Wednesday, January 17, 2024

 

Parents more likely to attempt suicide in first years after child’s cancer diagnosis


However, parents are not more likely to die by suicide, finds study of parents in Denmark and Sweden

Peer-Reviewed Publication

PLOS





Parents who have a child with cancer are more likely to attempt suicide during the first years after diagnosis, according to a new study conducted by Qianwei Liu of Southern Medical University, China, and colleagues, published January 16th in the open access journal PLOS Medicine.

Receiving a cancer diagnosis for a child is an incredibly stressful and distressing experience for parents. These parents, especially mothers, face an increased risk of psychiatric disorders, but little is known about the risk of suicide. In the new study, researchers looked at the number of suicide attempts in more than 100,000 parents who had a child diagnosed with cancer in Denmark (1978-2016) or Sweden (1973-2014). For comparison, they looked at rates of suicide attempts in siblings of the parents of children with cancer, and in more than 1 million parents whose children did not have cancer.

The team saw an increased risk of a suicide attempt during the first years after a child’s cancer diagnosis, especially when the child was diagnosed under the age of 18 or had an aggressive or fatal form of cancer. However, there was no increased risk of parental suicide attempt later on, and no higher risk of death by suicide any time after the cancer diagnosis.

The new findings suggest that medical professionals should be more vigilant for possible suicide attempts among parents of children with cancer, especially during the first few years after diagnosis. The researchers propose that future studies should investigate whether these findings can be generalized to other countries with different healthcare systems, cultures, and cancer rates, as compared to Denmark and Sweden.

Liu adds, “Parents of children with cancer experienced an increased risk of suicide attempt during first few years after a child’s cancer diagnosis, but had no altered risk of death by suicide at any time.”

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In your coverage, please use this URL to provide access to the freely available paper in PLOS Medicinehttp://journals.plos.org/plosmedicine/article?id=10.1371/journal.pmed.1004322

Citation: Liu Q, László KD, Wei D, Yang F, Fall K, Valdimarsdóttir U, et al. (2024) Suicide attempt and death by suicide among parents of young individuals with cancer: A population-based study in Denmark and Sweden. PLoS Med 21(1): e1004322. https://doi.org/10.1371/journal.pmed.1004322

Author Countries: Sweden, United States, Denmark

Funding: This study was supported by the Swedish Cancer Society (grant number: 20 0846 PjF to FF), Karolinska Institutet (Senior Researcher Award and Strategic Research Area in Epidemiology to FF), the China Scholarship Council (grant number: 201700260291 to QL; grant number: 201700260276 to DW), the Novo Nordisk Foundation (grant number: NNF18OC0052029 to JL), the Independent Research Fund Denmark (grant numbers: DFF-6110-00019B, DFF-9039-00010B, and 1030-00012B to JL), the Nordic Cancer Union (grant number: R275-A15770 and R278-A15877 to JL), the Karen Elise Jensens Fond (2016 to JL), and the Swedish Research Council for Health, Working Life and Welfare (grant numbers: 2017-00531 to FF and 2015-00837 to KDL). The funders had no role in study design, data collection and analysis, decision to publish, or preparation of the manuscript.

 

E-cigarettes help pregnant smokers quit without risks to pregnancy


Peer-Reviewed Publication

QUEEN MARY UNIVERSITY OF LONDON





A new analysis of trial data on pregnant smokers, led by researchers at Queen Mary University of London, finds that the regular use of nicotine replacement products during pregnancy is not associated with adverse pregnancy events or poor pregnancy outcomes.  

The PREP 2 study used data collected from over 1100 pregnant smokers attending 23 hospitals in England and 1 stop-smoking service in Scotland to compare pregnancy outcomes in women who did or did not use nicotine in the form of e-cigarettes (EC) or nicotine patches regularly during their pregnancy. Researchers took measurements of salivary cotinine levels at baseline and towards the end of pregnancy, and gathered information about each participant’s use of cigarettes or types of NRT, respiratory symptoms, and the birth weight and other data of their babies at birth. 

The study found that e-cigarettes were more commonly used in the group studied than nicotine patches (47% compared with 21%), and also confirmed previous unexpected findings that EC use may reduce respiratory infections in vapers, possibly because the main ingredients of EC, aerosol, propylene glycol, and glycerine, have antibacterial effects.  

Women who smoked and also used one of the nicotine replacement products during their pregnancy had babies with the same birth weights as women who only smoked, while babies born to women who did not smoke during pregnancy did not differ in birth weight, whether the women did or did not use nicotine products. Regular use of nicotine products was not associated with any adverse effects in mothers or their babies. 

Lead researcher, Professor Peter Hajek from the Wolfson Institute of Population Health, Queen Mary University of London, said: "The trial contributes answers to two important questions, one practical and one concerning our understanding of risks of smoking. E-cigarettes helped pregnant smokers quit without posing any detectable risks to pregnancy compared with stopping smoking without further nicotine use. Using nicotine containing aids to stop smoking in pregnancy thus appears safe. The harms to pregnancy from smoking, in late pregnancy at least, seem to be due to other chemicals in tobacco smoke rather than nicotine." 

Prof Tim Coleman from the University of Nottingham’s Smoking in Pregnancy Research Group, which led trial recruitment said: “Smoking in pregnancy is a massive public health problem and nicotine containing aids can help pregnant women to stop smoking, but some clinicians are reticent about providing NRT or e-cigarettes in pregnancy.  This study provides further, reassuring evidence that tobacco smoke chemicals rather than nicotine are responsible for smoking-related harms, so  using nicotine containing aids to quit is vastly preferable to continuing to smoke when pregnant.” 

Professor Linda Bauld, Bruce and John Usher Chair in Public Health at the University of Edinburgh and a study co-investigator said: “Clinicians, pregnant women and their families have questions about the safety of using nicotine replacement therapy (NRT) or e-cigarettes during pregnancy.  Women who continue to smoke during pregnancy often find it difficult to stop but products like NRT or e-cigarettes can help them to do so. These results suggest that NRT or vaping can be used as part of a quit attempt without adverse effects. Our findings should be reassuring, and provide further important evidence to guide decision-making on smoking cessation during pregnancy.” 

The study, conducted by researchers at Queen Mary University of London, University of New South Wales (Australia), University of Nottingham, St George’s University of London, University of Stirling, University of Edinburgh, and King’s College London, and St George’s University Hospitals NHS Foundation Trust, analysed data collected in the Pregnancy Trial of E-cigarettes and Patches (PREP) randomised controlled trial, funded by the National Institute for Health and Care Research (NIHR). 

 

ENDS 

 

NOTES TO EDITORS 

Contact: Honey Lucas 

Faculty Communications Officer – Medicine and Dentistry 

Queen Mary University of London Email: h.lucas@qmul.ac.uk or contact press@qmul.ac.uk  

 

The published paper: 

“Safety of e-cigarettes and nicotine patches as stop-smoking aids in pregnancy: Secondary analysis of the Pregnancy Trial of E-cigarettes and Patches (PREP) randomised controlled trial”. 

Journal: Addiction 

Publication date and embargo: Embargoed until 8AM (UK TIME) WEDNESDAY 17 JANUARY 2024 

DOI: 10.1111/add.16422 

Available after publication at: https://onlinelibrary.wiley.com/doi/10.1111/add.16422  

 

Authors: 

Francesca Pesola, PhD (1), Katie Myers Smith, PhD (1), Anna Phillips-Waller, BSc (1) , Dunja Przulj, PhD (1), Christopher Griffiths, D.Phil (1), Robert Walton MD (2), Hayden McRobbie PhD (3), Tim Coleman MD (4), Sarah Lewis, PhD (4), Rachel Whitemore, BA (4), Miranda Clark BSc (4), Michael Ussher, PhD (5), Lesley Sinclair MSc (6), Emily Seager PhD (1), Sue Cooper, PhD (4), Linda Bauld, PhD (6), Felix Naughton, PhD (7), Peter Sasieni, PhD (8), Isaac Manyonda PhD (9), Peter Hajek, PhD (1). 

1) Wolfson Institute of Population Health, Queen Mary University of London. 

2) Blizard Institute, Queen Mary University of London. 

3) National Drug and Alcohol Research Centre, University of New South Wales, Sydney, Australia. 

4) Centre for Academic Primary Care, University of Nottingham. 

5) Division of Population Health Sciences and Education, St. George’s, University of London and Institute of Social Marketing and Health, University of Stirling. 

6) Usher Institute and SPECTRUM Consortium, University of Edinburgh. 

7) School of Health Sciences, University of East Anglia. 

8) The Cancer Research UK and King’s College London Cancer Prevention Trials Unit, King’s College London, UK. Please note, Peter Sasieni is now Professor of Cancer Epidemiology, Centre Co-Lead for the Centre for Cancer Screening, Prevention and Early Diagnosis, in the Wolfson Institute of Population Health at Queen Mary University of London. 

9) St George’s University Hospitals NHS Foundation Trust. 

 

Funding information: 

The study was funded by the National Institute for Health and Care Research (NIHR), ref: 15/57/85. 

 

About Queen Mary www.qmul.ac.uk 

At Queen Mary University of London, we believe that a diversity of ideas helps us achieve the previously unthinkable. 

Throughout our history, we’ve fostered social justice and improved lives through academic excellence. And we continue to live and breathe this spirit today, not because it’s simply ‘the right thing to do’ but for what it helps us achieve and the intellectual brilliance it delivers. 

Our reformer heritage informs our conviction that great ideas can and should come from anywhere. It’s an approach that has brought results across the globe, from the communities of east London to the favelas of Rio de Janeiro. 

We continue to embrace diversity of thought and opinion in everything we do, in the belief that when views collide, disciplines interact, and perspectives intersect, truly original thought takes form. 

 

About the National Institute for Health and Care Research (NIHR) 

The mission of the National Institute for Health and Care Research (NIHR) is to improve the health and wealth of the nation through research. We do this by: 

  • Funding high quality, timely research that benefits the NHS, public health and social care; 

  • Investing in world-class expertise, facilities and a skilled delivery workforce to translate discoveries into improved treatments and services; 

  • Partnering with patients, service users, carers and communities, improving the relevance, quality and impact of our research; 

  • Attracting, training and supporting the best researchers to tackle complex health and social care challenges; 

  • Collaborating with other public funders, charities and industry to help shape a cohesive and globally competitive research system; 

  • Funding applied global health research and training to meet the needs of the poorest people in low and middle income countries. 

NIHR is funded by the Department of Health and Social Care. Its work in low and middle income countries is principally funded through UK Aid from the UK government. 

 

 

 

Amnesia caused by head injury reversed in early mouse study


Peer-Reviewed Publication

GEORGETOWN UNIVERSITY MEDICAL CENTER




WASHINGTON - A mouse study designed to shed light on memory loss in people who experience repeated head impacts, such as athletes, suggests the condition could potentially be reversed. The research in mice finds that amnesia and poor memory following head injury is due to inadequate reactivation of neurons involved in forming memories.

The study, conducted by researchers at Georgetown University Medical Center in collaboration with Trinity College Dublin, Ireland, is reported January 16, 2024, in the Journal of Neuroscience.

Importantly for diagnostic and treatment purposes, the researchers found that the memory loss attributed to head injury was not a permanent pathological event driven by a neurodegenerative disease.  Indeed, the researchers could reverse the amnesia to allow the mice to recall the lost memory, potentially allowing cognitive impairment caused by head impact to be clinically reversed.

The Georgetown investigators had previously found that the brain adapts to repeated head impacts by changing the way the synapses in the brain operate. This can cause trouble in forming new memories and remembering existing memories. In their new study, investigators were able to trigger mice to remember memories that had been forgotten due to head impacts.

“Our research gives us hope that we can design treatments to return the head-impact brain to its normal condition and recover cognitive function in humans that have poor memory caused by repeated head impacts,” says the study’s senior investigator, Mark Burns, PhD, a professor and Vice-Chair in Georgetown’s Department of Neuroscience and director of the Laboratory for Brain Injury and Dementia.

In the new study, the scientists gave two groups of mice a new memory by training them in a test they had never seen before. One group was exposed to a high frequency of mild head impacts for one week (similar to contact sport exposure in people) and one group were controls that didn’t receive the impacts. The impacted mice were unable to recall the new memory a week later.

“Most research in this area has been in human brains with chronic traumatic encephalopathy (CTE), which is a degenerative brain disease found in people with a history of repetitive head impact,” said Burns. “By contrast, our goal was to understand how the brain changes in response to the low-level head impacts that many young football players regularly experience.”

Researchers have found that, on average, college football players receive 21 head impacts per week with defensive ends receiving 41 head impacts per week. The number of head impacts to mice in this study were designed to mimic a week of exposure for a college football player, and each single head impact by itself was extraordinarily mild.

Using genetically modified mice allowed the researchers to see the neurons involved in learning new memories, and they found that these memory neurons (the "memory engram") were equally present in both the control mice and the experimental mice.

To understand the physiology underlying these memory changes, the study’s first author, Daniel P. Chapman, Ph.D., said, “We are good at associating memories with places, and that's because being in a place, or seeing a photo of a place, causes a reactivation of our memory engrams. This is why we examined the engram neurons to look for the specific signature of an activated neuron. When the mice see the room where they first learned the memory, the control mice are able to activate their memory engram, but the head impact mice were not. This is what was causing the amnesia.”

The researchers were able to reverse the amnesia to allow the mice to remember the lost memory using lasers to activate the engram cells. “We used an invasive technique to reverse memory loss in our mice, and unfortunately this is not translatable to humans,” Burns adds. “We are currently studying a number of non-invasive techniques to try to communicate to the brain that it is no longer in danger, and to open a window of plasticity that can reset the brain to its former state.”

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In addition to Burns and Chapman the authors include Stefano Vicini at Georgetown University and Sarah D. Power and Tomás J. Ryan at Trinity College Dublin, Ireland.

This work was supported by the Mouse Behavior Core in the Georgetown University Neuroscience Department and by the National Institutes of Health (NIH) / National Institute of Neurological Disorders and Stroke (NINDS) grants R01NS107370 & R01NS121316. NINDS also supported F30 NS122281 and the Neural Injury and Plasticity Training Grant housed in the Center for Neural Injury and Recovery at Georgetown University (T32NS041218). Seed funding is from the CTE Research Fund at Georgetown.

The authors report having no personal financial interests related to the study.

 

Canadian Science Publishing goes live on OA switchboard


Business Announcement

CANADIAN SCIENCE PUBLISHING





As part of our open science strategy, Canadian Science Publishing (CSP) is pleased to announce our new partnership with OA Switchboard, a mission-driven, community led initiative designed to simplify the sharing of information between stakeholders about open access publications throughout the whole publication journey.

“We’re thrilled to partner with the OA Switchboard to improve the visibility of the work we publish,” says Elaine Stott, Chief Executive Officer of CSP. “This initiative enables institutions, consortia and funders to report open access information from all participating publishers within a singular data format.”

As of January 1, 2024, all open access manuscripts published in CSP journals, trigger an automatic P1 message (a set of metadata related to a specific article publication) upon version of record publication to the affiliated librarian or research funder confirming the published article’s details. These will be sent to libraries, consortia, and funders active within the OA Switchboard program.

As an independent intermediary, OA Switchboard aims to connect parties and systems, streamlining and simplifying the exchange of OA related publication-level information.

The OA Switchboard:

  • offers standardised and authoritative publication metadata for internal and external reporting and purchasing decisions
  • enables libraries to monitor deal compliance across many publishers and confirm author and article compliance
  • delivers structured version of record metadata format (JSON and Excel)
  • feeds data automatically into existing funder, institution and library systems for further integration, processing and analysis
  • adopts the ESAC and Jisc standard reporting recommendations

“OA Switchboard shapes collaborative infrastructure to make the ecosystem work better for everyone. It is a mission-driven practical solution, that thrives on collaboration. The more stakeholders connect, the better the service for everyone. We are delighted to have Canadian Science Publishing, with their OA ambitions, participate in the initiative,” says Yvonne Campfens, Executive Director of Stichting OA Switchboard.

For more information on how you can join the OA Switchboard, contact Yvonne Campfens, Executive Director. You can also learn more about OA Switchboard in this three-minute video.

About Canadian Science Publishing

Canadian Science Publishing (CSP) is an independent, not-for-profit leader in mobilizing science, making sure it is easy to discover, use, and share. Featuring content from a global community of researchers, CSP is Canada’s largest publisher of peer-reviewed science journals. 

About OA Switchboard

The OA Switchboard is a mission-driven, community led initiative designed to simplify the sharing of information between stakeholders about open access publications throughout the whole publication journey. It provides a standardised messaging protocol and shared infrastructure that is designed to operate and integrate with all stakeholder systems. It is built by and for the people who use it, and is leveraged with existing PID’s.

 

A new, rigorous assessment of OpenET accuracy for supporting satellite-based water management


A new study offers a comprehensive multi-model, large-scale accuracy assessment of an operational satellite-based data system to compute evapotranspiration


Peer-Reviewed Publication

DESERT RESEARCH INSTITUTE

photo 1 

IMAGE: 

AN IMAGE SHOWING THE OPENET DATA EXPLORER RASTER VIEW OF EVAPOTRANSPIRATION.

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CREDIT: DRI/OPENET





Sustainable water management is an increasing concern in arid regions around the world, and scientists and regulators are turning to remote sensing tools like OpenET to help track and manage water resources. OpenET uses publicly available data produced by NASA and USGS Landsat and other satellite systems to calculate evapotranspiration (ET), or the amount of water lost to the atmosphere through soil evaporation and plant transpiration, at the level of individual fields. This tool has the potential to revolutionize water management, allowing for field-scale operational monitoring of water use, and a new study provides a thorough analysis of the accuracy of OpenET data for various crops and natural land cover types.

In the study, published Jan. 15 in Nature WaterDRI scientists led a large team of researchers in a comparison of OpenET data to evapotranspiration data produced by 152 ground-based micrometeorological stations known as eddy covariance flux towers. The researchers found that OpenET data has high accuracy for assessing evapotranspiration in agricultural settings, particularly for annual crops like wheat, corn, soy, and rice. OpenET results for these crops were particularly reliable in arid regions like California and the Southwest, supporting the use of this tool to address an ongoing regional water sustainability crisis.

“One of the biggest questions for users of OpenET data is how accurate it is, given the magnitude and implications of the use of the data for water resource management,” said John Volk, Ph.D., lead author of the study and assistant research scientist and software engineer at DRI. “A lot of groups want to know what the expected rates of error are in agricultural lands, so that’s the major question that we wanted to address for this paper.”

The eddy covariance stations consist of instruments and techniques for calculating the flux of trace gases, like water vapor, coming off the land surface. They offer one of the best methods for quantifying evapotranspiration on the ground, Volk says, which provided the researchers the opportunity to compare the ground-based observations with those provided by satellites. Each station’s data was compared to the OpenET model ensemble, which combines six different Landsat-based models to produce an average, as well as data from each individual model. Then, the stations were grouped by land cover type and climate zone to assess how the accuracy of OpenET data changes across these variables.

“I was impressed by the level of performance of the OpenET system,” Volk said. “It’s kind of surprising how well the models did, and how well they agreed with one another in agricultural sites—particularly in the peak growing season when water demands are the highest.”

For annual crops, OpenET data for monthly, growing season, and annual evapotranspiration had an average error rate of approximately 10-20%, which is within the targeted range set by OpenET partners such as farmers and water management agencies. For annual crops growing in Mediterranean climates, monthly error rates were consistently below 10% during peak growing season, emphasizing the usefulness of this data. Accuracy for orchards was more variable (17%), which could be related to the way that shadows impact satellite data for taller vegetation, the authors say.

OpenET data can also be used for monitoring evapotranspiration in natural ecosystems and error rates for most natural land cover types was less than 1 mm per day at monthly to annual timesteps. However, ET rates are generally lower for these ecosystems, resulting in relative error rates that are higher in these environments than in croplands, and range from 35% for forests to 50% for shrublands. While the relative errors are higher for natural ecosystems, the ET data are still useful as indicators of drought impacts, vegetation water stress and water availability.

“Evapotranspiration is one of the hardest hydrologic fluxes to measure, and to think we are quantifying this flux from space with comparable or better accuracy to ground-based weather stations and meter data for agricultural lands is really remarkable,” said study co-author Justin Huntington, Ph.D., research professor at DRI. “The combined use of the Landsat-satellite archive with new Google Earth Engine cloud computing resources has been key, as has our collaboration across different research groups and use of multiple models to better understand model strengths and weaknesses and identify areas for improvement.”

Future research will focus on natural ecosystems and how OpenET models compare under different agricultural demand management and conservation actions, such as those being explored in the Colorado River Basin.

The study notes that although all OpenET models have room for improvement, the results show the remarkable progress achieved in developing fully automated remote sensing techniques for mapping evapotranspiration at large spatial scales and at the resolution of individual fields based on petabytes of Landsat satellite data and new cloud computing resources.

“Farmers and water managers increasingly need accurate, field-level data on water use,” said Maurice Hall, OpenET director and senior advisor, Climate Resilient Water Systems, Environmental Defense Fund. “This study helps confirm the vital role OpenET plays in providing a more granular, dynamic picture of water use that can meaningfully inform real-time water decision-making. We look forward to continuing to refine and expand the implementation of OpenET to ensure farmers, ranchers, and communities can thrive in a world of highly stressed and variable water supplies.”

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More information: The full study, Assessing the accuracy of OpenET satellite-based evapotranspiration data to support water resource and land management applications, is available from Nature Water: 10.1038/s44221-023-00181-7. For more information on OpenET visit https://openetdata.org/. OpenET users and scientists can find the most updated accuracy information at https://openetdata.org/accuracy/.

 

Additional Quotes: “It’s truly rewarding to see decades of careful research and hard work by this science community come together, and this study sets a new benchmark for satellite mapping of field-scale evapotranspiration with Landsat,” says Forrest Melton, senior research scientist with NASA Ames Research Center. “By documenting the accuracy of the OpenET data, I anticipate that this study will further accelerate the already rapid uptake and use of these data to help solve pressing water management challenges and open up new applications and areas of future study.”

 

Study authors includeJohn M. Volk and Justin L. Huntington (DRI),  Forrest S. Melton (NASA Ames, CSU Monterey Bay), Richard Allen, (U. of Idaho), Martha Anderson (USDA Agricultural Research Service), Joshua B. Fisher (UCLA), Ayse Kilic (University of Nebraska-Lincoln), Anderson Ruhoff (Universidade Federal do Rio Grande do Sul), Gabriel B. Senay (U.S. Geological Survey Earth Resources Observation and Science Center), Blake Minor (DRI), Charles Morton (DRI), Thomas Ott (DRI), Lee Johnson (NASA Ames, CSU Monterey Bay), Bruno Comini de Andrade (Universidade Federal do Rio Grande do Sul), Will Carrara (NASA Ames, CSU Monterey Bay), Conor Doherty (NASA Ames), Christian Dunkerly (DRI), MacKenzie Friedrichs (KBR, Inc), Alberto Guzman (NASA Ames, CSU Monterey Bay), Christopher Hain (NASA Marshall Space Flight Center), Gregory Halverson (NASA Jet Propulsion Lab), Yanghui Kang (UC Berkeley) , Kyle Knipper (USDA Agricultural Research Service), Leonardo Laipelt (Universidade Federal do Rio Grande do Sul), Samuel Ortega-Salazar (University of Nebraska-Lincoln), Christopher Pearson (DRI), Gabriel E.L. Parrish (Innovate!, Inc.), A.J. Purdy (NASA Ames, CSU Monterey Bay), Peter ReVelle (University of Nebraska-Lincoln), Tianxin Wang (UC Berkeley), Yun Yang (Mississippi State University)

 

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About OpenET

OpenET is a public-private collaboration with input from more than 100 farmers, water managers, and other stakeholders, and led by OpenET, Inc., Desert Research Institute, NASA, Environmental Defense Fund, and the U.S. Geological Survey. Additional partners include Google, U.S. Department of Agriculture, California State University Monterey Bay, Mississippi State University, HabitatSeven, University of Idaho, University of Maryland, University of Nebraska-Lincoln, UCLA, and Universidade Federal do Rio Grande do Sul in Brazil.

 

About DRI

The Desert Research Institute (DRI) is a recognized world leader in basic and applied environmental research. Committed to scientific excellence and integrity, DRI faculty, students who work alongside them, and staff have developed scientific knowledge and innovative technologies in research projects around the globe. Since 1959, DRI’s research has advanced scientific knowledge on topics ranging from humans’ impact on the environment to the environment’s impact on humans. DRI’s impactful science and inspiring solutions support Nevada’s diverse economy, provide science-based educational opportunities, and inform policymakers, business leaders, and community members. With campuses in Las Vegas and Reno, DRI serves as the non-profit research arm of the Nevada System of Higher Education. For more information, please visit www.dri.edu.

 

 

Study reveals a reaction at the heart of many renewable energy technologies


New insights into how proton-coupled electron transfers occur at an electrode could help researchers design more efficient fuel cells and electrolyzers.


Peer-Reviewed Publication

MASSACHUSETTS INSTITUTE OF TECHNOLOGY

Applying an electric potential causes a proton to transfer from a hydronium ion (at right) to an electrode's surface. 

IMAGE: 

APPLYING AN ELECTRIC POTENTIAL CAUSES A PROTON TO TRANSFER FROM A HYDRONIUM ION (AT RIGHT) TO AN ELECTRODE'S SURFACE. USING ELECTRODES WITH MOLECULARLY DEFINED PROTON BINDING SITES, MIT RESEARCHERS DEVELOPED A GENERAL MODEL FOR THESE INTERFACIAL PROTON-COUPLED ELECTRON TRANSFER REACTIONS.

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CREDIT: MIT





CAMBRIDGE, MA — A key chemical reaction — in which the movement of protons between the surface of an electrode and an electrolyte drives an electric current — is a critical step in many energy technologies, including fuel cells and the electrolyzers used to produce hydrogen gas.

For the first time, MIT chemists have mapped out in detail how these proton-coupled electron transfers happen at an electrode surface. Their results could help researchers design more efficient fuel cells, batteries, or other energy technologies.

“Our advance in this paper was studying and understanding the nature of how these electrons and protons couple at a surface site, which is relevant for catalytic reactions that are important in the context of energy conversion devices or catalytic reactions,” says Yogesh Surendranath, a professor of chemistry and chemical engineering at MIT and the senior author of the study.

Among their findings, the researchers were able to trace exactly how changes in the pH of the electrolyte solution surrounding an electrode affect the rate of proton motion and electron flow within the electrode.

MIT graduate student Noah Lewis is the lead author of the paper, which appears today in Nature Chemistry. Ryan Bisbey, a former MIT postdoc; Karl Westendorff, an MIT graduate student; and Alexander Soudackov, a research scientist at Yale University, are also authors of the paper.

 

Passing protons

Proton-coupled electron transfer occurs when a molecule, often water or an acid, transfers a proton to another molecule or to an electrode surface, which stimulates the proton acceptor to also take up an electron. This kind of reaction has been harnessed for many energy applications.

“These proton-coupled electron transfer reactions are ubiquitous. They are often key steps in catalytic mechanisms, and are particularly important for energy conversion processes such as hydrogen generation or fuel cell catalysis,” Surendranath says.

In a hydrogen-generating electrolyzer, this approach is used to remove protons from water and add electrons to the protons to form hydrogen gas. In a fuel cell, electricity is generated when protons and electrons are removed from hydrogen gas and added to oxygen to form water.

Proton-coupled electron transfer is common in many other types of chemical reactions, for example, carbon dioxide reduction (the conversion of carbon dioxide into chemical fuels by adding electrons and protons). Scientists have learned a great deal about how these reactions occur when the proton acceptors are molecules, because they can precisely control the structure of each molecule and observe how electrons and protons pass between them. However, when proton-coupled electron transfer occurs at the surface of an electrode, the process is much more difficult to study because electrode surfaces are usually very heterogenous, with many different sites that a proton could potentially bind to.

To overcome that obstacle, the MIT team developed a way to design electrode surfaces that gives them much more precise control over the composition of the electrode surface. Their electrodes consist of sheets of graphene with organic, ring-containing compounds attached to the surface. At the end of each of these organic molecules is a negatively charged oxygen ion that can accept protons from the surrounding solution, which causes an electron to flow from the circuit into the graphitic surface.

“We can create an electrode that doesn’t consist of a wide diversity of sites but is a uniform array of a single type of very well-defined sites that can each bind a proton with the same affinity,” Surendranath says. “Since we have these very well-defined sites, what this allowed us to do was really unravel the kinetics of these processes.”

Using this system, the researchers were able to measure the flow of electrical current to the electrodes, which allowed them to calculate the rate of proton transfer to the oxygen ion at the surface at equilibrium — the state when the rates of proton donation to the surface and proton transfer back to solution from the surface are equal. They found that the pH of the surrounding solution has a significant effect on this rate: The highest rates occurred at the extreme ends of the pH scale — pH 0, the most acidic, and pH 14, the most basic.

To explain these results, researchers developed a model based on two possible reactions that can occur at the electrode. In the first, hydronium ions (H3O+), which are in high concentration in strongly acidic solutions, deliver protons to the surface oxygen ions, generating water. In the second, water delivers protons to the surface oxygen ions, generating hydroxide ions (OH-), which are in high concentration in strongly basic solutions.

However, the rate at pH 0 is about four times faster than the rate at pH 14, in part because hydronium gives up protons at a faster rate than water.

 

A reaction to reconsider

The researchers also discovered, to their surprise, that the two reactions have equal rates not at neutral pH 7, where hydronium and hydroxide concentrations are equal, but at pH 10, where the concentration of hydroxide ions is 1 million times that of hydronium. The model suggests this is because the forward reaction involving proton donation from hydronium or water contributes more to the overall rate than the backward reaction involving proton removal by water or hydroxide.

Existing models of how these reactions occur at electrode surfaces assume that the forward and backward reactions contribute equally to the overall rate, so the new findings suggest that those models may need to be reconsidered, the researchers say.

“That’s the default assumption, that the forward and reverse reactions contribute equally to the reaction rate,” Surendranath says. “Our finding is really eye-opening because it means that the assumption that people are using to analyze everything from fuel cell catalysis to hydrogen evolution may be something we need to revisit.”

The researchers are now using their experimental setup to study how adding different types of ions to the electrolyte solution surrounding the electrode may speed up or slow down the rate of proton-coupled electron flow.

“With our system, we know that our sites are constant and not affecting each other, so we can read out what the change in the solution is doing to the reaction at the surface,” Lewis says.

 

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The research was funded by the U.S. Department of Energy Office of Basic Energy Sciences.


Wrongly-enforced rules over “digital surrogates” by museums censors research and creative use, study warns


 NEWS RELEASE 

UNIVERSITY OF EXETER





Cultural institutions are censoring research, learning and creativity because of the way they police the reuse of digital copies of out-of-copyright artworks and artefacts, a new study warns.

Cultural institutions have created a “mess” by claiming and enforcing new rights over the reproduction images of works in their collections.

This allows museums and other organisations to refuse requests for the use of the images in education or research or charge high fees. This impedes free and creative expression and amounts to censorship, according to Dr Andrea Wallace from the University of Exeter Law School.

Researchers, educators and others regularly ask to use images of objects in museum and art gallery collections, but it is often complicated, too expensive or difficult to get permission. The way organisations charge or refuse rights to use “digital surrogates” are outdated and conflict with public missions, the study says.

It warns the UK cultural sector has not kept up with efforts to promote open access to digital collections ongoing elsewhere around the world and there is more concern with generating income through image licensing. This impedes the legitimate use of the public domain for those researching and studying, as well as for artists, the creative industries, and the public for learning and new creations.

The study proposes a new framework to help staff in cultural institutions make more accurate assessments of copyright rights in digital surrogates.

Dr Wallace said: “The current system is a mess, but this new framework can help to disentangle the use of surrogate rights from the ways that cultural institutions manage their collections. It allows lawyers, directors, and heritage practitioners to mend things themselves by distinguishing original from non-original reproduction media. This better captures the vast potential of our public domain cultural heritage in this digital age.

“Of course, cultural institutions cannot and should not uncritically digitize and publish all collections and data for free and unfettered reuse. But there is a clear need to provide access and improve legal certainty for the public who would like to use out-of-copyright collections.”

The framework aims to reduce barriers to people using collections while protecting legitimate intellectual property, curatorial and educational expertise. By encouraging cultural institutions to publish high-quality images online, visitors onsite and online will know they can get the best possible surrogate directly from the source.

Experience shows this can bring new relevance to cultural institutions and drive new income streams, as there may be business opportunities and partnerships made possible by open access.

Dr Wallace said: “The framework can also improve legal certainty around public reuse of surrogate images in the public domain while bolstering their compliance with legitimate reuse restrictions. Imagine how simple it would be if we could identify the artwork and assess its copyright status using the lifetime of the original artist, rather than the claim of the cultural institution asserting a surrogate copyright in the image.

“The data already tells us that most cultural institutions lose money by operating a copyright licensing service. They rarely bring in enough income to cover the costs of running them. Nor is a surrogate copyright necessary to generate revenue or enforce rights in the collection. Cultural institutions can still charge service fees for image creation and delivery. And rather than basing claims on surrogate copyright, institutions can focus infringement notices on legitimate claims, such as trademark, false advertising, or concerns with the specific use, thereby reducing operating costs and inefficiencies.

“The short-term benefits will be to help cultural institutions comply with copyright law, meet their public missions in a digital age and explore more sustainable business models around open access collections. The long-term benefits will be to support the publication of data that is better fit for purpose in the 21st century. Open datasets are invaluable for computational processing, machine learning, and artificial intelligence. If cultural institutions view collections data as within public domain and therefore are more wary of these risks, it may improve the pre-publication assessments of what materials should be digitized. Cultural institutions can then use technological safeguards to revise or restructure data, embed relevant context or information in the metadata, and provide guidelines to support more appropriate reuse and reduce harm.”