@unpublished{8125, abstract = {Context, such as behavioral state, is known to modulate memory formation and retrieval, but is usually ignored in associative memory models. Here, we propose several types of contextual modulation for associative memory networks that greatly increase their performance. In these networks, context inactivates specific neurons and connections, which modulates the effective connectivity of the network. Memories are stored only by the active components, thereby reducing interference from memories acquired in other contexts. Such networks exhibit several beneficial characteristics, including enhanced memory capacity, high robustness to noise, increased robustness to memory overloading, and better memory retention during continual learning. Furthermore, memories can be biased to have different relative strengths, or even gated on or off, according to contextual cues, providing a candidate model for cognitive control of memory and efficient memory search. An external context-encoding network can dynamically switch the memory network to a desired state, which we liken to experimentally observed contextual signals in prefrontal cortex and hippocampus. Overall, our work illustrates the benefits of organizing memory around context, and provides an important link between behavioral studies of memory and mechanistic details of neural circuits.SIGNIFICANCEMemory is context dependent — both encoding and recall vary in effectiveness and speed depending on factors like location and brain state during a task. We apply this idea to a simple computational model of associative memory through contextual gating of neurons and synaptic connections. Intriguingly, this results in several advantages, including vastly enhanced memory capacity, better robustness, and flexible memory gating. Our model helps to explain (i) how gating and inhibition contribute to memory processes, (ii) how memory access dynamically changes over time, and (iii) how context representations, such as those observed in hippocampus and prefrontal cortex, may interact with and control memory processes.}, author = {Podlaski, William F. and Agnes, Everton J. and Vogels, Tim P}, booktitle = {bioRxiv}, publisher = {Cold Spring Harbor Laboratory}, title = {{High capacity and dynamic accessibility in associative memory networks with context-dependent neuronal and synaptic gating}}, doi = {10.1101/2020.01.08.898528}, year = {2022}, } @article{7577, abstract = {Weak convergence of inertial iterative method for solving variational inequalities is the focus of this paper. The cost function is assumed to be non-Lipschitz and monotone. We propose a projection-type method with inertial terms and give weak convergence analysis under appropriate conditions. Some test results are performed and compared with relevant methods in the literature to show the efficiency and advantages given by our proposed methods.}, author = {Shehu, Yekini and Iyiola, Olaniyi S.}, issn = {1563-504X}, journal = {Applicable Analysis}, number = {1}, pages = {192--216}, publisher = {Taylor & Francis}, title = {{Weak convergence for variational inequalities with inertial-type method}}, doi = {10.1080/00036811.2020.1736287}, volume = {101}, year = {2022}, } @article{14355, abstract = {Purpose: The mediator (MED) multisubunit-complex modulates the activity of the transcriptional machinery, and genetic defects in different MED subunits (17, 20, 27) have been implicated in neurologic diseases. In this study, we identified a recurrent homozygous variant in MED11 (c.325C>T; p.Arg109Ter) in 7 affected individuals from 5 unrelated families. Methods: To investigate the genetic cause of the disease, exome or genome sequencing were performed in 5 unrelated families identified via different research networks and Matchmaker Exchange. Deep clinical and brain imaging evaluations were performed by clinical pediatric neurologists and neuroradiologists. The functional effect of the candidate variant on both MED11 RNA and protein was assessed using reverse transcriptase polymerase chain reaction and western blotting using fibroblast cell lines derived from 1 affected individual and controls and through computational approaches. Knockouts in zebrafish were generated using clustered regularly interspaced short palindromic repeats/Cas9. Results: The disease was characterized by microcephaly, profound neurodevelopmental impairment, exaggerated startle response, myoclonic seizures, progressive widespread neurodegeneration, and premature death. Functional studies on patient-derived fibroblasts did not show a loss of protein function but rather disruption of the C-terminal of MED11, likely impairing binding to other MED subunits. A zebrafish knockout model recapitulates key clinical phenotypes. Conclusion: Loss of the C-terminal of MED subunit 11 may affect its binding efficiency to other MED subunits, thus implicating the MED-complex stability in brain development and neurodegeneration. (C) 2022 The Authors. Published by Elsevier Inc. on behalf of American College of Medical Genetics and Genomics.}, author = {Cali, Elisa and Lin, Sheng-Jia and Rocca, Clarissa and Sahin, Yavuz and Al Shamsi, Aisha and El Chehadeh, Salima and Chaabouni, Myriam and Mankad, Kshitij and Galanaki, Evangelia and Efthymiou, Stephanie and Sudhakar, Sniya and Athanasiou-Fragkouli, Alkyoni and Celik, Tamer and Narli, Nejat and Bianca, Sebastiano and Murphy, David and Moreira, Francisco Martins De Carvalho and Accogli, Andrea and Petree, Cassidy and Huang, Kevin and Monastiri, Kamel and Edizadeh, Masoud and Nardello, Rosaria and Ognibene, Marzia and De Marco, Patrizia and Ruggieri, Martino and Zara, Federico and Striano, Pasquale and Sahin, Yavuz and Al-Gazali, Lihadh and Warde, Marie Therese Abi and Gerard, Benedicte and Zifarelli, Giovanni and Beetz, Christian and Fortuna, Sara and Soler, Miguel and Valente, Enza Maria and Varshney, Gaurav and Maroofian, Reza and Salpietro, Vincenzo and Houlden, Henry and Grp, SYNaPS Study}, issn = {1098-3600}, journal = {Genetics in Medicine}, keywords = {Human mediator complex, MED11, MEDopathies}, number = {10}, pages = {2194--2203}, publisher = {Elsevier}, title = {{A homozygous MED11 C-terminal variant causes a lethal neurodegenerative disease}}, doi = {10.1016/j.gim.2022.07.013}, volume = {24}, year = {2022}, } @article{14356, abstract = {Aminoacyl-tRNA synthetases (ARSs) are essential enzymes for faithful assignment of amino acids to their cognate tRNA. Variants in ARS genes are frequently associated with clinically heterogeneous phenotypes in humans and follow both autosomal dominant or recessive inheritance patterns in many instances. Variants in tryptophanyl-tRNA synthetase 1 (WARS1) cause autosomal dominantly inherited distal hereditary motor neuropathy and Charcot-Marie-Tooth disease. Presently, only one family with biallelic WARS1 variants has been described. We present three affected individuals from two families with biallelic variants (p.Met1? and p.(Asp419Asn)) in WARS1, showing varying severities of developmental delay and intellectual disability. Hearing impairment and microcephaly, as well as abnormalities of the brain, skeletal system, movement/gait, and behavior were variable features. Phenotyping of knocked down wars-1 in a Caenorhabditis elegans model showed depletion is associated with defects in germ cell development. A wars1 knockout vertebrate model recapitulates the human clinical phenotypes, confirms variant pathogenicity, and uncovers evidence implicating the p.Met1? variant as potentially impacting an exon critical for normal hearing. Together, our findings provide consolidating evidence for biallelic disruption of WARS1 as causal for an autosomal recessive neurodevelopmental syndrome and present a vertebrate model that recapitulates key phenotypes observed in patients.}, author = {Lin, Sheng-Jia and Vona, Barbara and Porter, Hillary M. and Izadi, Mahmoud and Huang, Kevin and Lacassie, Yves and Rosenfeld, Jill A. and Khan, Saadullah and Petree, Cassidy and Ali, Tayyiba A. and Muhammad, Nazif and Khan, Sher A. and Muhammad, Noor and Liu, Pengfei and Haymon, Marie-Louise and Rueschendorf, Franz and Kong, Il-Keun and Schnapp, Linda and Shur, Natasha and Chorich, Lynn and Layman, Lawrence and Haaf, Thomas and Pourkarimi, Ehsan and Kim, Hyung-Goo and Varshney, Gaurav K.}, issn = {1059-7794}, journal = {Human Mutation}, keywords = {autosomal recessive, biallelic variants, C, elegans, translation initiation sites, tryptophanyl-tRNA synthetase 1 (WARS1), WHEP domain, zebrafish}, number = {10}, pages = {1472--1489}, publisher = {Wiley}, title = {{Biallelic variants in WARS1 cause a highly variable neurodevelopmental syndrome and implicate a critical exon for normal auditory function}}, doi = {10.1002/humu.24435}, volume = {43}, year = {2022}, } @article{14357, abstract = {Aminoacylation of transfer RNA (tRNA) is a key step in protein biosynthesis, carried out by highly specific aminoacyl-tRNA synthetases (ARSs). ARSs have been implicated in autosomal dominant and autosomal recessive human disorders. Autosomal dominant variants in tryptophanyl-tRNA synthetase 1 (WARS1) are known to cause distal hereditary motor neuropathy and Charcot-Marie-Tooth disease, but a recessively inherited phenotype is yet to be clearly defined. Seryl-tRNA synthetase 1 (SARS1) has rarely been implicated in an autosomal recessive developmental disorder. Here, we report five individuals with biallelic missense variants in WARS1 or SARS1, who presented with an overlapping phenotype of microcephaly, developmental delay, intellectual disability, and brain anomalies. Structural mapping showed that the SARS1 variant is located directly within the enzyme’s active site, most likely diminishing activity, while the WARS1 variant is located in the N-terminal domain. We further characterize the identified WARS1 variant by showing that it negatively impacts protein abundance and is unable to rescue the phenotype of a CRISPR/Cas9 wars1 knockout zebrafish model. In summary, we describe two overlapping autosomal recessive syndromes caused by variants in WARS1 and SARS1, present functional insights into the pathogenesis of the WARS1-related syndrome and define an emerging disease spectrum: ARS-related developmental disorders with or without microcephaly.}, author = {Boegershausen, Nina and Krawczyk, Hannah E. and Jamra, Rami A. and Lin, Sheng-Jia and Yigit, Goekhan and Huening, Irina and Polo, Anna M. and Vona, Barbara and Huang, Kevin and Schmidt, Julia and Altmueller, Janine and Luppe, Johannes and Platzer, Konrad and Doergeloh, Beate B. and Busche, Andreas and Biskup, Saskia and Mendes, I, Marisa and Smith, Desiree E. C. and Salomons, Gajja S. and Zibat, Arne and Bueltmann, Eva and Nuernberg, Peter and Spielmann, Malte and Lemke, Johannes R. and Li, Yun and Zenker, Martin and Varshney, Gaurav K. and Hillen, Hauke S. and Kratz, Christian P. and Wollnik, Bernd}, issn = {1059-7794}, journal = {Human Mutation}, keywords = {aminoacylation, aminoacyl-tRNA synthetase, ARS, CRISPR, Cas9, intellectual disability, microcephaly, SARS1, tRNA, WARS1, zebrafish}, number = {10}, pages = {1454--1471}, publisher = {Wiley}, title = {{WARS1 and SARS1: Two tRNA synthetases implicated in autosomal recessive microcephaly}}, doi = {10.1002/humu.24430}, volume = {43}, year = {2022}, } @misc{14520, abstract = {This dataset comprises all data shown in the figures of the submitted article "Compact vacuum gap transmon qubits: Selective and sensitive probes for superconductor surface losses" at arxiv.org/abs/2206.14104. Additional raw data are available from the corresponding author on reasonable request.}, author = {Zemlicka, Martin and Redchenko, Elena and Peruzzo, Matilda and Hassani, Farid and Trioni, Andrea and Barzanjeh, Shabir and Fink, Johannes M}, publisher = {Zenodo}, title = {{Compact vacuum gap transmon qubits: Selective and sensitive probes for superconductor surface losses}}, doi = {10.5281/ZENODO.8408897}, year = {2022}, } @unpublished{14597, abstract = {Phase-field models such as the Allen-Cahn equation may give rise to the formation and evolution of geometric shapes, a phenomenon that may be analyzed rigorously in suitable scaling regimes. In its sharp-interface limit, the vectorial Allen-Cahn equation with a potential with N≥3 distinct minima has been conjectured to describe the evolution of branched interfaces by multiphase mean curvature flow. In the present work, we give a rigorous proof for this statement in two and three ambient dimensions and for a suitable class of potentials: As long as a strong solution to multiphase mean curvature flow exists, solutions to the vectorial Allen-Cahn equation with well-prepared initial data converge towards multiphase mean curvature flow in the limit of vanishing interface width parameter ε↘0. We even establish the rate of convergence O(ε1/2). Our approach is based on the gradient flow structure of the Allen-Cahn equation and its limiting motion: Building on the recent concept of "gradient flow calibrations" for multiphase mean curvature flow, we introduce a notion of relative entropy for the vectorial Allen-Cahn equation with multi-well potential. This enables us to overcome the limitations of other approaches, e.g. avoiding the need for a stability analysis of the Allen-Cahn operator or additional convergence hypotheses for the energy at positive times.}, author = {Fischer, Julian L and Marveggio, Alice}, booktitle = {arXiv}, title = {{Quantitative convergence of the vectorial Allen-Cahn equation towards multiphase mean curvature flow}}, doi = {10.48550/ARXIV.2203.17143}, year = {2022}, } @unpublished{14600, abstract = {We study the problem of learning controllers for discrete-time non-linear stochastic dynamical systems with formal reach-avoid guarantees. This work presents the first method for providing formal reach-avoid guarantees, which combine and generalize stability and safety guarantees, with a tolerable probability threshold $p\in[0,1]$ over the infinite time horizon. Our method leverages advances in machine learning literature and it represents formal certificates as neural networks. In particular, we learn a certificate in the form of a reach-avoid supermartingale (RASM), a novel notion that we introduce in this work. Our RASMs provide reachability and avoidance guarantees by imposing constraints on what can be viewed as a stochastic extension of level sets of Lyapunov functions for deterministic systems. Our approach solves several important problems -- it can be used to learn a control policy from scratch, to verify a reach-avoid specification for a fixed control policy, or to fine-tune a pre-trained policy if it does not satisfy the reach-avoid specification. We validate our approach on $3$ stochastic non-linear reinforcement learning tasks.}, author = {Zikelic, Dorde and Lechner, Mathias and Henzinger, Thomas A and Chatterjee, Krishnendu}, booktitle = {arXiv}, title = {{Learning control policies for stochastic systems with reach-avoid guarantees}}, doi = {10.48550/ARXIV.2210.05308}, year = {2022}, } @unpublished{14601, abstract = {In this work, we address the problem of learning provably stable neural network policies for stochastic control systems. While recent work has demonstrated the feasibility of certifying given policies using martingale theory, the problem of how to learn such policies is little explored. Here, we study the effectiveness of jointly learning a policy together with a martingale certificate that proves its stability using a single learning algorithm. We observe that the joint optimization problem becomes easily stuck in local minima when starting from a randomly initialized policy. Our results suggest that some form of pre-training of the policy is required for the joint optimization to repair and verify the policy successfully.}, author = {Zikelic, Dorde and Lechner, Mathias and Chatterjee, Krishnendu and Henzinger, Thomas A}, booktitle = {arXiv}, title = {{Learning stabilizing policies in stochastic control systems}}, doi = {10.48550/arXiv.2205.11991}, year = {2022}, } @misc{13064, abstract = {Genetically informed, deep-phenotyped biobanks are an important research resource and it is imperative that the most powerful, versatile, and efficient analysis approaches are used. Here, we apply our recently developed Bayesian grouped mixture of regressions model (GMRM) in the UK and Estonian Biobanks and obtain the highest genomic prediction accuracy reported to date across 21 heritable traits. When compared to other approaches, GMRM accuracy was greater than annotation prediction models run in the LDAK or LDPred-funct software by 15% (SE 7%) and 14% (SE 2%), respectively, and was 18% (SE 3%) greater than a baseline BayesR model without single-nucleotide polymorphism (SNP) markers grouped into minor allele frequency–linkage disequilibrium (MAF-LD) annotation categories. For height, the prediction accuracy R 2 was 47% in a UK Biobank holdout sample, which was 76% of the estimated h SNP 2 . We then extend our GMRM prediction model to provide mixed-linear model association (MLMA) SNP marker estimates for genome-wide association (GWAS) discovery, which increased the independent loci detected to 16,162 in unrelated UK Biobank individuals, compared to 10,550 from BoltLMM and 10,095 from Regenie, a 62 and 65% increase, respectively. The average χ2 value of the leading markers increased by 15.24 (SE 0.41) for every 1% increase in prediction accuracy gained over a baseline BayesR model across the traits. Thus, we show that modeling genetic associations accounting for MAF and LD differences among SNP markers, and incorporating prior knowledge of genomic function, is important for both genomic prediction and discovery in large-scale individual-level studies.}, author = {Orliac, Etienne and Trejo Banos, Daniel and Ojavee, Sven and Läll, Kristi and Mägi, Reedik and Visscher, Peter and Robinson, Matthew Richard}, publisher = {Dryad}, title = {{Improving genome-wide association discovery and genomic prediction accuracy in biobank data}}, doi = {10.5061/DRYAD.GTHT76HMZ}, year = {2022}, } @misc{13066, abstract = {Chromosomal inversions have been shown to play a major role in local adaptation by suppressing recombination between alternative arrangements and maintaining beneficial allele combinations. However, so far, their importance relative to the remaining genome remains largely unknown. Understanding the genetic architecture of adaptation requires better estimates of how loci of different effect sizes contribute to phenotypic variation. Here, we used three Swedish islands where the marine snail Littorina saxatilis has repeatedly evolved into two distinct ecotypes along a habitat transition. We estimated the contribution of inversion polymorphisms to phenotypic divergence while controlling for polygenic effects in the remaining genome using a quantitative genetics framework. We confirmed the importance of inversions but showed that contributions of loci outside inversions are of similar magnitude, with variable proportions dependent on the trait and the population. Some inversions showed consistent effects across all sites, whereas others exhibited site-specific effects, indicating that the genomic basis for replicated phenotypic divergence is only partly shared. The contributions of sexual dimorphism as well as environmental factors to phenotypic variation were significant but minor compared to inversions and polygenic background. Overall, this integrated approach provides insight into the multiple mechanisms contributing to parallel phenotypic divergence.}, author = {Koch, Eva and Ravinet, Mark and Westram, Anja M and Jonannesson, Kerstin and Butlin, Roger}, publisher = {Dryad}, title = {{Data from: Genetic architecture of repeated phenotypic divergence in Littorina saxatilis ecotype evolution}}, doi = {10.5061/DRYAD.M905QFV4B}, year = {2022}, } @misc{13076, abstract = {The source code for replicating experiments presented in the paper. The implementation of the designed priority schedulers can be found in Galois-2.2.1/include/Galois/WorkList/: StealingMultiQueue.h is the StealingMultiQueue. MQOptimized/ contains MQ Optimized variants. We provide images that contain all the dependencies and datasets. Images can be pulled from npostnikova/mq-based-schedulers repository, or downloaded from Zenodo. See readme for more detail.}, author = {Postnikova, Anastasiia and Koval, Nikita and Nadiradze, Giorgi and Alistarh, Dan-Adrian}, publisher = {Zenodo}, title = {{Multi-queues can be state-of-the-art priority schedulers}}, doi = {10.5281/ZENODO.5733408}, year = {2022}, } @inproceedings{13239, abstract = {Brains are thought to engage in predictive learning - learning to predict upcoming stimuli - to construct an internal model of their environment. This is especially notable for spatial navigation, as first described by Tolman’s latent learning tasks. However, predictive learning has also been observed in sensory cortex, in settings unrelated to spatial navigation. Apart from normative frameworks such as active inference or efficient coding, what could be the utility of learning to predict the patterns of occurrence of correlated stimuli? Here we show that prediction, and thereby the construction of an internal model of sequential stimuli, can bootstrap the learning process of a working memory task in a recurrent neural network. We implemented predictive learning alongside working memory match-tasks, and networks emerged to solve the prediction task first by encoding information across time to predict upcoming stimuli, and then eavesdropped on this solution to solve the matching task. Eavesdropping was most beneficial when neural resources were limited. Hence, predictive learning acts as a general neural mechanism to learn to store sensory information that can later be essential for working memory tasks.}, author = {Van Der Plas, Thijs L. and Vogels, Tim P and Manohar, Sanjay G.}, booktitle = {Proceedings of Machine Learning Research}, issn = {2640-3498}, pages = {518--531}, publisher = {ML Research Press}, title = {{Predictive learning enables neural networks to learn complex working memory tasks}}, volume = {199}, year = {2022}, } @article{13240, abstract = {Ustilago maydis is a biotrophic phytopathogenic fungus that causes corn smut disease. As a well-established model system, U. maydis is genetically fully accessible with large omics datasets available and subject to various biological questions ranging from DNA-repair, RNA-transport, and protein secretion to disease biology. For many genetic approaches, tight control of transgene regulation is important. Here we established an optimised version of the Tetracycline-ON (TetON) system for U. maydis. We demonstrate the Tetracycline concentration-dependent expression of fluorescent protein transgenes and the system’s suitability for the induced expression of the toxic protein BCL2 Associated X-1 (Bax1). The Golden Gate compatible vector system contains a native minimal promoter from the mating factor a-1 encoding gene, mfa with ten copies of the tet-regulated operator (tetO) and a codon optimised Tet-repressor (tetR*) which is translationally fused to the native transcriptional corepressor Mql1 (UMAG_05501). The metabolism-independent transcriptional regulator system is functional both, in liquid culture as well as on solid media in the presence of the inducer and can become a useful tool for toxin-antitoxin studies, identification of antifungal proteins, and to study functions of toxic gene products in Ustilago maydis.}, author = {Ingole, Kishor D. and Nagarajan, Nithya and Uhse, Simon and Giannini, Caterina and Djamei, Armin}, issn = {2673-6128}, journal = {Frontiers in Fungal Biology}, publisher = {Frontiers Media}, title = {{Tetracycline-controlled (TetON) gene expression system for the smut fungus Ustilago maydis}}, doi = {10.3389/ffunb.2022.1029114}, volume = {3}, year = {2022}, } @inproceedings{13241, abstract = {Addressing fairness concerns about machine learning models is a crucial step towards their long-term adoption in real-world automated systems. Many approaches for training fair models from data have been developed and an implicit assumption about such algorithms is that they are able to recover a fair model, despite potential historical biases in the data. In this work we show a number of impossibility results that indicate that there is no learning algorithm that can recover a fair model when a proportion of the dataset is subject to arbitrary manipulations. Specifically, we prove that there are situations in which an adversary can force any learner to return a biased classifier, with or without degrading accuracy, and that the strength of this bias increases for learning problems with underrepresented protected groups in the data. Our results emphasize on the importance of studying further data corruption models of various strength and of establishing stricter data collection practices for fairness-aware learning.}, author = {Konstantinov, Nikola H and Lampert, Christoph}, booktitle = {Proceedings of Machine Learning Research}, issn = {2640-3498}, pages = {59--83}, publisher = {ML Research Press}, title = {{On the impossibility of fairness-aware learning from corrupted data}}, volume = {171}, year = {2022}, } @unpublished{13345, abstract = {The self-assembly of inorganic nanoparticles (NPs) into ordered structures (superlattices) has led to a wide range of nanomaterials with unique optical, magnetic, electronic, and catalytic properties. Various interactions have been employed to direct the crystallization of NPs, including van der Waals forces, hydrogen bonding, as well as electric and magnetic dipolar interactions. Among them, Coulombic interactions—ubiquitous in nature and the main driving force behind the formation of many minerals, such as fluorite or rock salt—have remained largely underexplored, owing to the rapid charge exchange between NPs bearing high densities of opposite charges (superionic NPs). Here, we worked with superionic NPs under conditions (room temperature, concentrated salt solutions) that preserved their native surface charge density. We demonstrate that under these conditions, the Coulombic interactions between superionic NPs are reminiscent of short-range intermolecular interactions. Our methodology was used to assemble oppositely charged NPs into high-quality superlattices exhibiting Catalan shapes. Depending on their size ratio, the NPs assembled into either rhombic dodecahedra or triakis tetrahedra with structures mimicking those of the ionic solids CsCl and Th3P4, respectively. We envision that the methodology described here can be applied to a wide range of charged NPs of various sizes, shapes, and compositions, thus facilitating the discovery of new nanomaterials.}, author = {Bian, Tong and Lobato, Ivan and Wang, Ji and Nitka, Tara A. and Peled, Tzuf Shay and Lee, Byeongdu and Van Aert, Sandra and Bals, Sara and Vuković, Lela and Altantzis, Thomas and Král, Petr and Klajn, Rafal}, booktitle = {ChemRxiv}, title = {{Catalan solids from superionic nanoparticles}}, doi = {10.26434/chemrxiv-2022-klncg}, year = {2022}, } @article{13347, abstract = {Confining molecules within well-defined nanosized spaces can profoundly alter their physicochemical characteristics. For example, the controlled aggregation of chromophores into discrete oligomers has been shown to tune their optical properties whereas encapsulation of reactive species within molecular hosts can increase their stability. The resazurin/resorufin pair has been widely used for detecting redox processes in biological settings; yet, how tight confinement affects the properties of these two dyes remains to be explored. Here, we show that a flexible PdII6L4 coordination cage can efficiently encapsulate both resorufin and resazurin in the form of dimers, dramatically modulating their optical properties. Furthermore, binding within the cage significantly decreases the reduction rate of resazurin to resorufin, and the rate of the subsequent reduction of resorufin to dihydroresorufin. During our studies, we also found that upon dilution, the PdII6L4 cage disassembles to afford PdII2L2 species, which lacks the ability to form inclusion complexes – a process that can be reversed upon the addition of the strongly binding resorufin/resazurin guests. We expect that the herein disclosed ability of a water-soluble cage to reversibly modulate the optical and chemical properties of a molecular redox probe will expand the versatility of synthetic fluorescent probes in biologically relevant environments.}, author = {Yanshyna, Oksana and Białek, Michał J. and Chashchikhin, Oleg V. and Klajn, Rafal}, issn = {2399-3669}, journal = {Communications Chemistry}, keywords = {Materials Chemistry, Biochemistry, Environmental Chemistry, General Chemistry}, publisher = {Springer Nature}, title = {{Encapsulation within a coordination cage modulates the reactivity of redox-active dyes}}, doi = {10.1038/s42004-022-00658-8}, volume = {5}, year = {2022}, } @article{13348, abstract = {Molecular confinement effects can profoundly alter the physicochemical properties of the confined species. A plethora of organic molecules were encapsulated within the cavities of supramolecular hosts, and the impact of the cavity size and polarity was widely investigated. However, the extent to which the properties of the confined guests can be affected by the symmetry of the cage─which dictates the shape of the cavity─remains to be understood. Here we show that cage symmetry has a dramatic effect on the equilibrium between two isomers of the encapsulated spiropyran guests. Working with two Pd-based coordination cages featuring similarly sized but differently shaped hydrophobic cavities, we found a highly selective stabilization of the isomer whose shape matches that of the cavity of the cage. A Td-symmetric cage stabilized the spiropyrans’ colorless form and rendered them photochemically inert. In contrast, a D2h-symmetric cage favored the colored isomer, while maintaining reversible photoswitching between the two states of the encapsulated spiropyrans. We also show that the switching kinetics strongly depend on the substitution pattern on the spiropyran scaffold. This finding was used to fabricate a time-sensitive information storage medium with tunable lifetimes of the encoded messages.}, author = {Wang, Jinhua and Avram, Liat and Diskin-Posner, Yael and Białek, Michał J. and Stawski, Wojciech and Feller, Moran and Klajn, Rafal}, issn = {1520-5126}, journal = {Journal of the American Chemical Society}, keywords = {Colloid and Surface Chemistry, Biochemistry, General Chemistry, Catalysis}, number = {46}, pages = {21244--21254}, publisher = {American Chemical Society}, title = {{Altering the properties of spiropyran switches using coordination cages with different symmetries}}, doi = {10.1021/jacs.2c08901}, volume = {144}, year = {2022}, } @article{13350, abstract = {Confinement within molecular cages can dramatically modify the physicochemical properties of the encapsulated guest molecules, but such host-guest complexes have mainly been studied in a static context. Combining confinement effects with fast guest exchange kinetics could pave the way toward stimuli-responsive supramolecular systems—and ultimately materials—whose desired properties could be tailored “on demand” rapidly and reversibly. Here, we demonstrate rapid guest exchange between inclusion complexes of an open-window coordination cage that can simultaneously accommodate two guest molecules. Working with two types of guests, anthracene derivatives and BODIPY dyes, we show that the former can substantially modify the optical properties of the latter upon noncovalent heterodimer formation. We also studied the light-induced covalent dimerization of encapsulated anthracenes and found large effects of confinement on reaction rates. By coupling the photodimerization with the rapid guest exchange, we developed a new way to modulate fluorescence using external irradiation.}, author = {Gemen, Julius and Białek, Michał J. and Kazes, Miri and Shimon, Linda J.W. and Feller, Moran and Semenov, Sergey N. and Diskin-Posner, Yael and Oron, Dan and Klajn, Rafal}, issn = {2451-9294}, journal = {Chem}, keywords = {Materials Chemistry, Biochemistry (medical), General Chemical Engineering, Environmental Chemistry, Biochemistry, General Chemistry}, number = {9}, pages = {2362--2379}, publisher = {Elsevier}, title = {{Ternary host-guest complexes with rapid exchange kinetics and photoswitchable fluorescence}}, doi = {10.1016/j.chempr.2022.05.008}, volume = {8}, year = {2022}, } @article{13351, abstract = {Molecular recognition is at the heart of the noncovalent synthesis of supramolecular assemblies and, at higher length scales, supramolecular materials. In a recent publication in Nature, Stoddart and co-workers demonstrate that the formation of host-guest complexes can be catalyzed by one of the simplest possible catalysts: the electron.}, author = {Gemen, Julius and Klajn, Rafal}, issn = {2451-9294}, journal = {Chem}, keywords = {Materials Chemistry, Biochemistry (medical), General Chemical Engineering, Environmental Chemistry, Biochemistry, General Chemistry}, number = {5}, pages = {1183--1186}, publisher = {Elsevier}, title = {{Electron catalysis expands the supramolecular chemist’s toolbox}}, doi = {10.1016/j.chempr.2022.04.022}, volume = {8}, year = {2022}, }