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BCGC Wins Cash Award for Role in Developing Novel Preservative for GC3/InnoCentive Challenge

Berkeley – On August 6th the Berkeley College of Chemistry reported that the Berkeley Center for Green Chemistry (BCGC) would be sharing a $35,000 cash award for its entry in the “Developing New Preservatives for Personal Care & Household Products” challenge held by the Green Chemistry & Commerce Council (GC3) and InnoCentive.  BCGC was part of an academic/industry/government team comprising researchers from the Western Regional Research Center (Albany, CA) of the USDA, University of Victoria, the household products manufacturer Method Products, and the green chemistry venture capital fund Safer Made. The challenge required teams to develop, test, and present a preservative compound that prevented bacterial and fungal growth in cleaning and personal care products. Nearly 50 teams entered the contest, which launched April, 2017, and offered a first place prize of $150,000.

The BCGC team was one of four first place finalists who split the top prize. Their winning entry was a “reversible” preservative compound, which was active in higher concentrations, as a product, but inactive once it was diluted, causing its two subunits to split apart harmlessly in wastewater and or the environment. The research and development of this novel preservative built on research and collaborations that started with the Greener Solutions class of 2014, and have grown through a series of internships, research projects and industrial partnerships.

The work required an interdisciplinary team of chemists, microbiologists, toxicologists, and product formulators. Several members of the winning research team are associates of BCGC: Heather Buckley (former board member of BCGC and Greener Solutions Student, now Assistant Professor at University of Victoria), William Hart-Cooper (current associate director and co-instructor of the Greener Solutions course, now Research Chemist at the USDA), Kaj Johnson (Green Chef at Method Products and Greener Solutions partner), and Marty Mulvihill (former Executive Director of BCGC and  Greener Solutions instructor, current BCGC board member and co-founder of Safer Made). All have been a part of the BCGC preservatives work from the very beginning, and carried the project through its many phases as their careers have progressed. David Faulkner (former SAGE student and current BCGC postdoc) joined the research project in 2015. In 2017, the team published a report of some of their initial findings in the search for safer preservatives, and the article was selected for inclusion in the ACS Virtual Special Issue on Promoting the Development and Use of Quantitative Sustainability Metrics in the journal ACS Sustainable Chemistry and Engineering.

The BCGC is proud of its role in the work on this award-winning project, and we are excited to continue it, developing safer preservative compounds and advancing the role of green chemistry in personal care products.

The formal announcement can be found here.

Chemical safety information online

Last year, PubChem introduced a new feature called Laboratory Chemical Safety Summary (LCSS). This is a new way to get the type of health & safety information normally found in material safety data sheets (MSDS)—except that you may find even more information, more easily. As of today, 3,290 compounds have LCSS information available in the database, and you can find all of them here.

LCSS is a commendable example of information about health and environmental hazards being neatly integrated, organized, and presented alongside other valuable types of information—in this case within the huge data infrastructure of PubChem.

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Toxicity of Iron Nanoparticles

“Stabilization or Oxidation of Nanoscale Zerovalent Iron at Environmentally Relevant Exposure Changes Bioavailability and Toxicity in Medaka Fish” Chen, P-J; Tan, S-W; Wu, W-L. Environ. Sci. Technol. 2012, ASAP. DOI: 10.1021/es3006783

We’ve posted before on iron-catalyzed reactions (see here for a recent post) as greener alternatives to more traditional platinum group catalyzed reactions. However, even iron has toxicity concerns as described in this paper from National Taiwan University on the toxicity in medaka fish of  zerovalent iron (nZVI) nanoparticles (NPs). This is particularly pertinent research in light of the increased usage of iron(0) nanomaterials in remediation.

The study investigates the effects of four different iron dosing ‘solutions’ on the molecular, cellular and organismal health of medaka larvae: (i) carboxymethylcellulose stabilized nZVI (CMC-nZVI), (ii) non-stabilized nZVI (nZVI), (iii) magnetite NPs (nFe3O4), and (iv) soluble Fe(II).

They first characterize the dosing solutions. The sizes of their nanoparticles are 75 nm, 25-75 nm, and 27 nm for CMC-nZVI, nZVI, and nFe3O4 respectively. The zeta potentials were measured to show, not surprisingly, that the CMC-stabilized particles are much more stable to aggregation than the non-stabilized nZVI.

Interestingly, of the four iron dosing solutions, CMC-nZVI has the most significant impact on the level of dissolved oxygen, decreasing it to zero where it remained for 12 hours. Furthermore, this aerobic oxidation of CMC-nZVI leads to a release of 45 mg/L of soluble Fe(II) in 10 min from an initial concentration of 100 mg/L CMC-nZVI as well as an increase in reactive oxygen species (ROS). In contrast, nZVI and nFe3O4 are 20 – 40 % aggregated within 10 min and release less than 20 mg/L of Fe(II) during this time. Only nZVI induces the production of ROS with nFe3O4 and soluble Fe(II) showing no increase in ROS relative to the control. The following figure details these findings for CMC-nZVI; analogous graphs are found in the supplementary information for the other solutions.

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Benign By Design: Synthetic Guidelines for Low Chronic Aquatic Toxicity

“Towards Rational Molecular Design for Reduced Chronic Aquatic Toxicity” Voutchkova-Kostal, A. M.; Kostal, J.; Connors, K. A.; Brooks, B. W.; Anastas, P. T.; Zimmerman, J. B. Green Chem. 2012, 14, 1001-1008. DOI: 10.1039/C2GC16385C

As a synthetic chemist with little (actually zero) training in toxicology, it’s difficult for me to imagine how to design safer chemicals at the start of a project. I can avoid nasty solvents, use safer reagents, but when designing a new molecule I haven’t a clue of its potential toxicological impact. This is frustrating and as the authors of the above paper in Green Chemistry point out, “with the growing number of new chemicals being introduced into the market, it is not economically or ethically reasonable to assume that each can undergo systematic toxicological testing […]”. Thus, possessing a set of easy-to-implement synthetic guidelines to reduce the toxicity of a synthetic target during the design stage, while maintaining (or better yet, augmenting) its function, is of high importance.

Recently, the Zimmerman group reported on guidelines for reducing acute aquatic toxicity and have now extended their work to chronic aquatic toxicity. This is an important next step because chronic toxicity studies are necessarily longer-term (and thus more resource intensive) than acute toxicity studies.

In the current work, they explore the relationships between 38 physicochemical properties of 865 chemicals with chronic aquatic toxicity toward three model organisms: the Japanese medaka, a cladoceran, and a green algae. The 38 properties include, for example, molecular weight, number of freely rotatable bonds, aqueous solubility, and number of hydrogen bond donors and acceptors. (more…)

Toxicity Prediction via Hard-Soft Acid-Base Theory

“Application of the Hard and Soft, Acids and Bases (HSAB) Theory to Toxicant–Target Interactions” LoPachin, R. M.; Gavin, T; DeCaprio, A.; Barber, D. S. Chem. Res. Toxicol. 201225, 239-251. DOI: 10.1021/tx2003257

I considered posting about the Carreira group‘s work on enantioselective amination of allylic alcohols, because I think it is an awesome example of direct functionalization of hydroxylated substrates–an issue that will be of increasing importance in terms of biomass utilization. However I chose instead to stray into the less familiar territory of the bioactivity of organic molecules. I am semi-familiar with quantitative structure activity relationship (QSAR) modeling, wherein a database of known molecules and their bioactivity is used to predict the bioactivity of a molecule about which there is no bioactivity data. However, relying solely on computers leaves me wanting a more intuitive grasp on which molecules are expected to be toxic/non-toxic and why. That’s why I got excited about the recent perspective article about using the familiar Hard-Soft Acid-Base theory to predict toxicant-target interactions.

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Learning from past mistakes – Dioxins

“Dioxins: An Overview and History”  Hites, R. A.  Environ. Sci. Technol. 2010, ASAP.  DOI 10.1021/es1013664

One of my main reasons for drinking the green chemistry kool-aid is that I believe it allows me to still do cool chemistry as well as to contribute to building a more sustainable civilization (at least that’s the idea).  The focus, in my eyes, is on the positive things you can do with chemistry.  However, as the Spanish-American philosopher George Santayana first said, “Those who cannot remember the past are condemned to repeat it.”  With that in mind, this post is about one of the most well-studied mistakes in the history of the chemical enterprise, polychlorinated dibenzo-p-dioxins (PCDDs), often referred to collectively in the literature as dioxins.  In Ronald Hites’ recent ES&T feature article on dioxins, he tells the story of the most toxic of the 75 dioxin congeners, 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD).

The most sinister aspect of dioxins, from a chemists’ perspective, is the (more…)