green chemistry newsletter · prof. zhang’s contributions to the field of fluorous chemistry...

Green Chemistry NewsletterIssue 4 - Winter 2015-16

TABLE OF CONTENTS

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PageNEWSA look at what has been going on in and around the University of Massachusetts, Boston green chemistry community

RECENT PUBLICATIONSWhat our chemists have been working on

INTERVIEWDaniela Graf Stillfried Barreto interviews Dr. John Warner about the beginnings of green chemistry and his career in the sciences.

The editorial staff for the Universtiy of Massachusetts, Boston Green Chemistry Newsletter is Raymond Borg (Editor-in-chief), Daniela Graf Stillfried Barreto (correspondent and editor), and Andrew Gnann (art, layout, and editor). Questions or comments should be directed to Raymond Borg at [email protected].

“. . . there is a moral and ethical responsibility of anyone in education to ensure that every student—not just the motivated, not just the interested—learns about mechanistic toxicology, environ-mental impact, the 12 principles of green chemistry.”JOHN C. WARNER,President and Chief Technology Officer of Warner Babcock Institute for Green Chemistry

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1Green Chemistry Newsletter UMass Boston

News

The faculty and students at the UMass Boston Center for Green Chemistry have been very active designing symposia and hosting conferences related green chemistry.

The UMass Boston Center for Green Chemistry hosted the Third Annual Symposium and Workshop of the Global Green Chemistry Centres (G2C2) in Aug. 2015. Delegations from the ACS Green Chemistry Institute, University of York’s Green Chemistry Centre of Excellence (UK), and center directors from universities in the US, Tanzania, UK, Brazil, Singapore, Nigeria, China and Mexico attended. Guest speakers from the Royal Society of Chemistry, Green Chemistry and Commerce Council (GC3), Beyond Benign, Sigma Aldrich, and Ely Lilly also attended. This event was built on the success of the last two G2C2 meetings in Delhi (2013) and Cape Town (2014).

UMB graduate students Meg McKinnon and Ray Borg started the UMass Sustainable Scientists group at UMB in September. They have been working closely with the UMB Department of Health and Safety to improve laboratory safety in UMB chemistry laboratories. Recently, they co-hosted a Chemistry Trivia Night with the local ACS Younger Chemists Committee.

Prof. Berkeley Cue was a keynote speaker in the Pharmaceu-tical Green Chemistry session of the 19th Green Chemistry and Engineering Conference in North Bethesda, MD. His talk was titled “The ACS Green Chemistry Institute Pharmaceutical Roundtable: A Perspective from One of Its Founders” (Jul. 2015).

Prof. Berkeley Cue was an advisor to co-editors Peterson and Manley for their book recently published by the Royal Society of Chemistry titled “Green Chemistry Strategies for Drug Discovery” (Oct. 2015).

Profs. Berkeley Cue and Wei Zhang have been appointed to the International Advisory Board of the Drug Discovery & Therapy World Congress (DDTW) 2016. This is the 3rd year they are serving on the Board since they co-chaired a green chemistry session for DDTW in 2013.

Prof. Wei Zhang was a co-chair of the symposium “New Green Techniques for Medicinal Chemistry”, and gave two talks on sustainable organocatalysis and green

Attendees of the Third G2C2 Symposium and Workshop at UMass Boston, August 2015.

Prof. Berkeley Cue cutting the cake at the 19th Green Chemistry and Engineering Conference in North Bethesda, MD.

At the Third G2C2 Symposium and Workshop held at UMass Boston in Aug. 2015, Prof. Berkeley Cue gave a talk “An Analysis of the Adoption of Green Chemistry by Big Pharma, Bio Pharma, and Generic Drug Sectors: Barriers, Perceived and Real, and Ways to Overcome Them”. Prof. Wei Zhang gave a talk “Green Chemistry at UMass Boston.”

UMB graduate students Maria Kipreos and Ray Borg collab-orated with National Presence Younger Chemist Committee member Wasiu Lawal to host a green chemistry symposium at the 250th ACS National Meeting in Boston. The symposium was titled “Careers for Young Professionals in Green Chemistry: Breaking Bad Chemistry Habits” (Aug. 2015).


chemistry education at PacifiChem in Hawaii (Dec. 2015).

Prof. Wei Zhang served as an organizing committee member for the 2nd Int. Conference on Past and Present Research Systems of Green Chemistry held in Orlando, FL (Sep. 2015).

Prof. Wei Zhang received the International Fluorous

Rochford, J., Ngo, K. T., Narayanan, R. P., Mahanti, B., McKinnon, M. “Ligand cooperativity in electrocatalytic CO2 reduction by Mn(I) and Re(I) tricarbonyl complexes”

Lee, N. A., Ngo, K. T., Gilligan, G. E., Anzalone, Z., Lamberto, M., Rochford, J. “Photoelectrochemical characterization of non-innocent ligand ruthenium beta-diketonate complexes in dye-sensitized solar cells”

Huang, X.; Yi, W.-B.; Zhang, W. “Asymmet-ric Synthesis of Organofluorine Compounds with Recyclable Fluorous Organocatalysts”

Zhang, W. “Green Synthesis of Diverse Heterocyclic Scaffolds”

Posters

Narayanan, R. P., Ngo, K. T., Reed, B., Groysman, S., Rochford, J. “Bis(aldimino)pyridine nickel complexes as electrocatalysts for the reduction of CO2”

McKinnon, M., Ngo, K. T., Narayanan, R. P., Rochford, J. “Electrocatalytic CO2 reduction and redox non-in-nocence of Mn(I) tricarbonyl oxyquinolate complexes”

Ngo, K. T., Mahanti, B., Lee, N. A., Rochford, J. “Photochem-istry and redox non-innocence of electron rich fac-Re(I) tricarbonyl beta-diketonate and oxyquinolate complexes: A fundamental study toward the application of CO2 reduction”

Lee, N. A., Ngo, K. T., Gilligan, G. E., Anzalone, Z., Lamberto, M., Rochford, J. “Photoelectrochemical characterization of ruthenium flavonoid complexes in a dye-sensitized solar cell”

Gilligan, G. E., Lee, N. A., Bag, S., Rochford, J. “Struc-ture-activity properties of curcuminoid ruthenium polypyridyl photosensitizers in dye sensitized solar cells”

Qian, J. Yi, W. Huang, Y.; Zhang, J.; Cai, C.; Zhang, W. “One-Pot Synthesis of 3,5-Disubstituted and Polysubstituted Phenols”

Liu, S.; Yosief, H.; McKeown, M. R.; Fu, H.; Buckley, D. L.; Justin, R. M.; Qi, J.; Bradner, J. B.; Zhang, W. “Biased Multicom-ponent Reactions to Develop Novel Bromodomain Inhibitors”

Recent Publications Huang, X.; Pham, K.; Yi, W.; Zhang, X.; Clamens C.; Hyatt, J. P.; Jasinsk, J. P.; Tayvah, U.; Zhang, W. “Recyclable Organocatalyst-promoted One-pot Asymmetric Synthesis of Spirooxindoles Bearing Multiple Stereogenic Centers” Adv. Synth. Catal. 2015, 357, 3820-3824.

Jiang, L.; Yi, W.-B.; Lu, G.; Cai, C.; Zhang, W. “Direct Trifluoromethylthiolation and Perfluoroalkylthiola-tion of sp² C-H Bonds with NaSO2CF3 or NaSO2Rf” Angew. Chem. Int. Ed. 2015, 54, 14965-14969.

Professor Wei Zhang’s Fluorous Technology Award, presented at the Sixth International Symposium on Fluorous Technologies in Como, Italy.

Technology Award at the Sixth International Symposium on Fluorous Technologies in Como, Italy. This award recognizes Prof. Zhang’s contributions to the field of fluorous chemistry including applications in medicinal and green chemistry. He presented a plenary talk “Fluorous Technologies for Medicinal Chemistry and Organocatalysis” at the conference (Aug. 2015).

Prof. Wei Zhang delivered the opening Plenary Lecture “Green Chemistry at UMass Boston” at the 5th Inter-national Conference for Young Chemists in Penang, Malaysia. The theme of this conference was Green Chemistry towards a Sustainable Tomorrow (Aug. 2015).

The UMass Boston ACS Chapter, advised by Prof. Jonathan Rochford, was certified for the Green Chemistry ACS Student Chapter for the 3rd year running (Oct. 2015)

The ASBMB Undergraduate Chapter, advised by Prof. Daniel Dowling, did an outreach event with local 8th

graders at the McCormack-Dever Middle School that focused on photosynthesis and understanding CO2 as a greenhouse gas that gets converted to sugars by using model kits to build these molecules (Oct. 2015).

At the 250th ACS National Meeting in Boston, faculty and graduate students made the following green chemistry-related oral presentations:

Talks

Ngo, K. T., Narayanan, R. P., Mahanti, B., Reed, B., Groysman, S., Rochford, J. (oral) “Electrocat-alytic reduction of CO2 with manganese catalyst supported by pendant Bronsted-Lowry acid ligands”


Huang, X.; Pham, K.; Zhang, X.; Yi, W.-B.; Hyatt, J. P.; Tran, A. P.; Jasinski, J. P.; Zhang, W. “Recyclable Organocata-lyst-promoted One-pot Michael/aza-Henry/lactamization Sequence for Fluorinated 2-Piperidinones Bearing Four Stereogenic Centers” RSC Advances 2015, 5, 71071-71075.

G. Banks, M. Clinchot, S. Cullipher, R. Huie, J. Lambertz, R. Lewis, C. Ngai, H. Sevian, G. Sztein-berg, V. Talanquer, M. Weinrich. “Uncovering chemical thinking in students’ decision making: A fuel-choice scenario.” J. Chem. Educ. 2015, 92, 1610-1618 .

S. Cullipher, H. Sevian, V. Talanquer. “Reasoning about benefits, costs, and risks of chemical substances: Mapping different levels of sophistica-tion.” Chem. Educ. Res. Pract. 2015, 16, 377-392.

An Interview with John WarnerConducted by Daniela Graf Stillfried Barreto

You are considered one of the founders of green chemistry. Tell us about the beginning of green chemistry.When I look at the beginning of green chemistry, I actually see two unmet needs to society. The first unmet need was that I saw brilliant scientists coming out of academia, working in industry, coming up with great ideas, but they never amounted to a product. The reason for this was that there was a certain impracticality about what they were doing. They were using solvents that were too expensive and toxic, they were using reagents that were too expensive, and for a company to benefit from their inventions they literally had to invent it a second time to be practical in the real world. I saw this as a problem because about 85% of the scientists would probably get jobs in industry, and I didn’t see that they were being trained to solve problems in industry. They were getting trained to publish papers, but, when they got a job in industry, they weren’t as valuable as they could be because they didn’t understand the requirements of the real world. And, interestingly enough, usually the difference between the impractical and the practical had to do with environmental and toxicological things. So there was a body of knowledge that was missing. And I saw that as an unmet need. The second aspect, and this one is more personal, is that I lost a child to a birth defect. I started questioning why it was that I had no knowledge of what mechanistically makes molecules toxic. I got nervous, upset and sad wondering if I had inadvertently worked with a material that exposed myself, my wife, my future son to some chemical that ended up causing this birth defect. I am confident now that I didn’t and it was some neonatal virus. The point is that I had no information to allow me to assess that question. This was the other unmet need. Why wouldn’t I have had a class or a seminar in this topic when I was being trained as a chemist? These two things together were my motivation and reasons for why the world needed green chemistry.

What inspired you and Paul Anastas to come up with the 12 Principles of Green Chemistry? Would you change anything about the principles now?The principles have survived 23 years. I wouldn’t change anything. I think that they are fine the way they are. Are they perfect, or are there other ways for phrasing them? Maybe, maybe not. But the reality is that I think they are doing fine. No one in 20 years has come to me and presented something that I didn’t feel was captured by the 12 principles. I am very happy. The important thing about the 12 principles of green chemistry that is super critical to understand is that in the field of sustainability there are tons and tons of different organizations that tell people what they should do. The 12 principles of green chemistry are the only examples that I know of that show how to change the behavior of a material to become better to human health and the environment. They speak directly to the inventive scientist on how to change the

picture. They are not a scorecard that allow people to evaluate the goodness or badness of a product. They are a research tool. This is why green chemistry, in my opinion, is a science and not a policy or a philosophy; it is a principle-based science.

What can you tell us about the Warner-Babcock Institute for Green Chemistry and Beyond Benign?As a professor, there came a point in time when I thought that going to industry saying “you should do green chemistry” was effective but wasn’t as effective as it could be. Here I am, a full tenure professor, in a very stable

position, but I wanted to have more impact. If I started a full-process company, played by the rules of business, didn’t take charity, didn’t get government grants, but was strictly a business—a profiting company—doing exclusively green chemistry, and be successful at that, what better example that green chemistry is the right way to go? There are no subsidies, there is no artificial support, so I wanted to start a for-profit company that did that, and I think we did a good job there. At the same time, when I was in UMass I received what was called the Presidential Award for Excellence in Science Mentoring by the President of the United States of America, and I was called one of the country’s top science professors. Education was an important aspect. What we did at UMass—people don’t fully appreciate it—we didn’t have a lot of grants, we didn’t have funding, but anyone doing research in my group at UMass had to go once or twice a month to a third grade class or a seventh grade class to talk about their research and explain the science. Over the years we created a great network of high schools and middle schools in which people of my world were going and visiting, and, when I started the WBI, I didn’t want that to stop. So UMass Boston’s first person to get a PhD in green chemistry agreed to lead Beyond Benign, the non-profit organization, in order to continue that education outreach. When I left the University I couldn’t just profit from research; I needed to have a way of continuing that educational component. There was a bifurcation into the WBI, which is the profit institute,


and Beyond Benign, for non-profit education and outreach. So in a way you can see the aspects of what I was in the university that have translated into two buckets.

Your CV says that you have over 250 patents, papers and books. How have you accomplished such a feat?Who knows? It is an interesting question. I think it is one of the critical abnormalities that I suffer from. I feel that University education oftentimes trains somebody to believe they are a tiny little box. Sometimes people come out of the university having this tiny self-definition of who and what they are. I feel that is incredibly tragic. In fact, what someone does when they graduate may or may not have anything to do with what they arbitrarily chose to do as an undergraduate or graduate student. It is a training to solve problems and to work in the

scientific world. I never looked at myself as being a specific type of chemist. Throughout my career, if I wanted to work on neurochemistry, I worked on neurochemistry, if I wanted to work on cosmetics, I worked on cosmetics, and so on. I think that I’m no smarter, no better than anybody else. So anyone can do what I do if they push down the barriers.

What are some of the new products coming out of WBI?Coming out of the institute there is Alzheimer’s technology, an Alzheimer’s drug, an oncology drug, an ALS-Parkinson’s drug and technology, a hair coloring technology, an asphalt pavement technology, a wood composite technology, and the list goes on and on.

What are the 5 elements of innovation by John Warner?I have a book that is going to be coming out in 2016, by Island Press. Right now the working title is “The Missing Elements”. One of the chapters in that book will be about innovation and the elements of innovation. This is something that I have started to discuss in my work. The first element is “all innovation begins with science fiction.” By definition science fiction is imagining science that can’t be done, and, if you want to invent something, you invent something that can’t currently be done. So the very act of imagining what you are going to invent is, in fact, writing science fiction. There are certain skills for which, if one was in the field of English in writing and composition, there are exercises one does to broaden the mind and be able to write and do creative writing. In an interesting way, scientists should be trained to be able to write science fiction essays because no invention could happen without that part. The second element is that “innovation happens not in the field of focus but in the periphery”. People say innovation happens in the intersection between biology and physics, or between chemistry and biology, but I don’t really see it that way. The reason it appears to people like that, is because they are focusing in the middle of their discipline, and so what happens at the interface necessarily is in the periphery. If someone defines themselves as working in the periphery and they pull the focus there, interestingly enough, now the center of the field that’s in the periphery is where the invention is happening. It is at the interface, it is at the edge of our vision and wherever we are looking, that invention is going to happen. The third element is a little controversial. It talks about how “encyclopedic knowledge is innovation in the absence of intuitive knowledge”. What I mean by that is education has evolved to measure that which is measurable. We tend to look at encyclopedic things that have gradable answers as the right things, but that is wrong. Being able to do that very quickly is extremely valuable. People who can do that are important and need to be rewarded. It is a super important thing to be able to sit down and say in 2011 such and such group published a paper doing this. Encyclopedic knowledge makes people fast, makes people draft a body of information, but it’s always half the battle. The other half of the battle is the intuition, the self-confidence to look at a problem and say “I have never worked in this field before, but I think this is probably what is going on.” This is critical for innovation. What happens oftentimes is the intuitive people

appear fuzzy, they appear not logical, disjointed, while the encyclopedic knowledge people look really crisp and sharp. So oftentimes in organizations work overly focuses on rewarding encyclopedic people, which is fine, as long as it doesn’t get to a point of drowning out the intuitive people. There must be a balance. The fourth element is “the ability to innovate is simultaneously proportional to wisdom and the tolerance of intellectual risk.” What I mean by that is, if I am in front of a group of ten people and expose to them two ideas, and everybody likes idea number one, and nobody likes the other one, but a week later they both work, which one was the one that was more innovative? Not the one that everybody knew was going to work in the first place. The one everybody thought wouldn’t work will evolve to assist people in getting funding and grant them the ability to do things because they have convinced people that it’s going to work—that is the innovative one. In a weird and twisted way that works for innovation and creativity. The fifth element is “innovation is autonomous to complexity”. The only reason I say this is because a lot of times people say “keep it simple; simple is always the best answer.” That is true, but the answer is important regardless. If it is simple, that is wonderful, but if the answer is complicated, well… that is ok too. Those things have nothing to do with innovation. To say you have to innovate with simplicity—there is an important discussion there—but simplicity is not a part of innovation, so, if you are trying to put a value in simplicity or complexity, you are missing the point.

Do you miss being a professor?Yes, I do. But if I were a professor, I would miss being an entrepreneur. If I were an entrepreneur, I would miss being an industrial chemist. I am somebody that loves to do a lot of different things. The more you imagine what you would like to do, if you are not careful, the more you become very unhappy and very sad. You really have to focus on the things you are doing, and you must love and be enthusiastic about whatever you chose. I teach classes at other universities and colleges every second or third semester. I teach a class at Simmons. I am constantly being asked to give lectures at many universities. So I still have my teaching roll.

What is the Green Chemistry Commitment?The Green Chemistry Commitment is the invention of Amy Cannon, the executive director of Beyond Benign. It is, in my opinion, the single most important thing that has evolved. The reason for that is if someone were to ask “where is green chemistry happening?” I will argue that green chemistry is happening in industry much faster than it is happening in academia. Most companies have green chemistry programs, most companies have embraced green chemistry, and they are asking themselves “why isn’t this taught at the univer-sities?” Many universities, and I would say almost every university, has a champion of green chemistry. I think that at every university there are a few professors that get it, care about it, and it is a part of who they are and what they do. The problem is that only the students exposed to those faculty will learn about green chemistry. I feel, if a student is motivated, if a student wants to know how to not make

toxic materials, wants to know how to make things that won’t hurt the environment, they will go and find the way to be trained. There are places now that do that. My problem is what about the ones that have no clue and have no idea about the impact of what chemistry does and are never exposed to understanding that impact? They are going to go and graduate and work and invent the next generations of materials. So I feel there is a moral and ethical responsibility of anyone in education to ensure that every student—not just the motivated, not just the interested—learns about mecha-nistic toxicology, environmental impact, the 12 principles of green chemistry. Universities will have a little program that has students voluntarily signing into, but the time has come for the field of chemistry to realize that we have a moral and ethical responsibility. If we are the only people in the universe that know how to make a molecule, we should not do so until we have some understanding of the potential negative impact. So the Green Chemistry Commitment realizes that this is a very difficult thing to do, because no faculty has ever had this training. It is a very simple thing that asks a chemistry department to agree to work on a plan to introduce green chemistry into their curriculum. It is not restrictive; it doesn’t say how. It doesn’t matter how they do it. What we want is for universities to start signing on and sharing their practices for incorporating green chemistry into their curriculum so that it accelerates in the next generation of schools that are interested in learning from the first school and so on. At some point in time, every university will be training chemists to do what I consider to be a right thing. It is an exciting program, and many universities are signing quite often.

You started in UMass, Boston as a music major. Why did you make a 180 degree change to chemistry?To be clear, I went to UMass intending to be a music major. It just so happens that I had a band called “The Elements,” and it was going very successfully, and things were looking promising. Then a disaster hit, in which my really good friend, the drummer, ended up getting leukemia and unfortunately passed away. That caused me to just be concerned about the whole thing, so all of a sudden all this time I was spending to do music went into a little hiatus, and I happened to stumble into professor Jean-Pierre Anselme’s research lab at UMass, Boston, and I fell in love with chemistry—fell in love with the similarities between the arts and the sciences and decided to dedicate myself to that. I didn’t abandon the music; I am still a musician and play, but I fell in love with chemistry.

Would you have imagined as a UMass student that you were going to be so successful?I don’t even know what successful means. Am I successful now? I guess. Can I be more successful? Yes. Can I be less successful? Yes. So I don’t know what the word is. What is the line to say when one is successful or not? What I can say is that for anybody that has ever asked me what I would be doing in five years, my answer would have been wrong. I suspect that is still the case (laughing), and that is again the wonder of the world. We live in a society that allows us to pursue our dreams and passions, and no one is static. The


way we look at things is constantly evolving and changing, and I am thrilled to have the opportunity to be pursuing my passion. Never in my life have I ever thought of work as work, so when I was at school that wasn’t work, that was what I did, when I was at UMass, that wasn’t work, that was what I did. I never looked at work as work. It is all about who I am. So I am very, very lucky to have that.

Do you have any regrets? If you could change one thing, what would it be?Sure, you know, everyone has regrets. I look back in my past at how I handled different situations. I certainly wish I had handled some situations differently. I think all of us have the same regrets. I don’t think I would change anything; I

would just have handled it differently. I am very happy with the majority of the decisions that I have made. I wish I could change the nuances about how I went about certain things, but not the big picture.

What advice do you have for a young chemist?Believe in yourself. Believe that you can do anything, that creativity and imagining things that do not exist is a path to happiness. Don’t let anybody tell you what you can’t do. there is a bunch of people that you’ll encounter that will enable you—that are going to help you, that will mentor you—but there are also other people that are going to tell you what you can’t do, but put your fingers in your ears.


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