Tag Archives: Franz M. Geiger

How do nanoparticles interact with the environment and with humans over time?

I meant to get this piece published sooner but good intentions don’t get you far.

At Northwestern University, scientists have researched the impact engineered nanoparticles (ENPs) might have as they enter the food chain. An October 18, 2019 Northwestern University news release (also on EurekAlert) by Megan Fellman describes research on an investigation of ENPs and their interaction with living organisms,

Personal electronic devices — smartphones, computers, TVs, tablets, screens of all kinds — are a significant and growing source of the world’s electronic waste. Many of these products use nanomaterials, but little is known about how these modern materials and their tiny particles interact with the environment and living things.

Now a research team of Northwestern University chemists and colleagues from the national Center for Sustainable Nanotechnology has discovered that when certain coated nanoparticles interact with living organisms it results in new properties that cause the nanoparticles to become sticky. Fragmented lipid coronas form on the particles, causing them to stick together and grow into long kelp-like strands. Nanoparticles with 5-nanometer diameters form long structures that are microns in size in solution. The impact on cells is not known.

“Why not make a particle that is benign from the beginning?” said Franz M. Geiger, professor of chemistry in Northwestern’s Weinberg College of Arts and Sciences. He led the Northwestern portion of the research.

“This study provides insight into the molecular mechanisms by which nanoparticles interact with biological systems,” Geiger said. “This may help us understand and predict why some nanomaterial/ligand coating combinations are detrimental to cellular organisms while others are not. We can use this to engineer nanoparticles that are benign by design.”

Using experiments and computer simulations, the research team studied how gold nanoparticles wrapped in strings having positively charged beads interact with a variety of bilayer membrane models. The researchers found that a nearly circular layer of lipids forms spontaneously around the particles. Formation of these “fragmented lipid coronas” have never been seen before to form from membranes.

The study points to solving problems with chemistry. Scientists can use the findings to design a better ligand coating for nanoparticles that avoids the ammonium-phosphate interaction, which causes the aggregation. (Ligands are used in nanomaterials for layering.)

The results will be published Oct. 18 [2018] in the journal Chem.

Geiger is the study’s corresponding author. Other authors include scientists from the Center for Sustainable Nanotechnology’s other institutional partners. Based at the University of Wisconsin-Madison, the center studies engineered nanomaterials and their interaction with the environment, including biological systems — both the negative and positive aspects.

“The nanoparticles pick up parts of the lipid cellular membrane like a snowball rolling in a snowfield, and they become sticky,” Geiger said. “This unintended effect happens because of the presence of the nanoparticle. It can bring lipids to places in cells where lipids are not meant to be.”

The experiments were conducted in idealized laboratory settings that nevertheless are relevant to environments found during the late summer in a landfill — at 21-22 degrees Celsius and a couple feet below ground, where soil and groundwater mix and the food chain begins.

By pairing spectroscopic and imaging experiments with atomistic and coarse-grain simulations, the researchers identified that ion pairing between the lipid head groups of biological membranes and the polycations’ ammonium groups in the nanoparticle wrapping leads to the formation of fragmented lipid coronas. These coronas engender new properties, including composition and stickiness, to the particles with diameters below 10 nanometers.

The study’s insights help predict the impact that the increasingly widespread use of engineered nanomaterials has on the nanoparticles’ fate once they enter the food chain, which many of them may eventually do.

“New technologies and mass consumer products are emerging that feature nanomaterials as critical operational components,” Geiger said. “We can upend the existing paradigm in nanomaterial production towards one in which companies design nanomaterials to be sustainable from the beginning, as opposed to risking expensive product recalls — or worse — down the road.” [emphases mine]

Here’s an image illustrating the work,

Caption: This is a computer simulation of a lipid corona around a 5-nanometer nanoparticle showing ammonium-phosphate ion pairing. Credit: Northwestern University

The curious can find the paper here,

Lipid Corona Formation from Nanoparticle Interactions with Bilayers by Laura L. Olenick, Julianne M. Troiano, Ariane Vartanian, Eric S. Melby, Arielle C. Mensch, Leili Zhang, Jiewei Hong, Oluwaseun Mesele, Tian Qiu, Jared Bozich, Samuel Lohse, Xi Zhang, Thomas R. Kuech, Augusto Millevolte, Ian Gunsolus, Alicia C. McGeachy, Merve Doğangün, Tianzhe Li, Dehong Hu, Stephanie R. Walter, Aurash Mohaimani, Angela Schmoldt, Marco D. Torelli, Katherine R. Hurley, Joe Dalluge, Gene Chong, Z. Vivian Feng, Christy L. Haynes, Robert J. Hamers, Joel A. Pedersen, Qiang Cui, Rigoberto Hernandez, Rebecca Klaper, Galya Orr, Catherine J. Murphy, Franz M. Geiger. Chem Volume 4, ISSUE 11, P2709-2723, November 08, 2018 DOI:https://doi.org/10.1016/j.chempr.2018.09.018 Published:October 18, 2018

This paper is behind a paywall.

Measurably fewer nanoparticles in São Paulo’s (Brazil) air after ethanol use

An Aug. 28, 2017 news item on Nanotechnology Now features news about nanoparticles and the environment in São Paulo, Brazil,

When ethanol prices at the pump rise for whatever reason, it becomes economically advantageous for drivers of dual-fuel vehicles to fill up with gasoline. However, the health of the entire population pays a high price: substitution of gasoline for ethanol leads to a 30% increase in the atmospheric concentration of ultrafine particulate matter, which consists of particles with a diameter of less than 50 nanometers (nm).

An Aug. 23, 2017 Fundação de Amparo à Pesquisa do Estado de São Paulo (The São Paulo Research Foundation [FAPESP]) press release, which originated the news item, explains further,

The phenomenon was detected in São Paulo City, Brazil, in a study supported by FAPESP and published in July 2017 in Nature Communications.

“These polluting nanoparticles are so tiny that they behave like gas molecules. When inhaled, they can penetrate the respiratory system’s defensive barriers and reach the pulmonary alveoli, so that potentially toxic substances enter the bloodstream and may increase the incidence of respiratory and cardiovascular problems,” said Paulo Artaxo, Full Professor at the University of São Paulo’s Physics Institute (IF-USP) and a co-author of the study.

Levels of ultrafine particulate matter in the atmosphere are neither monitored nor regulated by environmental agencies not only in Brazil but practically anywhere in the world, according to Artaxo. The São Paulo State Environmental Corporation (CETESB), for example, routinely monitors only solid particles with diameters of 10,000 nm (PM10) and 2,500 nm (PM2.5) – as well as other gaseous pollutants such as ozone (O3), carbon monoxide (CO) and nitrogen dioxide (NO2).

“Between 75% and 80% of the mass of the nanoparticles we measured in this study corresponds to organic compounds emitted by motor vehicles – carbon in different chemical forms. What these compounds are exactly and how they affect health are questions that require further research,” Artaxo said.

He added that a consensus is forming in the United States and Europe based on recent research indicating that these emissions are a potential health hazard and should be regulated. Several US states, such as California, have laws requiring a 20%-30% ethanol blend in gasoline, which also helps reduce emissions of ultrafine particulate matter.

Methodology

The data analyzed in the study were collected during the period of January-May 2011, when ethanol prices fluctuated sharply compared with gasoline prices, owing to macroeconomic factors such as variations in the international price of sugar (Brazilian ethanol is made from sugarcane).

Collection was performed at the top of a ten-story building belonging to IF-USP in the western part of São Paulo City. According to Artaxo, the site was chosen because it is relatively distant from the main traffic thoroughfares so that the aerosols there are “older” in the sense that they have already interacted with other substances present in the atmosphere.

“Generally speaking, the pollution we inhale every day at home or at work isn’t what comes out of vehicular exhaust pipes but particles already processed in the atmosphere,” he explained. “For this reason, we chose a site that isn’t directly impacted by primary vehicle emissions.”

The study was conducted during Joel Ferreira de Brito’s postdoctoral research, which Artaxo supervised. The model used to analyze the data was developed by Brazilian economist Alberto Salvo, a professor at the National University of Singapore and first author of the article. Franz Geiger, a chemist at Northwestern University in the US, also collaborated.

“We adapted a sophisticated statistical model originally developed for economic analysis and used here for the first time to analyze the chemistry of atmospheric nanoparticles,” Artaxo said. “The main strength of this tool is that it can work with a large number of variables, such as the presence or absence of rainfall, wind direction, traffic intensity, and levels of ozone, carbon monoxide and other pollutants.”

Analyses were performed before, during and after a sharp fluctuation in ethanol prices leading consumers to switch motor fuels in São Paulo City. While no significant changes were detected in levels of inhalable fine particulate matter (PM2.5 and PM10), the study proved in a real, day-to-day situation that choosing ethanol reduces emissions of ultrafine particles. To date, this phenomenon had only been observed in the laboratory.

“These results reinforce the need for public policies to encourage the use of biofuels, as they clearly show that the public lose in health what they save at the pump when opting for gasoline,” Artaxo said.

In São Paulo, a city with 7 million motor vehicles and the largest urban fleet of flexible-fuel cars, it would be feasible to run all buses on biofuel. “We have the technology for this in Brazil – and at a competitive price,” he said.

The fact that the city’s bus fleet still depends on diesel, Artaxo warned, creates an even worse health hazard in the shape of emissions of black carbon, one of the main components of soot and a pollutant that contributes to global warming. Alongside electricity generation, the transportation sector is the largest emitter of pollutants produced by the burning of fossil fuels.

For Artaxo, incentives for electric, hybrid or biofuel vehicles are vital to reduce greenhouse gas emissions. “By incentivizing biofuels, we could solve several problems at once,” he said. “We could combat climate change, reduce harm to health and foster advances in automotive technology by offering a stimulus for auto makers to develop more economical and efficient cars fueled by ethanol.”

Here’s a link to and a citation for the paper,

Reduced ultrafine particle levels in São Paulo’s atmosphere during shifts from gasoline to ethanol use by Alberto Salvo, Joel Brito, Paulo Artaxo, & Franz M. Geiger. Nature Communications 8, Article number: 77 (2017) doi:10.1038/s41467-017-00041-5 Published online: 18 July 2017

This paper is open access.