BUSCADOR RECOLECTA

28 pages. -- PDF file includes: Experimental Procedures; Simulation of hard polyhedral particles in spherical confinement. -- Figure S1. (a) Scheme and FESEM image of an as-synthesized C-ZIF-8 particle, highlighting the edge length (f). Scale bar: 500 nm. (b) Left: Representative FE-SEM image of C-ZIF-8 particles. Scale bar: 1 μm. Middle: Size-distribution histogram of as-synthesized C-ZIF-8 particles with a mean f of 191 ± 9 nm. Right: PXRD patterns of simulated (black) and as-synthesized C-ZIF-8 particles (red). -- Figure S2. (a) Scheme and FESEM image of an as-synthesized TRD-ZIF-8 particle, highlighting the particle size (f) and edge length (x). Scale bar: 500 nm. (b-e) TRD ZIF-8 particles (t= 0.68) with a mean f of 181 ± 9 nm (b), 198 ± 10 nm (c), 229 ± 9 nm (d) and 247 ± 10 nm (e). Left: Representative FE-SEM images; Middle: Size-distribution histograms; and Right: PXRD patterns of simulated (black) and assynthesized TRD-ZIF-8 particles (red). -- Figure S3. (a) Scheme and FESEM image of an as-synthesized RD-ZIF-8 particle, highlighting the particle size (f). Scale bar: 500 nm. (b-e) RD ZIF-8 particles with a mean f of 246 ± 12 nm (b), 267 ±12 nm (c), and 293 ± 13 nm (d). Left: Representative FE-SEM images; Middle: Size-distribution histograms; and Right: PXRD patterns of simulated (black) and as-synthesized RD-ZIF-8 particles (red). -- Figure S4. (a) Scheme and FESEM image of an as-synthesized O-UiO-66 particle, highlighting the edge length of particles (f). Scale bar: 500 nm. O-UiO-66 particles a mean f of 194 ± 12 nm (b), 238 ± 13 nm (c), and 247 ± 13 nm (d). Left: Representative FE-SEM images; Middle: Size-distribution histograms; and Right: PXRD patterns of simulated (black) and as-synthesized RD-ZIF-8 particles (red). -- Figure S5. Representative FESEM images of polydisperse C-ZIF-8 (a) and O-UiO-66 (b) supraparticles prepared by shaking emulsifying, with a size of 21 ± 5.6 μm (26% polydispersity) and 9.9 ± 3.4 μm (34% polydispersity, approximately 500 counts), respectively. -- Figure S6. Representative FESEM images of monodispersed RD-ZIF-8 (a) and TRD-ZIF-8 (b) supraparticles prepared using a droplet-based microfluidic device, with a size of 20.1 ± 0.6 μm (3% polydispersity) and 10.4 ± 0.5 μm (5% polydispersity, approximately 200 counts), respectively. -- Figure S7. Transmissive X-ray image of MOF supraparticles of a) RD-ZIF-8, showing few onion-like layers near the surface; b) TRD-ZIF-8, showing thick onion-like layers, as well as some lattice fringes; c) C-ZIF-8, showing thick onion-like layers, as well as some lattice fringes; and d) O-UiO-66 particles, showing only little onion-like layer structures. -- Figure S8. Cross-section of RD-ZIF-8 supraparticles revealed by focused-ion beam milling. -- Figure S9. Cross-section of TRD-ZIF-8 supraparticles revealed by focused-ion beam milling. -- Figure S10. Cross-section of C-ZIF-8 supraparticles revealed by focused-ion beam milling. -- Figure S11. Cross-section of O-UiO-66 supraparticles revealed by focused-ion beam milling. -- Figure S12. A TRD-ZIF-8 supraparticle exhibiting local five-fold symmetric surface pattern, marked with blue colour. -- Figure S13. Cross-sectional images of simulated supraparticles of hard polyhedra in spherical confinement. -- Figure S14. Photograph of the self-assembled superstructures resulting from the centrifugation of different aqueous colloidal MOF particles (from left to right: RD-ZIF-8, TRD-ZIF-8, C-ZIF-8 and OUiO-66). -- Figure S15. Relationship between MOF particle size of different shapes and layer distance. -- Figure S16. Optical setup to measure reflectance spectra directly from MOF supraparticles suspended in liquid in a glass vial. -- Figure S17. Angle-dependent reflection spectra of four types of MOF supraparticles measured directly from liquid suspension. -- Figure S18. Shift of the reflectance peak with increasing viewing angle for four types of MOF supraparticles. -- Figure S19. Buckled RD-ZIF-8 supraparticles. 1.0 mL 1 wt% Lutensol TO8 surfactant is added to 0.5 mL 2 wt% RD-ZIF-8 particle dispersion. -- Figure S20. Angle-dependent reflection spectra of buckled MOF supraparticles measured directly from suspension. -- Figure S21. Hypothesized surface grating effects of MOF supraparticles. -- Figure S22. Buckled RD-ZIF-8 supraparticles exhibit ordered surface features, visualized in scanning electron microscopy. -- Figure S23. The surface packing of RD ZIF-8 supraparticles shows a sawtooth groove profile, as seen in scanning electron microscopy., ICN2 is supported by the Severo Ochoa program from the Spanish MINECO (Grant No. SEV-2017-0706)., Peer reviewed

This PDF file includes: Sections S1 to S10 Figs. S1 to S9 Tables S1 to S3 References, Peer reviewed

Peer reviewed

1 table. -- Excel file includes multiple sheets. -- Original file: contains the originally extracted articles from the OA-ICC database. it contains 564 items with many duplications and articles not related to the Mediterranean. -- Edited file: Missing items from the OA-ICC database (without key) were added. The duplications, non-Mediterranean and non-existent items were removed. We have 534 items as a final outcome., Ocean acidification (OA) is a serious consequence of climate change with complex organism-to-ecosystem effects that have been observed through field observations but are mainly derived from experimental studies. Although OA trends and the resulting biological impacts are likely exacerbated in the semi-enclosed and highly populated Mediterranean Sea, some fundamental knowledge gaps still exist. These gaps are at tributed to both the uneven capacity for OA research that exists between Mediterranean countries, as well as to the subtle and long-term biological, physical and chemical interactions that define OA impacts. In this paper, we systematically analyzed the different aspects of OA research in the Mediterranean region based on two sources: the United Nation’s International Atomic Energy Agency’s (IAEA) Ocean Acidification International Coordination Center (OA-ICC) database, and an extensive survey. Our analysis shows that 1) there is an uneven geographic capacity in OA research, and illustrates that both the Algero-Provencal and Ionian sub-basins are currently the least studied Mediterranean areas, 2) the carbonate system is still poorly quantified in coastal zones, and long-term time-series are still sparse across the Mediterranean Sea, which is a challenge for studying its variability and assessing coastal OA trends, 3) the most studied groups of organisms are autotrophs (algae, phanerogams, phytoplankton), mollusks, and corals, while microbes, small mollusks (mainly pteropods), and sponges are among the least studied, 4) there is an overall paucity in socio-economic, paleontological, and modeling studies in the Mediterranean Sea, and 5) in spite of general resource availability and the agreement for improved and coordinated OA governance, there is a lack of consistent OA policies in the Mediterranean Sea. In addition to highlighting the current status, trends and gaps of OA research, this work also provides recommendations, based on both our literature assessment and a survey that targeted the Mediterranean OA scientific community. In light of the ongoing 2021-2030 United Nations Decade of Ocean Science for Sustainable Development, this work might provide a guideline to close gaps of knowledge in the Mediterranean OA research., Systematic Review Registration https://www.oceandecade.org/, Peer reviewed

Figure S1. Schematic representation of the systematic conformational search by changing the C-C-O-H dihedral angle by steps of 45º a similar procedure was used for the C-C-N-H dihedral angle. Figure S2. Complete bonding scheme from QTAIM topological analysis of p for 4,7-(NH2)2phen, intercalated between AT/TA base pairs via Minor Groove. For the considered interactions the corresponding BCPs, p (a.u.) and Ed (a.u.) are presented. Figure S3. Complete bonding scheme from QTAIM topological analysis of p for 4,7-(OH)2phen, intercalated between AT/TA base pairs via Minor Groove. For the considered interactions the corresponding BCPs, p (a.u.) and Ed (a.u.) are presented. Figure S4. Complete bonding scheme from QTAIM topological analysis of p for 4,7-(NH2)2phen, intercalated between AT/TA base pairs via Major Groove. For the considered interactions the corresponding BCPs, p (a.u.) and Ed (a.u.) are presented. Figure S5. Complete bonding scheme from QTAIM topological analysis of p for 4,7-(OH)2phen, intercalated between AT/TA base pairs via Major Groove. For the considered interactions the corresponding BCPs, p (a.u.) and Ed (a.u.) are presented. Figure S6. Complete bonding scheme from QTAIM topological analysis of p for 4,7-(NH2)2phen, intercalated between GC/CG base pairs via Minor Groove. For the considered interactions the corresponding BCPs, p (a.u.) and Ed (a.u.) are presented. Figure S7. Complete bonding scheme from QTAIM topological analysis of p for 4,7-(OH)2phen, intercalated between GC/CG base pairs via Minor Groove. For the considered interactions the corresponding BCPs, (a.u.) and Ed (a.u.) are presented. Figure S8. Complete bonding scheme from QTAIM topological analysis of p for 4,7-(NH2)2phen, intercalated between GC/CG base pairs via Major Groove. For the considered interactions the corresponding BCPs, p (a.u.) and Ed (a.u.) are presented. Figure S9. Complete bonding scheme from QTAIM topological analysis of p for 4,7-(OH)2phen, intercalated between GC/CG base pairs via Major Groove. For the considered interactions the corresponding BCPs, p (a.u.) and Ed (a.u.) are presented. Movies Cartesian coordinates for the optimized ring model systems at PM6-DH2 level, Peer reviewed

Full experimental details for the synthesis, characterization, and crystallographic data (PDF). Coordinates (XYZ)., Peer reviewed

1. 1H and 13C{1H} spectra and crystal structure data for the complexes 1–4 and 6: S2 2. Crystal structure determination of complexes 1-4 and 6: S7, Peer reviewed

15 pages. -- Figure S1. Sediment and depth data for each sampling station (station ID numbers correspond to Table S1). -- Figure S2. Relationships between oxygen and total faunal biomass and abundance collected using the box core (a, c) and dredge (b, d) for all sampling stations with oxygen concentrations above 3 ml l–1. -- Figure S3. Vertical abundance distribution of species in the sediment (showing the sum of all individuals across all stations). -- Figure S4. Vertical biomass (gram wet weight) distribution of species in the sediment (showing total biomass across all stations).-- Figure S5. Boxplot of oxygen concentrations for each seasonal quarter based on all data points in Fig. 3a, indicating lower median oxygen concentrations in quarter 3 and 4. -- Figure S6. Simulated daily oxygen concentrations for each sampling station. S describes the day of sampling. -- Figure S7. Comparison of time series of near-bed oxygen concentrations with model simulations at the same location from 2013 to 2018. -- Figure S8. Relationship between annual trawling intensities at Station 9 and the minimum, average and maximum yearly near-bed oxygen concentration (as measured 3.7 km from Station 9, see Fig. 1 and 3). -- Table S1. Overview of environmental conditions. -- Table S2. Wet weight (WW) to shell-free wet weight (SFWW) conversions for bivalve species. -- Table S3. Length-weight relationships for all species identified in the box corer. -- Table S4. PerMANOVA analyses based on Bray-Curtis dissimilarities using longevity biomass data. Table S5. PerMANOVA analyses based on Bray-Curtis dissimilarities using biomass (a) and abundance (b) data in four vertical sediment sections (0–2, 2–4, 4–8 and >8 cm) in relation to changes in oxygen concentrations and trawling intensity. -- Supplementary Text S1: Information on longevity of Astarte elliptica. -- Supplementary Text S2: Calculation of benthic impact from fishing., Peer reviewed

1H and 13C NMR spectra of the organometallic compounds and N-methylated amines, catalyst screening and optimization, isotopic labeling experiments, and DFT-optimized structures (PDF). Coordinates (XYZ)., Peer reviewed

The supporting information: Figures S1–S26: NMR spectra of the complexes; Figure S27: UV–Vis spectra of the complexes; Figure S28: Measurement of the intracellular levels of ROS., Peer reviewed