Past Hancock Memorial Award Winners

Please see the archive for winners prior to 2010.

2013

Sponsored by the ACS Division of Environmental Chemistry:

Cristina de Salas, University of Erlangen-Nürnberg
"SynDeNOx, recycling of nitrogen monoxide through carbonitrosation reactions"

Innovation and Benefits. Nitrogen monoxide (NO) is a frequently occurring waste gas in electrical power generation, waste combustion, and many other industrial activities. While not harmful itself, NO oxidizes into toxic nitrogen dioxide (NO2) in the atmosphere. Removal of nitrogen from the air is typically carried out by various denitrification processes that reduce NO to nitrogen (N2)—a harmless yes low value substance. The aim of this research is to design new chemical reactions that can make the most of nitrogen monoxide arising as waste gas.

Christina de Salas, a doctoral student of Professor Markus Heinrich, was selected for her research on the synthesis of valuable oximes from the nitrogen monoxide by complexation with iron (II) salts. She developed a new carbonitrosation reaction where a C-C bond and a C-N bond are created in one step using simple starting materials.

Christina’s research contributes towards a potential replacement of existing industrial denitrification processes which either, a) require high process temperatures and additional inputs, pose sensitivity issues with the catalysis process, and result in low value nitrogen, or b) require ethylenediaminetetraacetic acid (EDTA), expensive enzymes, a long reaction time, and produce low value nitrogen. Comparatively the new process uses a cheap iron-sulfate and olefinic subrate, a simple reaction condition, and produces valuable oximes as end products.

Sponsored by the National Institute of Standards & Technology:

Lindsay Soh, Yale University
“Towards efficient biodiesel production using carbon dioxide”

Innovation and Benefits. Transportation fuels made from sustainable and renewable sources are a key national interest because of their contribution to energy independence and their improved environmental profile over standard petrochemical-based fuels. This research focuses on the sustainable production of biodiesel from renewable feedstocks and use of carbon dioxide (CO2) as a benign solvent. The process is designed to minimize hazard and energy/material burdens of fuel production.

Lindsay Soh, a doctoral student of Professor Julie Zimmerman, was selected for her research in combining lipid extraction and conversion to fuel in a one-step process. Using carbon dioxide, methanol, and a catalyst, she created an efficient and sustainable process for the production of biodiesel.

Lindsay’s research contributes towards using CO2 in a biorefinery for the extraction, conversion, and separation of algal lipids. This chemistry can also be applied to other valuable co-products such as phospholipids or pigments, realizing a complete and efficient use of biomass which would allow for a viable, economical, and sustainable energy future.

2012

Sponsored by the National Institute of Standards & Technology:

Keary Mark Engle, The Scripps Research Institute
“Ligand-Accelerated Catalysis in Palladium(II)-Mediated C-H Functionalization”

Innovation and Benefits. The synthesis of organic molecules is often a complex process requiring large amounts of energy and materials. Organic chemists seek to simplify and streamline reactions in order to reduce the overall energy consumed and waste generated. This research focuses on the development of synthetically versatile, environmentally friendly, and operationally simple reactions to convert non-activated carbon–hydrogen (C–H) bonds into carbon–carbon (C–C) bonds using transition metal catalysis.

Keary, a doctoral student of Professor Jin-Quan Yu, was selected for his research on developing new ligand scaffolds to accelerate Pd(II)-catalyzed C–H functionalization reactions. Keary’s work represents the first example of ligands that affect a >10-fold rate increase in C–H functionalization along a Pd(II)/Pd(0) catalytic cycle. In addition to high reactivity, the Pd(II)–amino acid catalysts are robust, giving TONs >450 under 1 atm O2 (among the best values observed for this class of reactions). His research shows that this ligand scaffold is compatible with reactions that contain fundamentally different steps in the catalytic cycle, such as C–H/R–BX2 cross-coupling, and with other synthetically versatile substrates beyond aryl carboxylic acids. All told, this research has led to the discovery of novel green catalytic processes and demonstrated their synthetic utility in a range of diverse settings.

Keary’s research contributes towards fundamentally altering how chemists construct molecules in academic and industrial laboratories in order to reduce reaction time, lower energy consumption, minimize step count, and eliminate chemical waste. These objectives are of great interest to the pharmaceutical, medicinal, agrochemical, and process chemistry industries.


Sponsored by the ACS Division of Environmental Chemistry:

Sean Mercer, Queen’s University
“The Development of ‘Switchable Water’: A CO2 Switchable Aqueous Solvent”

Innovations and Benefits. Water is used extensively in nearly all industrial processes, after which the “waste-water” requires treatment before recycling or release. Salt is a common pollutant in industrial wastewater yet there is no efficient and low-cost solution for removing salts from water. This research focuses on developing a greener method of performing industrial-scale separations in aqueous solutions in order to recycle process water.

Sean, a doctoral student of Professor Philip Jessop, was selected for his research on developing a CO2-switchable ionic strength aqueous solvent. He found that additives such as amines and polyamines, triggered by the benign gas CO2, could raise and lower the ionic strength of the water and salt-out water-miscible organic compounds. Essentially, the system offers a means of separating solutes from aqueous solutions without the means of traditional distillation steps, or the addition of large amounts of raw materials such as salts.

Sean’s research has shown that switchable water can be used in industry, a) as a means to reversibly break organic/water emulsions stabilized with commercial surfactants, b) to enhance settling of model strip mining slurries with easy recycling of process water, and c) as a reactor for homogeneous catalysis in a monophasic system which is later turned biphasic to easily separate products from the catalysts. These research applications point towards a potentially large cost-savings and equally large reduction in environmental impact compared to existing water separation methods.

2011

Sponsored by the ACS Division of Environmental Chemistry:

Swapnil Jadhav, The City College of New York
“Functional Molecular Gelators from Crop-Based Feedstock”

Innovation and Benefits. Molecular gelators (MGs) are emerging as alternative materials for a diverse range of applications. This research shows that the biorefinery concept can be implemented to design MGs that are sustainable, biocompatible and multifunctional. Specifically, MGs based on open chain sugar fatty acid conjugates were developed and found to be potential alternative materials for oil-spill recovery and controlled release of biopesticides, among other applications.

Swapnil Jadhav, a doctoral student of Professor George John, was selected for his research on discovering open-chain sugar fatty acid conjugates as molecular gelators as well as areas in which these MGs are effective. These new MGs are greener since they are non-toxic, biodegradable and derived from renewable resources.

To create these MGs the synthesis utilizes enzyme catalysis. Lipase-mediated regioselective transesterification was used to quantitatively conjugate sugars with fatty acids (C4-C14 acids) to obtain structurally diverse gelators.

Swapnil discovered that these new MGs are not only greener, they are also extremely efficient in several different applications. These non-toxic and readily biodegradable amphiphiles, specifically C8-derivatives, exhibited unprecedented gelation in crude oil fractions, liquid pheromones and edible oil. Their efficacy and versatility has been successfully demonstrated in the following areas: as oil spill recovery materials, as controlled release devices for biopesticides and as healthy and alternative vegetable oil structuring agents.


Sponsored by the National Institute of Standards & Technology:

Huan Cong, Boston University
“Silver Nanoparticles: A Novel Catalyst for Green and Biomimetic Synthesis of Anticancer Natural Products”

Innovation and Benefits. Silver nanoparticles (AgNPs) are newly discovered green catalysts for the Diels-Alder cycloadditions of 2′-hydroxychalcones. The benefits of this new silica-supported AgNP green catalyst are its ease of separation and recycling, high activity and low toxicity. Furthermore, silver is one of the cheapest and least toxic noble metals, making the catalyst ec Huan Cong, a doctoral student of Professor John A. Porco, Jr., was selected for his research on showing the ability of silver nanoparticles to catalyze the Diels-Alder cycloadditions of 2′-hydroxychalcones. Not only is this catalyst incredibly green, it can also be used in concise syntheses of complex anticancer natural products.

The novel silica-supported AgNP catalyst is prepared by loading chromatography-grade silica with in situ generated AgNPs, followed by calcination. Diels-Alder cycloadditions of 2′-hydroxychalcones and dienes provide biomimetic and atom-economical access to the core structure shared by over fifty biologically active natural products including panduratin A and nicolaioidesin C, which have shown promising anticancer, anti-HIV and anti-inflammatory activities. The AgNP catalyst enables the production of these compounds, while having low toxicity, ease of use and low cost.

The AgNP catalyst described herein should inspire broad, creative applications in emerging yet underdeveloped fields employing metal nanoparticle catalysts, which would benefit medical, pharmaceutical and materials research.

2010

Sponsored by the ACS Division of Environmental Chemistry:

Laura J. Allen, Yale University
“Atom Economical Alcohol Activation with Inexpensive and Non-toxic Catalysts”

Innovation and Benefits. Pharmaceuticals and other specialized organic molecules often require multiple and expensive synthetic steps that involve the use of toxic chemicals and generation of waste. This research demonstrates an alternative 1-step reaction that replaces a common 3-step procedure, while eliminating the hazardous and costly derivatives and catalysts, and minimizing waste.

Laura Allen, a doctoral student of Professor Robert Crabtree at Yale University, was selected for her research on catalysts to replace toxic second and third row transition metals with much safer and less expensive first row transition metals and even alkali metals, for organic transformations.

One such organic transformation is the β-alkylation of secondary alcohols with primary alcohols, a reaction type identified by the pharmaceutical industry as needing a greener alternative. Previous research shortened the procedure from 3-steps to 1-pot.

Laura has improved the 1-pot reaction, discovering that toxic metal catalysts are not required—simple alkali metal bases, such as potassium hydroxide, are sufficient. The reaction shows promise in solventless conditions, to further reduce waste. These systems also avoid the use of protecting groups and maximize atom economy, leaving only water as a by-product.

Future plans include the use of iron, cobalt, and copper catalysts, to improve selectivity and yield and attaching these new catalysts to TiO2 nanoparticles for recycling.


Sponsored by the National Institute of Standards and Technology:

Madhav Ghanta, University of Kansas
“A Greener, Energy Efficient Process for Making Ethylene Oxide”

Innovation and Benefits. Ethylene oxide (EO) is a component of many chemical products and commodities that are consumed today. The current process of creating EO is energy intensive and emits large quantities of carbon dioxide as a by-product. This new process for converting ethylene to EO improves upon or eliminates these flaws, and makes an essential chemical intermediate more economical and efficient.

Madhav Ghanta, a doctoral student of Professor Bala Subramaniam at the University of Kansas, was selected for his research on improving the sustainability and efficiency of ethylene oxide (EO) production. Other research collaborators include Professor Daryle Busch and Dr. Hyun-Jin Lee. By using the catalyst methyl trioxorhenium and the oxygen donor hydrogen peroxide to facilitate ethylene oxidation, Madhav’s work improves upon the environmental, energy and safety aspects of the current system.

EO is a chemical intermediate for the production of antifreeze, surface active agents for detergents, and polyethylene terephthalate (PET), a common plastic. The current process is energy intensive and part of the feedstock and product are lost by combustion, producing carbon dioxide. The improved process almost exclusively produces EO and eliminates combustion and the resulting carbon dioxide emissions. The nearly complete utilization of ethylene to produce EO conserves feedstock, reducing hydrocarbon use.

The improved process shows promise in a having a large positive environmental impact due to the high volume of EO produced globally.