@article{14831, abstract = {Catalysis, the acceleration of product formation by a substance that is left unchanged, typically results from multiple elementary processes, including diffusion of the reactants toward the catalyst, chemical steps, and release of the products. While efforts to design catalysts are often focused on accelerating the chemical reaction on the catalyst, catalysis is a global property of the catalytic cycle that involves all processes. These are controlled by both intrinsic parameters such as the composition and shape of the catalyst and extrinsic parameters such as the concentration of the chemical species at play. We examine here the conditions that catalysis imposes on the different steps of a reaction cycle and the respective role of intrinsic and extrinsic parameters of the system on the emergence of catalysis by using an approach based on first-passage times. We illustrate this approach for various decompositions of a catalytic cycle into elementary steps, including non-Markovian decompositions, which are useful when the presence and nature of intermediate states are a priori unknown. Our examples cover different types of reactions and clarify the constraints on elementary steps and the impact of species concentrations on catalysis.}, author = {Sakref, Yann and Muñoz Basagoiti, Maitane and Zeravcic, Zorana and Rivoire, Olivier}, issn = {1520-5207}, journal = {The Journal of Physical Chemistry B}, keywords = {Materials Chemistry, Surfaces, Coatings and Films, Physical and Theoretical Chemistry}, number = {51}, pages = {10950--10959}, publisher = {American Chemical Society}, title = {{On kinetic constraints that catalysis imposes on elementary processes}}, doi = {10.1021/acs.jpcb.3c04627}, volume = {127}, year = {2023}, } @article{14833, abstract = {Understanding the factors that have shaped the current distributions and diversity of species is a central and longstanding aim of evolutionary biology. The recent inclusion of genomic data into phylogeographic studies has dramatically improved our understanding in organisms where evolutionary relationships have been challenging to infer. We used whole-genome sequences to study the phylogeography of the intertidal snail Littorina saxatilis, which has successfully colonized and diversified across a broad range of coastal environments in the Northern Hemisphere amid repeated cycles of glaciation. Building on past studies based on short DNA sequences, we used genome-wide data to provide a clearer picture of the relationships among samples spanning most of the species natural range. Our results confirm the trans-Atlantic colonization of North America from Europe, and have allowed us to identify rough locations of glacial refugia and to infer likely routes of colonization within Europe. We also investigated the signals in different datasets to account for the effects of genomic architecture and non-neutral evolution, which provides new insights about diversification of four ecotypes of L. saxatilis (the crab, wave, barnacle, and brackish ecotypes) at different spatial scales. Overall, we provide a much clearer picture of the biogeography of L. saxatilis, providing a foundation for more detailed phylogenomic and demographic studies.}, author = {Stankowski, Sean and Zagrodzka, Zuzanna B and Galindo, Juan and Montaño-Rendón, Mauricio and Faria, Rui and Mikhailova, Natalia and Blakeslee, April M H and Arnason, Einar and Broquet, Thomas and Morales, Hernán E and Grahame, John W and Westram, Anja M and Johannesson, Kerstin and Butlin, Roger K}, issn = {2752-938X}, journal = {Evolutionary Journal of the Linnean Society}, number = {1}, publisher = {Oxford University Press}, title = {{Whole-genome phylogeography of the intertidal snail Littorina saxatilis}}, doi = {10.1093/evolinnean/kzad002}, volume = {2}, year = {2023}, } @article{14835, abstract = {Aromatische Seitenketten sind wichtige Indikatoren für die Plastizität von Proteinen und bilden oft entscheidende Kontakte bei Protein‐Protein‐Wechselwirkungen. Wir untersuchten aromatische Reste in den beiden strukturell homologen cross‐β Amyloidfibrillen HET‐s und HELLF mit Hilfe eines spezifischen Ansatzes zur Isotopenmarkierung und Festkörper NMR mit Drehung am magischen Winkel. Das dynamische Verhalten der aromatischen Reste Phe und Tyr deutet darauf hin, dass der hydrophobe Amyloidkern starr ist und keine Anzeichen von “atmenden Bewegungen” auf einer Zeitskala von Hunderten von Millisekunden zeigt. Aromatische Reste, die exponiert an der Fibrillenoberfläche sitzen, haben zwar eine starre Ringachse, weisen aber Ringflips auf verschiedenen Zeitskalen von Nanosekunden bis Mikrosekunden auf. Unser Ansatz bietet einen direkten Einblick in die Bewegungen des hydrophoben Kerns und ermöglicht eine bessere Bewertung der Konformationsheterogenität, die aus einem NMR‐Strukturensemble einer solchen Cross‐β‐Amyloidstruktur hervorgeht.}, author = {Becker, Lea Marie and Berbon, Mélanie and Vallet, Alicia and Grelard, Axelle and Morvan, Estelle and Bardiaux, Benjamin and Lichtenecker, Roman and Ernst, Matthias and Loquet, Antoine and Schanda, Paul}, issn = {1521-3757}, journal = {Angewandte Chemie}, keywords = {General Medicine}, number = {19}, publisher = {Wiley}, title = {{Der starre Kern und die flexible Oberfläche von Amyloidfibrillen – Magic‐Angle‐Spinning NMR Spektroskopie von aromatischen Resten}}, doi = {10.1002/ange.202219314}, volume = {135}, year = {2023}, } @article{14844, abstract = {Many cell functions require a concerted effort from multiple membrane proteins, for example, for signaling, cell division, and endocytosis. One contribution to their successful self-organization stems from the membrane deformations that these proteins induce. While the pairwise interaction potential of two membrane-deforming spheres has recently been measured, membrane-deformation-induced interactions have been predicted to be nonadditive, and hence their collective behavior cannot be deduced from this measurement. We here employ a colloidal model system consisting of adhesive spheres and giant unilamellar vesicles to test these predictions by measuring the interaction potential of the simplest case of three membrane-deforming, spherical particles. We quantify their interactions and arrangements and, for the first time, experimentally confirm and quantify the nonadditive nature of membrane-deformation-induced interactions. We furthermore conclude that there exist two favorable configurations on the membrane: (1) a linear and (2) a triangular arrangement of the three spheres. Using Monte Carlo simulations, we corroborate the experimentally observed energy minima and identify a lowering of the membrane deformation as the cause for the observed configurations. The high symmetry of the preferred arrangements for three particles suggests that arrangements of many membrane-deforming objects might follow simple rules.}, author = {Azadbakht, Ali and Meadowcroft, Billie and Majek, Juraj and Šarić, Anđela and Kraft, Daniela J.}, issn = {1542-0086}, journal = {Biophysical Journal}, publisher = {Elsevier}, title = {{Nonadditivity in interactions between three membrane-wrapped colloidal spheres}}, doi = {10.1016/j.bpj.2023.12.020}, year = {2023}, } @inbook{14847, abstract = {Understanding the mechanisms of chaperones at the atomic level generally requires producing chaperone–client complexes in vitro. This task comes with significant challenges, because one needs to find conditions in which the client protein is presented to the chaperone in a state that binds and at the same time avoid the pitfalls of protein aggregation that are often inherent to such states. The strategy differs significantly for different client proteins and chaperones, but there are common underlying principles. Here, we discuss these principles and deduce the strategies that can be successfully applied for different chaperone–client complexes. We review successful biochemical strategies applied to making the client protein “binding competent” and illustrate the different strategies with examples of recent biophysical and biochemical studies.}, author = {Sučec, I. and Schanda, Paul}, booktitle = {Biophysics of Molecular Chaperones}, editor = {Hiller, Sebastian and Liu, Maili and He, Lichun}, isbn = {9781839162824}, pages = {136--161}, publisher = {Royal Society of Chemistry}, title = {{Preparing Chaperone–Client Protein Complexes for Biophysical and Structural Studies}}, doi = {10.1039/bk9781839165986-00136}, volume = {29}, year = {2023}, } @article{14849, abstract = {We establish a precise three-term asymptotic expansion, with an optimal estimate of the error term, for the rightmost eigenvalue of an n×n random matrix with independent identically distributed complex entries as n tends to infinity. All terms in the expansion are universal.}, author = {Cipolloni, Giorgio and Erdös, László and Schröder, Dominik J and Xu, Yuanyuan}, issn = {0091-1798}, journal = {The Annals of Probability}, keywords = {Statistics, Probability and Uncertainty, Statistics and Probability}, number = {6}, pages = {2192--2242}, publisher = {Institute of Mathematical Statistics}, title = {{On the rightmost eigenvalue of non-Hermitian random matrices}}, doi = {10.1214/23-aop1643}, volume = {51}, year = {2023}, } @misc{14861, abstract = {Cover Page}, author = {Becker, Lea Marie and Berbon, Mélanie and Vallet, Alicia and Grelard, Axelle and Morvan, Estelle and Bardiaux, Benjamin and Lichtenecker, Roman and Ernst, Matthias and Loquet, Antoine and Schanda, Paul}, booktitle = {Angewandte Chemie International Edition}, issn = {1521-3773}, keywords = {General Chemistry, Catalysis}, number = {19}, publisher = {Wiley}, title = {{Cover Picture: The rigid core and flexible surface of amyloid fibrils probed by Magic‐Angle‐Spinning NMR spectroscopy of aromatic residues}}, doi = {10.1002/anie.202304138}, volume = {62}, year = {2023}, } @inproceedings{14862, author = {Rella, Simon and Kulikova, Y and Minnegalieva, Aygul and Kondrashov, Fyodor}, booktitle = {European Journal of Public Health}, issn = {1464-360X}, keywords = {Public Health, Environmental and Occupational Health}, number = {Supplement_2}, publisher = {Oxford University Press}, title = {{Complex vaccination strategies prevent the emergence of vaccine resistance}}, doi = {10.1093/eurpub/ckad160.597}, volume = {33}, year = {2023}, } @inproceedings{14863, author = {Polesello, Andrea and Muller, Caroline J and Pasquero, Claudia and Meroni, Agostino N.}, booktitle = {EGU General Assembly 2023}, location = {Vienna, Austria & Virtual}, publisher = {European Geosciences Union}, title = {{Intensification mechanisms of tropical cyclones}}, doi = {10.5194/egusphere-egu23-6157}, year = {2023}, } @inproceedings{14864, author = {Stöllner, Andrea and Lenton, Isaac C and Muller, Caroline J and Waitukaitis, Scott R}, booktitle = {EGU General Assembly 2023}, location = {Vienna, Austria & Virtual}, publisher = {European Geosciences Union}, title = {{Measuring spontaneous charging of single aerosol particles}}, doi = {10.5194/egusphere-egu23-6166}, year = {2023}, } @inproceedings{14865, author = {Hwong, Yi-Ling and Colin, Maxime and Aglas, Philipp and Muller, Caroline J and Sherwood, Steven}, booktitle = {EGU General Assembly 2023}, location = {Vienna, Austria & Virtual}, publisher = {European Geosciences Union}, title = {{Evaluating memory properties in convection schemes using idealised tests}}, doi = {10.5194/egusphere-egu23-4968}, year = {2023}, } @inproceedings{14866, author = {Abramian, Sophie and Muller, Caroline J and Risi, Camille}, booktitle = {EGU General Assembly 2023}, location = {Vienna, Austria & Virtual}, publisher = {European Geosciences Union}, title = {{Extreme precipitation in tropical squall lines}}, doi = {10.5194/egusphere-egu23-15870}, year = {2023}, } @inproceedings{14867, abstract = {Starting with the empty graph on $[n]$, at each round, a set of $K=K(n)$ edges is presented chosen uniformly at random from the ones that have not been presented yet. We are then asked to choose at most one of the presented edges and add it to the current graph. Our goal is to construct a Hamiltonian graph with $(1+o(1))n$ edges within as few rounds as possible. We show that in this process, one can build a Hamiltonian graph of size $(1+o(1))n$ in $(1+o(1))(1+(\log n)/2K) n$ rounds w.h.p. The case $K=1$ implies that w.h.p. one can build a Hamiltonian graph by choosing $(1+o(1))n$ edges in an online fashion as they appear along the first $(0.5+o(1))n\log n$ rounds of the random graph process. This answers a question of Frieze, Krivelevich and Michaeli. Observe that the number of rounds is asymptotically optimal as the first $0.5n\log n$ edges do not span a Hamilton cycle w.h.p. The case $K=\Theta(\log n)$ implies that the Hamiltonicity threshold of the corresponding Achlioptas process is at most $(1+o(1))(1+(\log n)/2K) n$. This matches the $(1-o(1))(1+(\log n)/2K) n$ lower bound due to Krivelevich, Lubetzky and Sudakov and resolves the problem of determining the Hamiltonicity threshold of the Achlioptas process with $K=\Theta(\log n)$. We also show that in the above process one can construct a graph $G$ that spans a matching of size $\lfloor V(G)/2) \rfloor$ and $(0.5+o(1))n$ edges within $(1+o(1))(0.5+(\log n)/2K) n$ rounds w.h.p. Our proof relies on a robust Hamiltonicity property of the strong $4$-core of the binomial random graph which we use as a black-box. This property allows it to absorb paths covering vertices outside the strong $4$-core into a cycle.}, author = {Anastos, Michael}, booktitle = {Proceedings of the 12th European Conference on Combinatorics, Graph Theory and Applications}, issn = {2788-3116}, location = {Prague, Czech Republic}, pages = {36--41}, publisher = {Masaryk University Press}, title = {{Constructing Hamilton cycles and perfect matchings efficiently}}, doi = {10.5817/cz.muni.eurocomb23-005}, year = {2023}, } @misc{14892, abstract = {Code and data necessary to reproduce the simulations and data analyses reported in our manuscript: Tomé, D.F., Zhang, Y., Aida, T., Mosto, O., Lu, Y., Chen, M., Sadeh, S., Roy, D. S., Clopath, C. Dynamic and selective engrams emerge with memory consolidation. 2023.}, author = {Feitosa Tomé, Douglas}, publisher = {Zenodo}, title = {{douglastome/dynamic-engrams: Dynamic and selective engrams emerge with memory consolidation}}, doi = {10.5281/ZENODO.10251087}, year = {2023}, } @misc{14919, abstract = {GLACIER METEOROLOGICAL DATA SWISS ALPS -2022 }, author = {Shaw, Thomas and Buri, Pascal and McCarthy, Michael and Miles, Evan and Pellicciotti, Francesca}, publisher = {Zenodo}, title = {{Air temperature and near-surface meteorology datasets on three Swiss glaciers - Extreme 2022 Summer}}, doi = {10.5281/ZENODO.8277285}, year = {2023}, } @article{14920, abstract = {We consider fixpoint algorithms for two-player games on graphs with $\omega$-regular winning conditions, where the environment is constrained by a strong transition fairness assumption. Strong transition fairness is a widely occurring special case of strong fairness, which requires that any execution is strongly fair with respect to a specified set of live edges: whenever the source vertex of a live edge is visited infinitely often along a play, the edge itself is traversed infinitely often along the play as well. We show that, surprisingly, strong transition fairness retains the algorithmic characteristics of the fixpoint algorithms for $\omega$-regular games -- the new algorithms have the same alternation depth as the classical algorithms but invoke a new type of predecessor operator. For Rabin games with $k$ pairs, the complexity of the new algorithm is $O(n^{k+2}k!)$ symbolic steps, which is independent of the number of live edges in the strong transition fairness assumption. Further, we show that GR(1) specifications with strong transition fairness assumptions can be solved with a 3-nested fixpoint algorithm, same as the usual algorithm. In contrast, strong fairness necessarily requires increasing the alternation depth depending on the number of fairness assumptions. We get symbolic algorithms for (generalized) Rabin, parity and GR(1) objectives under strong transition fairness assumptions as well as a direct symbolic algorithm for qualitative winning in stochastic $\omega$-regular games that runs in $O(n^{k+2}k!)$ symbolic steps, improving the state of the art. Finally, we have implemented a BDD-based synthesis engine based on our algorithm. We show on a set of synthetic and real benchmarks that our algorithm is scalable, parallelizable, and outperforms previous algorithms by orders of magnitude.}, author = {Banerjee, Tamajit and Majumdar, Rupak and Mallik, Kaushik and Schmuck, Anne-Kathrin and Soudjani, Sadegh}, issn = {2751-4838}, journal = {TheoretiCS}, publisher = {EPI Sciences}, title = {{Fast symbolic algorithms for mega-regular games under strong transition fairness}}, doi = {10.46298/theoretics.23.4}, volume = {2}, year = {2023}, } @inproceedings{14921, abstract = {Neural collapse (NC) refers to the surprising structure of the last layer of deep neural networks in the terminal phase of gradient descent training. Recently, an increasing amount of experimental evidence has pointed to the propagation of NC to earlier layers of neural networks. However, while the NC in the last layer is well studied theoretically, much less is known about its multi-layered counterpart - deep neural collapse (DNC). In particular, existing work focuses either on linear layers or only on the last two layers at the price of an extra assumption. Our paper fills this gap by generalizing the established analytical framework for NC - the unconstrained features model - to multiple non-linear layers. Our key technical contribution is to show that, in a deep unconstrained features model, the unique global optimum for binary classification exhibits all the properties typical of DNC. This explains the existing experimental evidence of DNC. We also empirically show that (i) by optimizing deep unconstrained features models via gradient descent, the resulting solution agrees well with our theory, and (ii) trained networks recover the unconstrained features suitable for the occurrence of DNC, thus supporting the validity of this modeling principle.}, author = {Súkeník, Peter and Mondelli, Marco and Lampert, Christoph}, booktitle = {37th Annual Conference on Neural Information Processing Systems}, location = {New Orleans, LA, United States}, title = {{Deep neural collapse is provably optimal for the deep unconstrained features model}}, year = {2023}, } @inproceedings{14922, abstract = {We propose a novel approach to concentration for non-independent random variables. The main idea is to ``pretend'' that the random variables are independent and pay a multiplicative price measuring how far they are from actually being independent. This price is encapsulated in the Hellinger integral between the joint and the product of the marginals, which is then upper bounded leveraging tensorisation properties. Our bounds represent a natural generalisation of concentration inequalities in the presence of dependence: we recover exactly the classical bounds (McDiarmid's inequality) when the random variables are independent. Furthermore, in a ``large deviations'' regime, we obtain the same decay in the probability as for the independent case, even when the random variables display non-trivial dependencies. To show this, we consider a number of applications of interest. First, we provide a bound for Markov chains with finite state space. Then, we consider the Simple Symmetric Random Walk, which is a non-contracting Markov chain, and a non-Markovian setting in which the stochastic process depends on its entire past. To conclude, we propose an application to Markov Chain Monte Carlo methods, where our approach leads to an improved lower bound on the minimum burn-in period required to reach a certain accuracy. In all of these settings, we provide a regime of parameters in which our bound fares better than what the state of the art can provide.}, author = {Esposito, Amedeo Roberto and Mondelli, Marco}, booktitle = {Proceedings of 2023 IEEE International Symposium on Information Theory}, location = {Taipei, Taiwan}, publisher = {IEEE}, title = {{Concentration without independence via information measures}}, doi = {10.1109/isit54713.2023.10206899}, year = {2023}, } @inproceedings{14923, abstract = {We study the performance of a Bayesian statistician who estimates a rank-one signal corrupted by non-symmetric rotationally invariant noise with a generic distribution of singular values. As the signal-to-noise ratio and the noise structure are unknown, a Gaussian setup is incorrectly assumed. We derive the exact analytic expression for the error of the mismatched Bayes estimator and also provide the analysis of an approximate message passing (AMP) algorithm. The first result exploits the asymptotic behavior of spherical integrals for rectangular matrices and of low-rank matrix perturbations; the second one relies on the design and analysis of an auxiliary AMP. The numerical experiments show that there is a performance gap between the AMP and Bayes estimators, which is due to the incorrect estimation of the signal norm.}, author = {Fu, Teng and Liu, YuHao and Barbier, Jean and Mondelli, Marco and Liang, ShanSuo and Hou, TianQi}, booktitle = {Proceedings of 2023 IEEE International Symposium on Information Theory}, location = {Taipei, Taiwan}, publisher = {IEEE}, title = {{Mismatched estimation of non-symmetric rank-one matrices corrupted by structured noise}}, doi = {10.1109/isit54713.2023.10206671}, year = {2023}, } @inproceedings{14924, abstract = {The stochastic heavy ball method (SHB), also known as stochastic gradient descent (SGD) with Polyak's momentum, is widely used in training neural networks. However, despite the remarkable success of such algorithm in practice, its theoretical characterization remains limited. In this paper, we focus on neural networks with two and three layers and provide a rigorous understanding of the properties of the solutions found by SHB: \emph{(i)} stability after dropping out part of the neurons, \emph{(ii)} connectivity along a low-loss path, and \emph{(iii)} convergence to the global optimum. To achieve this goal, we take a mean-field view and relate the SHB dynamics to a certain partial differential equation in the limit of large network widths. This mean-field perspective has inspired a recent line of work focusing on SGD while, in contrast, our paper considers an algorithm with momentum. More specifically, after proving existence and uniqueness of the limit differential equations, we show convergence to the global optimum and give a quantitative bound between the mean-field limit and the SHB dynamics of a finite-width network. Armed with this last bound, we are able to establish the dropout-stability and connectivity of SHB solutions.}, author = {Wu, Diyuan and Kungurtsev, Vyacheslav and Mondelli, Marco}, booktitle = {Transactions on Machine Learning Research}, publisher = {ML Research Press}, title = {{Mean-field analysis for heavy ball methods: Dropout-stability, connectivity, and global convergence}}, year = {2023}, }