Thorsten Bartels-Rausch, Jessie Creamean, Jennie L. Thomas, Megan Willis and Paul Zieger
{"title":"Ten crucial unknowns in atmospheric chemistry in the cold","authors":"Thorsten Bartels-Rausch, Jessie Creamean, Jennie L. Thomas, Megan Willis and Paul Zieger","doi":"10.1039/D5FD00056D","DOIUrl":"10.1039/D5FD00056D","url":null,"abstract":"<p >The Southern Ocean, wintertime cities, the upper troposphere, the Arctic and Antarctica, and alpine mountains are places where atmospheric chemistry impacts human health, air quality, climate, or geochemical cycles and that are characterized by low temperatures where ice or snow can be present. The atmospheric impact is evident from the role of polar biogenic sulphur emissions on aerosol formation, multiphase nitrogen and sulphur chemistry on wintertime haze, and industrial emissions in snow-covered areas on the ozone budget. The Cryosphere and ATmospheric CHemistry community (CATCH) addresses the environmental processes within these coupled cryosphere–atmosphere systems, and here we present open research questions specific to the cold environments, focusing on the unique interplay of chemistry and physics. These research needs call for interdisciplinary approaches to address atmospheric science in a warming climate with changing human impact in Earth's cold regions.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"258 ","pages":" 10-22"},"PeriodicalIF":3.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/fd/d5fd00056d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144172069","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sarah Albertin, Markus Ammann, Thorsten Bartels-Rausch, James Brean, Lucy J. Carpenter, Rohit Chikkaraddy, Martyn P. Chipperfield, Giancarlo Ciarelli, Hugh Coe, Jenée D. Cyran, Barbara D’Anna, Bruno Delille, Valerio Ferracci, Markus M. Frey, Natasha Garner, Dwayne Heard, Zamin A. Kanji, Saewung Kim, Julia Kojoj, Alexis Lamothe, Kathy S. Law, Sönke Maus, Claudia Mohr, Jennifer G. Murphy, Christian Pfrang, Kerri Pratt, Tjarda Roberts, Jochen Stutz, Thomas Whale, Megan Willis, Xin Yang and Paul Zieger
{"title":"Aerosol, clouds and particles: general discussion","authors":"Sarah Albertin, Markus Ammann, Thorsten Bartels-Rausch, James Brean, Lucy J. Carpenter, Rohit Chikkaraddy, Martyn P. Chipperfield, Giancarlo Ciarelli, Hugh Coe, Jenée D. Cyran, Barbara D’Anna, Bruno Delille, Valerio Ferracci, Markus M. Frey, Natasha Garner, Dwayne Heard, Zamin A. Kanji, Saewung Kim, Julia Kojoj, Alexis Lamothe, Kathy S. Law, Sönke Maus, Claudia Mohr, Jennifer G. Murphy, Christian Pfrang, Kerri Pratt, Tjarda Roberts, Jochen Stutz, Thomas Whale, Megan Willis, Xin Yang and Paul Zieger","doi":"10.1039/D5FD90012C","DOIUrl":"10.1039/D5FD90012C","url":null,"abstract":"","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"258 ","pages":" 171-200"},"PeriodicalIF":3.4,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144172061","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Sarah Albertin, Markus Ammann, Patrick Ayotte, Thorsten Bartels-Rausch, Hendrik Bluhm, James Brean, Natalie Brett, Lucy V. Brown, Tillmann Buttersack, Lucy J. Carpenter, Rohit Chikkaraddy, Hugh Coe, Jenée D. Cyran, Natasha Garner, Dwayne Heard, Deanna Huff, Saewung Kim, Jingqiu Mao, Jennifer G. Murphy, Christian Pfrang, Kerri A. Pratt, Matti Rissanen, Joel Savarino, Céline Toubin, Thomas Whale and Megan Willis
{"title":"Multiphase chemistry: general discussion","authors":"Sarah Albertin, Markus Ammann, Patrick Ayotte, Thorsten Bartels-Rausch, Hendrik Bluhm, James Brean, Natalie Brett, Lucy V. Brown, Tillmann Buttersack, Lucy J. Carpenter, Rohit Chikkaraddy, Hugh Coe, Jenée D. Cyran, Natasha Garner, Dwayne Heard, Deanna Huff, Saewung Kim, Jingqiu Mao, Jennifer G. Murphy, Christian Pfrang, Kerri A. Pratt, Matti Rissanen, Joel Savarino, Céline Toubin, Thomas Whale and Megan Willis","doi":"10.1039/D5FD90014J","DOIUrl":"10.1039/D5FD90014J","url":null,"abstract":"","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"258 ","pages":" 419-440"},"PeriodicalIF":3.4,"publicationDate":"2025-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144118367","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Markus Ammann, James Brean, Lucy J. Carpenter, Rohit Chikkaraddy, Martyn P. Chipperfield, Barbara D’Anna, Valerio Ferracci, Markus M. Frey, Dwayne E. Heard, Saffron G. Heddell, Alicia Hoffman, Deanna Huff, Bianca Lauster, Kathy S. Law, Jingqiu Mao, Claudia Mohr, Jennifer G. Murphy, Peter K. Peterson, Kerri A. Pratt, Tjarda J. Roberts, Joel Savarino, Freya Squires, Jochen Stutz, Megan Willis and Xin Yang
{"title":"Transport and chemistry: general discussion†","authors":"Markus Ammann, James Brean, Lucy J. Carpenter, Rohit Chikkaraddy, Martyn P. Chipperfield, Barbara D’Anna, Valerio Ferracci, Markus M. Frey, Dwayne E. Heard, Saffron G. Heddell, Alicia Hoffman, Deanna Huff, Bianca Lauster, Kathy S. Law, Jingqiu Mao, Claudia Mohr, Jennifer G. Murphy, Peter K. Peterson, Kerri A. Pratt, Tjarda J. Roberts, Joel Savarino, Freya Squires, Jochen Stutz, Megan Willis and Xin Yang","doi":"10.1039/D5FD90013A","DOIUrl":"10.1039/D5FD90013A","url":null,"abstract":"","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"258 ","pages":" 328-356"},"PeriodicalIF":3.4,"publicationDate":"2025-05-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144118369","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Fusion of asymmetric membranes: the emergence of a preferred direction†","authors":"Petr Shendrik, Raya Sorkin and Gonen Golani","doi":"10.1039/D4FD00189C","DOIUrl":"10.1039/D4FD00189C","url":null,"abstract":"<p >The fusion of lipid membranes progresses through a series of intermediate steps with two significant energy barriers: hemifusion-stalk formation and fusion-pore expansion. The cell’s ability to tune these energy barriers is crucial as they determine the rate of many biological processes involving membrane fusion. However, a mechanism that allows the cell to manipulate both barriers in the same direction remains elusive, since membrane properties that the cell could dynamically tune during its life cycle, such as the lipids’ spontaneous curvatures and membrane tension, have an opposite effect on the two barriers: tension inhibits stalk formation while promoting fusion-pore expansion. In contrast, increasing the total membrane concentration of lipids with negative intrinsic curvatures, such as cholesterol, promotes hemifusion-stalk formation while inhibiting pore expansion, and <em>vice versa</em> for lipids with positive intrinsic curvatures. Therefore, changes in these membrane properties increase one energy barrier at the expense of the other, resulting in a mixed effect on the fusion reaction. A possible mechanism to change both barriers in the same direction is by inducing lipid composition asymmetry, which results in tension and spontaneous curvature differences between the monolayers. To test the feasibility of this mechanism, a continuum elastic model was used to simulate the fusion intermediates and calculate the changes in the energy barriers. The calculations showed that a reasonable lipid composition asymmetry could lead to a 10–20<em>k</em><small><sub>B</sub></small><em>T</em> difference in both energy barriers, depending on the direction from which fusion occurs. We further provide experimental support to the model predictions, demonstrating changes in the time to hemifusion upon asymmetry introduction. These results indicate that biological membranes, which are asymmetric, have a preferred direction for fusion.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"259 ","pages":" 416-436"},"PeriodicalIF":3.1,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144092213","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Spiers Memorial Lecture: A retrospective view on the non-classical features revealed by advanced imaging of biominerals","authors":"Laurie Gower","doi":"10.1039/D5FD00054H","DOIUrl":"10.1039/D5FD00054H","url":null,"abstract":"<p >Biominerals have unique morphologies and complex hierarchical microstructures, so the study of biomineralization has benefited greatly from the development of advanced microscopy and characterization tools. In my career, I witnessed a revolutionary change in the theories relating to biomineral formation mechanisms. While much of this was due to the advancements in imaging techniques, I present an argument to suggest that <em>in vitro</em> model systems played an important role in steering the biomineral community toward resolving the non-classical crystallization processes that are now understood to lie at the foundation of biological calcification processes. This retrospective review will discuss two case studies that are classic examples of biominerals, mollusk nacre for the invertebrates, and bone for the vertebrates. It will therefore be biased given my group's discovery of the Polymer-Induced Liquid-Precursor (PILP) process, which serendipitously emulated the morphologies and textures of these (and other) biominerals. The goal, however, is not to repeat that body of literature, but rather to demonstrate how the use of model systems has helped decipher mineralization mechanisms, and to propose new ideas that could be explored to further advance the field.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"261 ","pages":" 11-67"},"PeriodicalIF":3.1,"publicationDate":"2025-05-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/fd/d5fd00054h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144289361","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Spiers Memorial Lecture: Recent advances (and challenges) in supramolecular gels","authors":"Haozhe Zheng and Darrin J. Pochan","doi":"10.1039/D5FD00044K","DOIUrl":"10.1039/D5FD00044K","url":null,"abstract":"<p >Supramolecular hydrogels are physical hydrogels that are formed by non-covalent interactions such as hydrogen bonding, electrostatic attraction, hydrophobic interactions, and π–π stacking. Compared to typical, chemically cross-linked hydrogels, supramolecular networks commonly have stimuli-responsive behavior including reversibility and injectability, which are being widely studied for uses in drug delivery, tissue engineering, and wound healing. This review highlights recent developments in supramolecular network design and behavior focusing on the different possible molecular building blocks, including peptides, polysaccharides, synthetic polymers, and multicomponent systems. We further discuss self-assembly mechanisms of hydrogel formation, as well as recent advances in stimuli-responsive supramolecular hydrogels triggered by pH, temperature, and light. Advanced characterization techniques such as rheological analysis, spectroscopy, scattering methods, and electron microscopy are summarized to understand hydrogel structure, assembly pathways, and ultimate network properties. This review provides readers with an updated understanding of supramolecular hydrogels and highlights current research presented during the <em>Faraday Discussions</em> meeting on advances in supramolecular gels, promoting the rational design and development of novel materials to address complex biomedical and other technological challenges.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"260 ","pages":" 9-34"},"PeriodicalIF":3.1,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12131310/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144207160","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Teresa Rodríguez-García, Loretta Akakpo, Sadie L. Nickles, Ryan J. Schuck, Daiane S. Alves, Katherine G. Schaefer, Frederick A. Heberle, Gavin M. King and Francisco N. Barrera
{"title":"Engineering of lipid membranes asymmetrically functionalized with chondroitin sulfate†","authors":"Teresa Rodríguez-García, Loretta Akakpo, Sadie L. Nickles, Ryan J. Schuck, Daiane S. Alves, Katherine G. Schaefer, Frederick A. Heberle, Gavin M. King and Francisco N. Barrera","doi":"10.1039/D4FD00195H","DOIUrl":"10.1039/D4FD00195H","url":null,"abstract":"<p >One of the defining properties of the eukaryotic plasma membrane is the glycocalyx, which is formed by glycosylated lipids and proteins. The glycocalyx is arranged asymmetrically, as it is exclusive to the extracellular side of the membrane. Membrane asymmetry therefore includes both lipid and carbohydrate asymmetry, whereby the latter has the most skewed trans-leaflet imbalance. The glycocalyx plays a structural role that protects cell integrity and it also participates in mechanosensing and other cellular processes. However, our understanding of glycocalyx function is hampered by the lack of suitable model systems to perform biophysical investigation. Here, we describe the engineering of lipid bilayers that are chemically conjugated at the outer surface with one of the most abundant glycocalyx components, chondroitin sulfate (CS). Membranes were doped with a reactive phospholipid, which allowed thiol–maleimide conjugation of thiol-modified CS at the lipid headgroup. Our data show that we achieved CS conjugation of large unilamellar vesicles, supported lipid bilayers, and giant unilamellar vesicles. CS conjugation of vesicles allowed electrostatic recruitment of poly-<small>L</small>-lysine, which could recruit other CS-coated vesicles or CS in solution. Overall, we describe a simple and robust method for polysaccharide functionalization of vesicles which can be applied to gain new mechanistic understanding of the pathophysiological role of the glycocalyx.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"259 ","pages":" 168-181"},"PeriodicalIF":3.1,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12062790/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143953242","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Elucidating the mechanical properties of asymmetric membranes by direct derivation of their energetics†","authors":"Giacomo Fiorin and Lucy R. Forrest","doi":"10.1039/D5FD00006H","DOIUrl":"10.1039/D5FD00006H","url":null,"abstract":"<p >The asymmetry between the two leaflets of a plasma membrane (PM) is widely accepted as an essential condition for most PM-associated biochemical processes. However, recent work has also shown that asymmetric bilayers can be significantly stiffer upon bending than symmetric ones, suggesting that the same asymmetry may hinder the ability of the PM to remodel itself. Here, we address this issue by combining all-atom molecular dynamics (MD) simulations with an enhanced sampling scheme that explicitly induces membrane deformations to quantify their free-energy cost. Examining small asymmetric POPC/DOPC bilayers, we find that a small density imbalance between the leaflets increases their bending rigidity compared to bilayers with minimal imbalance, or to symmetric bilayers of the same two lipids. This result is consistent with recently proposed theoretical models that identify differential stress as the main source of stiffening in asymmetric membranes. The first-principles approach used in this study is broadly applicable to other types of membrane, enabling further exploration of the interplay between asymmetry and curvature, or the simulation of specific biological conditions of the PM.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"259 ","pages":" 437-453"},"PeriodicalIF":3.1,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143956892","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Nonequilibrium asymmetry in the living cell membrane†","authors":"Ajay Kumar Bansal and Madan Rao","doi":"10.1039/D4FD00207E","DOIUrl":"10.1039/D4FD00207E","url":null,"abstract":"<p >We will discuss how sustained nonequilibrium processes operating at the plasma membrane (PM) determine the dynamical organisation (both lateral and transverse) of lipids, their maintenance and control, under physiological conditions. These nonequilibrium processes include active contractile stresses arising from the inevitable interaction of the inner leaflet of the PM with the adjoining actomyosin cortex, and active flipping of specific lipids. Recently, we showed that the inner leaflet phosphatidylserine (PS) interacts with the actomyosin cortex and engages in a strong transbilayer coupling across the leaflets. Here we develop an active Flory–Huggins theory for the mesoscale segregation of liquid-ordered (lo)–liquid-disordered (ld) domains in an asymmetric membrane bilayer, that incorporates both active contractile stresses at the inner leaflet and transbilayer coupling across the leaflets. The interplay between chemical potential gradients, transbilayer coupling and active stresses drives a rich pattern of mesoscale lo domains – static, strongly fluctuating and moving active emulsions – even at temperatures beyond the equilibrium phase transition temperature. We study conditions under which domain registry and slippage could be observed. We end with a discussion on the role of active flippases on PS in maintaining the active mesoscale organisation.</p>","PeriodicalId":49075,"journal":{"name":"Faraday Discussions","volume":"259 ","pages":" 60-82"},"PeriodicalIF":3.1,"publicationDate":"2025-05-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143956230","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}