UV-light-driven prebiotic synthesis of iron–sulfur clusters

Iron–sulfur clusters are ancient cofactors that play a fundamental role in metabolism and may have impacted the prebiotic chemistry that led to life. However, it is unclear whether iron–sulfur clusters could have been synthesized on prebiotic Earth. Dissolved iron on early Earth was predominantly in the reduced ferrous state, but ferrous ions alone cannot form polynuclear iron–sulfur clusters. Similarly, free sulfide may not have been readily available. Here we show that UV light drives the synthesis of [2Fe–2S] and [4Fe–4S] clusters through the photooxidation of ferrous ions and the photolysis of organic thiols. Iron–sulfur clusters coordinate to and are stabilized by a wide range of cysteine-containing peptides and the assembly of iron–sulfur cluster-peptide complexes can take place within model protocells in a process that parallels extant pathways. Our experiments suggest that iron–sulfur clusters may have formed easily on early Earth, facilitating the emergence of an iron–sulfur-cluster-dependent metabolism

Streptavidin-binding peptides and uses thereof

The invention provides peptides with high affinity for streptavidin. These peptides may be expressed as part of fusion proteins to facilitate the detection, quantitation, and purification of proteins of interest

Real Time Global Tests of the ALICE High Level Trigger Data Transport Framework

The High Level Trigger (HLT) system of the ALICE experiment is an online event filter and trigger system designed for input bandwidths of up to 25 GB/s at event rates of up to 1 kHz. The system is designed as a scalable PC cluster, implementing several hundred nodes. The transport of data in the system is handled by an object-oriented data flow framework operating on the basis of the publisher-subscriber principle, being designed fully pipelined with lowest processing overhead and communication latency in the cluster. In this paper, we report the latest measurements where this framework has been operated on five different sites over a global north-south link extending more than 10,000 km, processing a ``real-time'' data flow.Comment: 8 pages 4 figure

Building zeolites from precrystallized units: nanoscale architecture

This is the peer reviewed version of the following article: Angew. Chem. Int. Ed. 2018, 57, 15330 15353, which has been published in final form at https://doi.org/10.1002/anie.201711422. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] Since the early reports by Barrer in the 1940s on converting natural minerals into synthetic zeolites, the use of precrystallized zeolites as crucial inorganic directing agents to synthesize other crystalline zeolites with improved physicochemical properties has become a very important research field, allowing the design, particularly in recent years, of new industrial catalysts. This Review highlights how the presence of some crystalline fragments in the synthesis media, such as small secondary building units (SBUs) or layered substructures, not only favors the crystallization of other zeolites with similar SBUs or layers, but also permits control over important parameters affecting their catalytic activity (chemical composition, crystal size, or porosity, etc.). Recent advances in the preparation of 3D and 2D zeolites through seeding and zeolite-to-zeolite transformation processes will be discussed extensively in this Review, including their preparation in the presence or absence of organic structure-directing agents (OSDAs). The aim is to introduce general guidelines for more efficient approaches for target zeolites.This work has been supported by the Spanish Government (MINECO through "Severo Ochoa" (SEV-2016-0683) and MAT2015-71261-R), by the European Union through ERC-AdG-2014-671093 (SynCatMatch), and by the Fundacion Ramon Areces (through the "Life and Materials Science" program).Li, C.; Moliner Marin, M.; Corma Canós, A. (2018). Building zeolites from precrystallized units: nanoscale architecture. Angewandte Chemie International Edition. 57(47):15330-15353. https://doi.org/10.1002/anie.201711422S15330153535747Cundy, C. S., & Cox, P. A. (2005). The hydrothermal synthesis of zeolites: Precursors, intermediates and reaction mechanism. Microporous and Mesoporous Materials, 82(1-2), 1-78. doi:10.1016/j.micromeso.2005.02.016Martínez, C., & Corma, A. (2011). Inorganic molecular sieves: Preparation, modification and industrial application in catalytic processes. 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Efficient synthesis of the Cu-SSZ-39 catalyst for DeNOx applications. Chemical Communications, 51(55), 11030-11033. doi:10.1039/c5cc03200hInagaki, S., Tsuboi, Y., Nishita, Y., Syahylah, T., Wakihara, T., & Kubota, Y. (2013). Rapid Synthesis of an Aluminum-Rich MSE-Type Zeolite by the Hydrothermal Conversion of an FAU-Type Zeolite. Chemistry - A European Journal, 19(24), 7780-7786. doi:10.1002/chem.201300125Zones, S. I., & Nakagawa, Y. (1995). Use of modified zeolites as reagents influencing nucleation in zeolite synthesis. Studies in Surface Science and Catalysis, 45-52. doi:10.1016/s0167-2991(06)81871-9Fan, W., Wu, P., Namba, S., & Tatsumi, T. (2004). A Titanosilicate That Is Structurally Analogous to an MWW-Type Lamellar Precursor. Angewandte Chemie International Edition, 43(2), 236-240. doi:10.1002/anie.200352723Fan, W., Wu, P., Namba, S., & Tatsumi, T. (2004). A Titanosilicate That Is Structurally Analogous to an MWW-Type Lamellar Precursor. Angewandte Chemie, 116(2), 238-242. doi:10.1002/ange.200352723De Baerdemaeker, T., Feyen, M., Vanbergen, T., Müller, U., Yilmaz, B., Xiao, F.-S., … Gies, H. (2014). From Layered Zeolite Precursors to Zeolites with a Three-Dimensional Porosity: Textural and Structural Modifications through Alkaline Treatment. Chemistry of Materials, 27(1), 316-326. doi:10.1021/cm504014dIyoki, K., Itabashi, K., & Okubo, T. (2014). Progress in seed-assisted synthesis of zeolites without using organic structure-directing agents. Microporous and Mesoporous Materials, 189, 22-30. doi:10.1016/j.micromeso.2013.08.008Honda, K., Itakura, M., Matsuura, Y., Onda, A., Ide, Y., Sadakane, M., & Sano, T. (2013). Role of Structural Similarity Between Starting Zeolite and Product Zeolite in the Interzeolite Conversion Process. Journal of Nanoscience and Nanotechnology, 13(4), 3020-3026. doi:10.1166/jnn.2013.7356Barrer, R. M. (1948). 33. Synthesis of a zeolitic mineral with chabazite-like sorptive properties. 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Factors affecting the formation of zeolites X and B. The Journal of Physical Chemistry, 72(4), 1385-1386. doi:10.1021/j100850a056Xie, B., Song, J., Ren, L., Ji, Y., Li, J., & Xiao, F.-S. (2008). Organotemplate-Free and Fast Route for Synthesizing Beta Zeolite. Chemistry of Materials, 20(14), 4533-4535. doi:10.1021/cm801167eMajano, G., Delmotte, L., Valtchev, V., & Mintova, S. (2009). Al-Rich Zeolite Beta by Seeding in the Absence of Organic Template. Chemistry of Materials, 21(18), 4184-4191. doi:10.1021/cm900462uKamimura, Y., Chaikittisilp, W., Itabashi, K., Shimojima, A., & Okubo, T. (2010). Critical Factors in the Seed-Assisted Synthesis of Zeolite Beta and «Green Beta» from OSDA-Free Na+-Aluminosilicate Gels. Chemistry - An Asian Journal, 5(10), 2182-2191. doi:10.1002/asia.201000234Xie, B., Zhang, H., Yang, C., Liu, S., Ren, L., Zhang, L., … Xiao, F.-S. (2011). Seed-directed synthesis of zeolites with enhanced performance in the absence of organic templates. 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Design of zeolite by inverse sigma transformation. Nature Materials, 11(12), 1059-1064. doi:10.1038/nmat3455Khodabandeh, S., & Davis, M. E. (1997). Zeolites P1 and L as precursors for the preparation of alkaline-earth zeolites. Microporous Materials, 12(4-6), 347-359. doi:10.1016/s0927-6513(97)00083-7Khodabandeh, S., & Davis, M. E. (1997). Alteration of perlite to calcium zeolites. Microporous Materials, 9(3-4), 161-172. doi:10.1016/s0927-6513(96)00100-9Van Tendeloo, L., Gobechiya, E., Breynaert, E., Martens, J. A., & Kirschhock, C. E. A. (2013). Alkaline cations directing the transformation of FAU zeolites into five different framework types. Chemical Communications, 49(100), 11737. doi:10.1039/c3cc47292bNedyalkova, R., Montreuil, C., Lambert, C., & Olsson, L. (2013). Interzeolite Conversion of FAU Type Zeolite into CHA and its Application in NH3-SCR. Topics in Catalysis, 56(9-10), 550-557. doi:10.1007/s11244-013-0015-4Ji, Y., Deimund, M. A., Bhawe, Y., & Davis, M. E. (2015). 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Seed-assisted, OSDA-free synthesis of MTW-type zeolite and «Green MTW» from sodium aluminosilicate gel systems. Microporous and Mesoporous Materials, 147(1), 149-156. doi:10.1016/j.micromeso.2011.05.038Kamimura, Y., Itabashi, K., Kon, Y., Endo, A., & Okubo, T. (2017). Seed-Assisted Synthesis of MWW-Type Zeolite with Organic Structure-Directing Agent-Free Na-Aluminosilicate Gel System. Chemistry -

Electrostatically gated membrane permeability in inorganic protocells

Although several strategies are now available to produce functional microcompartments analogous to primitive cell-like structures, little progress has been made in generating protocell constructs with self-controlled membrane permeability. Here we describe the preparation of water-dispersible colloidosomes based on silica nanoparticles and delineated by a continuous semipermeable inorganic membrane capable of self-activated, electrostatically gated permeability. We use crosslinking and covalent grafting of a pH-responsive copolymer to generate an ultrathin elastic membrane that exhibits selective release and uptake of small molecules. This behaviour, which depends on the charge of the copolymer coronal layer, serves to trigger enzymatic dephosphorylation reactions specifically within the protocell aqueous interior. This system represents a step towards the design and construction of alternative types of artificial chemical cells and protocell models based on spontaneous processes of inorganic self-organization

Toward homochiral protocells in noncatalytic peptide systems

The activation-polymerization-epimerization-depolymerization (APED) model of Plasson et al. has recently been proposed as a mechanism for the evolution of homochirality on prebiotic Earth. The dynamics of the APED model in two-dimensional spatially-extended systems is investigated for various realistic reaction parameters. It is found that the APED system allows for the formation of isolated homochiral proto-domains surrounded by a racemate. A diffusive slowdown of the APED network such as induced through tidal motion or evaporating pools and lagoons leads to the stabilization of homochiral bounded structures as expected in the first self-assembled protocells.Comment: 10 pages, 5 figure

On RAF Sets and Autocatalytic Cycles in Random Reaction Networks

The emergence of autocatalytic sets of molecules seems to have played an important role in the origin of life context. Although the possibility to reproduce this emergence in laboratory has received considerable attention, this is still far from being achieved. In order to unravel some key properties enabling the emergence of structures potentially able to sustain their own existence and growth, in this work we investigate the probability to observe them in ensembles of random catalytic reaction networks characterized by different structural properties. From the point of view of network topology, an autocatalytic set have been defined either in term of strongly connected components (SCCs) or as reflexively autocatalytic and food-generated sets (RAFs). We observe that the average level of catalysis differently affects the probability to observe a SCC or a RAF, highlighting the existence of a region where the former can be observed, whereas the latter cannot. This parameter also affects the composition of the RAF, which can be further characterized into linear structures, autocatalysis or SCCs. Interestingly, we show that the different network topology (uniform as opposed to power-law catalysis systems) does not have a significantly divergent impact on SCCs and RAFs appearance, whereas the proportion between cleavages and condensations seems instead to play a role. A major factor that limits the probability of RAF appearance and that may explain some of the difficulties encountered in laboratory seems to be the presence of molecules which can accumulate without being substrate or catalyst of any reaction.Comment: pp 113-12

Preparation of Large Monodisperse Vesicles

Preparation of monodisperse vesicles is important both for research purposes and for practical applications. While the extrusion of vesicles through small pores (∼100 nm in diameter) results in relatively uniform populations of vesicles, extrusion to larger sizes results in very heterogeneous populations of vesicles. Here we report a simple method for preparing large monodisperse multilamellar vesicles through a combination of extrusion and large-pore dialysis. For example, extrusion of polydisperse vesicles through 5-µm-diameter pores eliminates vesicles larger than 5 µm in diameter. Dialysis of extruded vesicles against 3-µm-pore-size polycarbonate membranes eliminates vesicles smaller than 3 µm in diameter, leaving behind a population of monodisperse vesicles with a mean diameter of ∼4 µm. The simplicity of this method makes it an effective tool for laboratory vesicle preparation with potential applications in preparing large monodisperse liposomes for drug delivery