Evaluation of the Wadden Sea Particularly sensitive Sea Area. On behalf of the Common Wadden Sea Secretariat.

The purpose of this document is to present the high level outcomes for the evaluation of the effectiveness of the Wadden Sea PSSA, seven years after its designation by the IMO. Key changes with regard to IMO and EU shipping policy are identified and described, followed by a review of ‘expert’ opinion focused on the issues relating to PSSAs. The development of an evaluative framework and the resulting findings are introduced and discussed in context. Using existing data against this evaluative framework we conclude that six key elements require action in order to fully describe the efficacy of the designation, and our recommendations to address these concerns are presented.<br/

Interference microscopy highlights properties and peculiarities of SAPO STA-7 crystals: Interference microscopy highlights properties and peculiarities ofSAPO STA-7 crystals

In the framework of this study a new generation of SAPO STA-7 crystals has been investigated with the help of Interference Microscopy. The ability of the abovementioned technique to record intracrystalline concentration profiles during uptake/release of guest molecules revealed oddities of the system under study. In other words, these crystals have the tendency to break in the middle, enhancing in this way diffusion. On the other hand, molecules have to confront high surface barriers when they try to diffuse through the other sides of the crystal, where it is not broken

Comparison of the effect of topology type and linker composition of zeolitic imidazolate framework fillers on the performance of mixed matrix membranes in CO2/N2 separation

The authors acknowledge EPSRC Grant SynHiSel (EP/V047078/1). QJ acknowledges funding from the Chinese Scholarship Council CSC scheme from the Chinese Government (201908140117). The authors also acknowledge the EPSRC Strategic Equipment Resource Grant EP/R023751/1 for the use of the Jeol JSM–IT800 electron microscope at University of St Andrews.Mixed matrix membranes (MMMs) combine the high separation performance of porous materials with the processibility of polymers and so possess potential for carbon capture from CO2-containing gas streams. Zeolitic imidazolate frameworks (ZIFs) are promising candidates as molecular-sieve fillers in MMMs due to their tunability and ease of synthesis. We have compared four ZIFs, all as nanoparticles of similar sizes (ca. 400 nm), as MMM fillers, to investigate the effects of ZIF structure and chemistry on MMM performance of pure gas (CO2, N2) permeation under the same conditions. The chosen ZIFs include two that exhibit strong CO2 adsorption (hybrid ZIF-7/COK-17 and ZIF-94) and two that have higher pore volumes but weaker CO2 interactions (ZIF-8 and a hybrid ZIF-11/ZIF-71). The hybrid ZIF-7/COK-17 and ZIF-94 are structurally related to ZIF-7 (rhombohedral sod topology) and ZIF-8 (cubic sod), respectively, via partial or complete substitution of benzimidazole or 2-methylimidazole by 4,5-dichloroimidazole or 4-methyl-5-imidazolecarboxaldehyde, while the hybrid ZIF-11/ZIF-71 has the rho topology but the same composition as the ZIF-7/COK-17 hybrid. In the first part of the comparative study, MMMs based on two types of commercial polymers, Matrimid®5218 and PEBAX-MH1657, were prepared containing the ZIF-7/COK-17 hybrid and also with ZIF-94. ZIF-94 shows much better compatibility with the polymers, forming homogeneous dispersions at all loadings attempted (≤35 % wt%) whereas the hybrid shows inhomogeneity above 12 wt% in each case. At 12 wt% loading, both fillers show an increase in CO2 permeability at 1.2 bar and 293 K compared to the pure membrane (in PEBAX, this increases from 49.5 to 60 and 68 Barrer) which is the result of increased solubility compensating for decreased diffusivity, and this improvement in permeability continues to increase at the higher levels of loading possible with ZIF-94. ZIF-7/COK-17 in PEBAX show higher selectivity, achieving a calculated CO2/N2 selectivity up to 70. Further investigation of CO2 and N2 permeation on MMMs with the four ZIFs at 12 wt% in PEBAX-MH1657 showed a clear distinction between the ZIF-94 and ZIF-7/COK-17 MMMs (which show higher membrane solubilities but lower diffusivities) compared to ZIF-8 and ZIF-11/ZIF-71 MMMs. At the loading chosen, the CO2 permeability increase achieved by the four ZIFs over PEBAX-MH1657 increases in the order ZIF-11/-71, ZIF-7-COK-17 (ca. 60 Barrer) < ZIF-94 (68) < ZIF-8 (81), reflecting the complex interplay between CO2 solubility (increasing with interaction strength) and diffusivity (increasing with available cage and window size). The calculated CO2/N2 selectivity is highest for the hybrid ZIF-7/COK-17 membrane (70), which is attributed to molecular sieving effects in the rhombohedral sod structure.Peer reviewe

An NMR crystallographic approach to monitoring cation substitution in the aluminophosphate STA-2

The authors thank the Leverhulme Trust (F/00 268/BJ), EPSRC (EP/E041825/1, EP/J501542/1, and EP/F018096/1) and the European Commission FP6 Marie Curie Research Training Network “INDENS” (MRTN-CT-2004–005503), and the Leverhulme Trust (F/00 268/BJ) for support. Accepted 23rd October 2014.The substitution of the divalent cations Mg2+ and Zn2+ into the aluminophosphate (AlPO) framework of STA-2 has been studied using an “NMR crystallographic” approach, combining multinuclear solid-state NMR spectroscopy, X-ray diffraction and first-principles calculations. Although the AlPO framework itself is inherently neutral, the positive charge of the organocation template in an as-made material is usually balanced either by the coordination to the framework of anions from the synthesis solution, such as OH− or F−, and/or by the substitution of aliovalent cations. However, the exact position and distribution of the substituted cations can be difficult to determine, but can have a significant impact upon the catalytic properties a material exhibits once calcined. For as-made Mg substituted STA-2, the positive charge of the organocation template is balanced by the substitution of Mg2+ for Al3+ and, where required, by hydroxide anions coordinated to the framework. [27] Al MAS NMR spectra show that Al is present in both tetrahedral and five-fold coordination, with the latter dependent on the amount of substituted cations, and confirms the bridging nature of the hydroxyl groups, while high-resolution MQMAS spectra are able to show that Mg appears to preferentially substitute on the Al1 site. This conclusion is also supported by first-principles calculations. The calculations also show that 31P chemical shifts depend not only on the topologically-distinct site in the SAT framework, but also on the number of next-nearest-neighbour Mg species, and the exact nature of the coordinated hydroxyls (whether the P atom forms part of a six-membered ring, P(OAl)2OH, where OH bridges between two Al atoms). The calculations demonstrate a strong correlation between the 31P isotropic chemical shift and the average bond angle. In contrast, for Zn substituted STA-2, both X-ray diffraction and NMR spectroscopy show less preference for substitution onto Al1 or Al2, with both appearing to be present, although that into Al1 appears slightly more favoured.PostprintPeer reviewe

Designed synthesis of STA-30 : a small pore zeolite catalyst with topology type SWY

R.G.C. thanks the University of St Andrews and Johnson Matthey for funding. P.A.W. thanks the EPSRC (Designed Synthesis of Zeolites: EP/S016201/1) and the Royal Society (Industry Fellowship INF\R2\192052) for support. A.M. acknowledges the Spanish Ministry of Science and Innovation through the Ramon y Cajal programme (RYC2018-024561-I), the Regional government of Aragon (DGA E13_20R), and to the National Natural Science Foundation of China (NFSC-21850410448; NSFC-21835002).Small-pore aluminosilicate zeolites are attractive targets for synthesis because of their activity as catalysts in important reactions, including ammonia-mediated selective catalytic reduction (SCR) of NOx in auto-exhaust emissions. Such a zeolite with SWY framework type, previously observed as a silicoaluminophosphate, has been prepared with high crystallinity via designed syntheses employing organic 1,8-(1,4-diazabicyclo[2.2.2]octane)octyl (diDABCO-C8) and K+ cations as templates. STA-30 (St Andrews microporous material 30) is an ABC-6 structure in the erionite-offretite family of zeolites that exhibits the 12-layer stacking sequence AABAABAACAAC. The framework, which can be prepared with a controllable Si/Al ratio, possesses columns of alternating d6r units and can cages, of which the latter are oriented to give an inter-column pore space comprising gme cages and swy cages connected via 8Rs. DiDABCO-C8 cations fill the swy cages of as-prepared STA-30, while K+ cations display high occupancy in the can cages. Removal of the template by calcination, followed by ammonium ion exchange of K+ cations residing outside the can cages and subsequent deammoniation, gives a highly crystalline zeolite (K3H6Al9Si72O144, P63/mmc, a = 12.9922(9) Å, c = 29.9624(12) Å) with solid acidity shown by solid-state 1H MAS NMR. Upon hydration, a portion of the Al adopts octahedral geometry, as demonstrated by two sharp resonances at −2.0 and −3.1 ppm in the 27Al MAS NMR. These octahedral species can be converted back to tetrahedral Al by ammonium exchange and are interpreted as distinct hydrated framework Al sites. The activated K,H-STA-30 is a small-pore solid acid with a three-dimensionally connected micropore volume of 0.31 cm3 g–1. In the copper-loaded form, it is an active catalyst for the SCR of NO by ammonia.PostprintPostprintPeer reviewe

Population Coding of Strategic Variables During Foraging in Freely Moving Macaques

Until now, it has been difficult to examine the neural bases of foraging in naturalistic environments because previous approaches have relied on restrained animals performing trial-based foraging tasks. Here we allowed unrestrained monkeys to freely interact with concurrent reward options while we wirelessly recorded population activity in the dorsolateral prefrontal cortex. The animals decided when and where to forage based on whether their prediction of reward was fulfilled or violated. This prediction was not solely based on a history of reward delivery, but also on the understanding that waiting longer improves the chance of reward. The task variables were continuously represented in a subspace of the high-dimensional population activity, and this compressed representation predicted the animal\u27s subsequent choices better than the true task variables and as well as the raw neural activity. Our results indicate that monkeys\u27 foraging strategies are based on a cortical model of reward dynamics as animals freely explore their environment

Mixed-metal MIL-100(Sc,M) (M=Al, Cr, Fe) for Lewis acid catalysis and tandem C−C bond formation and alcohol oxidation

The authors thank Johnson Matthey and the EPSRC for an Industrial CASE award to L.M. We gratefully acknowledge the IAESTE UK for a scholarship to B.E. They also thank the Leverhulme Trust (F/00 268/BJ), EPSRC (EP/J501542/1), and the EaStCHEM Research Computing Facility.The trivalent metal cations Al3+, Cr3+, and Fe3+ were each introduced, together with Sc3+, into MIL-100(Sc,M) solid solutions (M=Al, Cr, Fe) by direct synthesis. The substitution has been confirmed by powder X-ray diffraction (PXRD) and solid-state NMR, UV/Vis, and X-ray absorption (XAS) spectroscopy. Mixed Sc/Fe MIL-100 samples were prepared in which part of the Fe is present as α-Fe2O3 nanoparticles within the mesoporous cages of the MOF, as shown by XAS, TGA, and PXRD. The catalytic activity of the mixed-metal catalysts in Lewis acid catalysed Friedel–Crafts additions increases with the amount of Sc present, with the attenuating effect of the second metal decreasing in the order Al>Fe>Cr. Mixed-metal Sc,Fe materials give acceptable activity: 40 % Fe incorporation only results in a 20 % decrease in activity over the same reaction time and pure product can still be obtained and filtered off after extended reaction times. Supported α-Fe2O3 nanoparticles were also active Lewis acid species, although less active than Sc3+ in trimer sites. The incorporation of Fe3+ into MIL-100(Sc) imparts activity for oxidation catalysis and tandem catalytic processes (Lewis acid+oxidation) that make use of both catalytically active framework Sc3+ and Fe3+. A procedure for using these mixed-metal heterogeneous catalysts has been developed for making ketones from (hetero)aromatics and a hemiacetal.Peer reviewe

A gene × gene interaction between DRD2 and DRD4 is associated with conduct disorder and antisocial behavior in males

<p>Abstract</p> <p>Background</p> <p>Antisocial behaviors are complex polygenic phenotypes that are due to a multifactorial arrangement of genetic polymorphisms. Little empirical research, however, has been undertaken that examines gene × gene interactions in the etiology of conduct disorder and antisocial behavior. This study examined whether adolescent conduct disorder and adult antisocial behavior were related to the dopamine D2 receptor polymorphism (DRD2) and the dopamine D4 receptor polymorphism (DRD4).</p> <p>Methods</p> <p>A sample of 872 male participants from the National Longitudinal Study of Adolescent Health (Add Health) completed self-report questionnaires that tapped adolescent conduct disorder and adult antisocial behavior. DNA was genotyped for DRD2 and DRD4.</p> <p>Results</p> <p>Multivariate regression analysis revealed that neither DRD2 nor DRD4 had significant independent effects on conduct disorder or antisocial behavior. However, DRD2 interacted with DRD4 to predict variation in adolescent conduct disorder and in adult antisocial behavior.</p> <p>Conclusion</p> <p>The results suggest that a gene × gene interaction between DRD2 and DRD4 is associated with the development of conduct disorder and adult antisocial behavior in males.</p

Just a Pretty Picture? The practising artist and the influence of art education in the lives of visual arts graduates

Every year in Australia, around 2000 students graduate from higher education in the visual and performing arts. The intent of many of these visual arts courses in particular, is to produce practising artists. However. the occupation of practising artist is not an easy one in which to survive. In 1999 there were around 16,000 visual. community arts, and craft-persons practising professionally. Therefore, Questions arise as to how the majority of graduates apply their professional knowledge gained in art school? And what happens to these graduates in their later lives? These questions are of importance to tertiary visual art education because the majority of these art school graduates will sooner or later end up working in fields that are ditTerent from the one they trained in, that is, the profession of practising artist

Understanding the structure directing action of copper-polyamine complexes in the direct synthesis of Cu-SAPO-34 and Cu-SAPO-18 catalysts for the selective catalytic reduction of NO with NH3

This work has been supported by Johnson Matthey PLC, UK.Cu2+ cations complexed by linear polyamines have been studied as structure-directing agents (SDAs) for the direct synthesis of copper-containing microporous silicoaluminophosphate (SAPO) materials. The complexing ligands diethylenetriamine (DETA), N-(2-hydroxyethyl)ethylenediamine (HEEDA), triethylenetetramine (TETA), N,N′-bis(2-aminoethyl)-1,3-propanediamine (232), 1,2-bis(3-aminopropylamino)ethane (323), tetraethylenepentamine (TEPA) and pentaethylenehexamine (PEHA) have been investigated. For comparison, syntheses have been performed using the analogous nickel-polyamine complexes. Cu2+ and Ni2+ forms of both SAPO-18 and SAPO-34 materials have been prepared. While most polyamine complexes direct crystallisation to SAPO-34, SAPO-18 has been prepared with Cu2+(232), Ni2+(232) and Ni2+(TETA). The coordination geometry of the included metal complexes was studied by UV-visible and EPR spectroscopy and computer simulation. SAPO-18 is favoured by the smaller square planar complexes or octahedral species (with 2 water molecules) of 232 and TETA. Calcination leaves extra-framework Cu2+ and Ni2+ cations within SAPO-18 and SAPO-34 frameworks. In situ synchrotron IR spectroscopy of Ni-SAPO-18 has shown thermal template degradation occurs via nitrile intermediates. Rietveld structural analysis located extra-framework Cu2+ and Ni2+ cations released by calcination. In SAPO-34, Cu2+ and Ni2+ were located in the 8R window of the cha cage. A second site was found for Ni2+ at the centre of the six-membered rings (6Rs) of the double-six-ring (D6R) sub-units. In SAPO-18 both Cu2+ and Ni2+ cations were located only in the 6Rs of the D6R sub-units. Selected copper SAPO-18 and SAPO-34 samples were tested in the selective catalytic reduction of NO with ammonia (NH3-SCR); both showed high activity.PostprintPostprintPeer reviewe