts to deal with,” says Murray. But he points out that the larger number of manuscripts increases the scope of the journal and introduces new topics,

which makes up for the increased work for the AC editorial office. The part of the EIC’s role that caught Murray off guard was being the gatekeeper of scientific ethics and integrity. “You’re the detective, the judge, the jury, and the hangman,” says Murray. “It is not a complaint, but it’s not the most pleasant part of being an editorOto discover a misdoing and to have to deal with it in an appropriate way.”

The Royce Murray Quadrangle In 2004, UNC paid tribute to Murray’s contributions to the university. The $205 million Carolina Physical Science Complex is the largest construction project in the institution’s history and one for which Murray has been a strong advocate. Once completed, the complex will house teaching and research spaces for chemistry, math, physics, astronomy, computer sciences, and marine sciences. One of the largest of the green spaces planned for the complex is a quadrangle where students and faculty from a diverse range of disciplines can mingle, rest, and enjoy the outdoors. And in that quadrangle, the fundraising organizers for the complex saw an opportunity to acknowledge Murray’s more than four decades of service to UNC. “To me, that quadrangle was begging to have his name on it,” says Caudill, who spearheaded the fundraising with Thorp and bestowed $1 million for the quadrangle’s construction. “It was also my way of saying, ‘Thank you.’ I didn’t know as an undergrad at the age of 21 what I wanted to do and where I wanted to go, but he helped me to figure out at that stage what the next step was and helped me envision what could be. I’ll always be grateful for that.” Thorp adds, “It’s really hard to imagine someone who’s never held an administrative position higher than department chair [yet] who has had a bigger imprint on an institution than Royce Murray.” But rather than tell Murray over a cup of coffee that a part of the science

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complex was going to be named after him, Caudill, Thorp, and others launched an elaborate scheme to surprise him. Caudill had also donated money for a building within the new science complex. So, under the guise of celebrating the gift for the building, they planned a huge party at the Morehead Planetarium and Science Center on the UNC campus. All the chemistry faculty, their spouses, and the university provost were invited. And everyone, except Murray, was in on the surprise. On the day, Murray recalls being taken aback because when he walked into the party with his wife, Mirtha Uman ˜a-Murray, “who should I find there but two of my children, Kathy and Melissa. I thought, ‘What are they doing here?’ There was some kind of an excuse given that they were in town for some reason so they got invited.” “He knew something was up,” says Thorp, “but nobody told him what it was, and we made him sit through dinner.” After dinner, the provost and others went through the motions of talking about the gift for the building. But when Caudill stood up to say a few

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words about his gift, he announced that, by the way, there was an additional $1 million and “that’s why we’re here tonight.” Caudill says, “It was about the naming of the quadrangle. Boy, oh boyOhe had a look on his face of total surprise.” Once the standing ovation for Murray was over and he regained his composure, Murray was invited to say a few words. “I think what I said was, ‘You can do good science and people will remember your good science about as long as you’re still doing it. But there’s no permanent signpost that will be there forever. To have your name on a piece of a university campus as great as this one, that is going to stay thereOthat is so incredibly nice, in terms of feeling pleasure and loyalty for UNC.’” The evening has been chalked up as one of the great successes in the making of the new science complex because the surprise was so skillfully pulled off. Caudill says, “I look back on that evening as a real highlight, because we just flat-out snookered him.”

shows no signs of slowing down. He attributes his seemingly bottomless well of energy to the excitement of science and the fun he derives from it. “It’s really lucky to have a job that you love to do, which, by the way, you get paid for,” he says. “That makes it easier to stay engaged.” In the span of his career, Murray has written ⬎430 research articles and ⬎180 editorials. He holds 3 patents and has published 4 books. Prestigious awards have been heaped on him. More than 150 graduate and postgraduate students have emerged from his laboratory. He gets described as a scholar, a teacher, and a statesman. When asked what his father would think now of his career, Murray says with a smile in his voice, “Oh, I think he would quietly nod and not say very much.” —Rajendrani Mukhopadhyay

Going strong Now in his early 70s, Murray continues to add to his list of achievements and

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