Synthesis of Nanostructured Catalysts by Surfactant-Templating of Large-Pore Zeolites

Zeolites and related crystalline molecular sieves are utilised in a wide range of reactions and processes due to their regular microporous structure, strong acidity, shape selectivity and ion-exchange properties. However, their practical applications can be limited by the small size of the channels and cavities of the microporous structures, and therefore, a great deal of effort have been devoted to enhancing the transport of large-sized molecules in the host pores. Several commercially available zeolites, including faujasite (FAU), mordenite (MOR), beta (BEA), ZSM-5 (MFI) and zeolite L (LTL) have been exposed to a variety of acid and base treatments in the presence of a surfactant (cetyltrimethyl ammonium bromide, CTAB), which led to the controlled introduction of intracrystalline mesoporosity. A detailed characterisation of the obtained mesostructured zeolites has been carried out using FTIR spectroscopy, high resolution TEM, XRD, N2 adsorption, 29Si and 27Al MAS NMR. This work demonstrates a successful application of the supramolecular templating approach for generating tuneable mesoporosity in a range of zeolites possessing 12-membered ring channels, which has been applied to zeolite L for the first time, thus producing hierarchical meso-microporous materials with improved accessibility of active sites and enhanced catalytic performance in dealkylation of tri-isopropylbenzene

Prediction of the Caspian Sea level using ECMWF seasonal forecasts and reanalysis

This article is made available through the Brunel Open Access Publishing Fund. This article is distributed under the terms of the Creative Commons Attribution License which permits any use, distribution, and reproduction in any medium, provided the original author(s) and the source are credited.The hydrological budget of the Caspian Sea (CS) is investigated using the European Centre for Medium-Range Weather Forecasts interim reanalysis (ERAi) and seasonal forecast (FCST) data with the aim of predicting the Caspian Sea Level (CSL) some months ahead. Precipitation and evaporation are used. After precipitation events over the Volga River, the discharge (Volga River discharge (VRD)) follows with delays, which are parameterized. The components of the water budget from ERAi and FCSTs are integrated to obtain time series of the CSL. Observations of the CSL and the VRD are used for comparison and tuning. The quality of ERAi data is sufficiently good to calculate the time variability of the CSL with a satisfactory accuracy. Already the storage of water within the Volga Basin allows forecasts of the CSL a few months ahead, and using the FCSTs of precipitation improves the CSL forecasts. The evaporation in the seasonal forecasts is deficient due to unrealistic sea surface temperatures over the CS. Impacts of different water budget terms on the CSL variability are shown by a variety of validation tools. The importance of precipitation anomalies over the catchment of the Volga River is confirmed, but also impacts from the two southern rivers (Sefidrud and Kura River) and the evaporation over the CS become obvious for some periods. When pushing the FCSTs beyond the limits of the seasonal FCSTs to 1 year, considerable forecast skill can still be found. Validating only FCSTs by the present approach, which show the same trend as one based on a statistical method, significantly enhances the skill scores

Unravelling surface and interfacial structures of a metal–organic framework by transmission electron microscopy

Metal-organic frameworks (MOFs) are crystalline porous materials with designable topology, porosity and functionality, having promising applications in gas storage and separation, ion conduction and catalysis. It is challenging to observe MOFs with transmission electron microscopy (TEM) due to the extreme instability of MOFs upon electron beam irradiation. Here, we use a direct-detection electron-counting camera to acquire TEM images of the MOF ZIF-8 with an ultralow dose of 4.1 electrons per square ångström to retain the structural integrity. The obtained image involves structural information transferred up to 2.1 Å, allowing the resolution of individual atomic columns of Zn and organic linkers in the framework. Furthermore, TEM reveals important local structural features of ZIF-8 crystals that cannot be identified by diffraction techniques, including armchair-type surface terminations and coherent interfaces between assembled crystals. These observations allow us to understand how ZIF-8 crystals self-assemble and the subsequent influence of interfacial cavities on mass transport of guest molecules

Azimuthal Charged-Particle Correlations and Possible Local Strong Parity Violation

Parity-odd domains, corresponding to nontrivial topological solutions of the QCD vacuum, might be created during relativistic heavy-ion collisions. These domains are predicted to lead to charge separation of quarks along the system’s orbital momentum axis. We investigate a three-particle azimuthal correlator which is a P even observable, but directly sensitive to the charge separation effect. We report measurements of charged hadrons near center-of-mass rapidity with this observable in Au+Au and Cu+Cu collisions at √sNN=200  GeV using the STAR detector. A signal consistent with several expectations from the theory is detected. We discuss possible contributions from other effects that are not related to parity violation

Peripersonal Space and Margin of Safety around the Body: Learning Visuo-Tactile Associations in a Humanoid Robot with Artificial Skin

This paper investigates a biologically motivated model of peripersonal space through its implementation on a humanoid robot. Guided by the present understanding of the neurophysiology of the fronto-parietal system, we developed a computational model inspired by the receptive fields of polymodal neurons identified, for example, in brain areas F4 and VIP. The experiments on the iCub humanoid robot show that the peripersonal space representation i) can be learned efficiently and in real-time via a simple interaction with the robot, ii) can lead to the generation of behaviors like avoidance and reaching, and iii) can contribute to the understanding the biological principle of motor equivalence. More specifically, with respect to i) the present model contributes to hypothesizing a learning mechanisms for peripersonal space. In relation to point ii) we show how a relatively simple controller can exploit the learned receptive fields to generate either avoidance or reaching of an incoming stimulus and for iii) we show how the robot can select arbitrary body parts as the controlled end-point of an avoidance or reaching movement

Iron Behaving Badly: Inappropriate Iron Chelation as a Major Contributor to the Aetiology of Vascular and Other Progressive Inflammatory and Degenerative Diseases

The production of peroxide and superoxide is an inevitable consequence of aerobic metabolism, and while these particular "reactive oxygen species" (ROSs) can exhibit a number of biological effects, they are not of themselves excessively reactive and thus they are not especially damaging at physiological concentrations. However, their reactions with poorly liganded iron species can lead to the catalytic production of the very reactive and dangerous hydroxyl radical, which is exceptionally damaging, and a major cause of chronic inflammation. We review the considerable and wide-ranging evidence for the involvement of this combination of (su)peroxide and poorly liganded iron in a large number of physiological and indeed pathological processes and inflammatory disorders, especially those involving the progressive degradation of cellular and organismal performance. These diseases share a great many similarities and thus might be considered to have a common cause (i.e. iron-catalysed free radical and especially hydroxyl radical generation). The studies reviewed include those focused on a series of cardiovascular, metabolic and neurological diseases, where iron can be found at the sites of plaques and lesions, as well as studies showing the significance of iron to aging and longevity. The effective chelation of iron by natural or synthetic ligands is thus of major physiological (and potentially therapeutic) importance. As systems properties, we need to recognise that physiological observables have multiple molecular causes, and studying them in isolation leads to inconsistent patterns of apparent causality when it is the simultaneous combination of multiple factors that is responsible. This explains, for instance, the decidedly mixed effects of antioxidants that have been observed, etc...Comment: 159 pages, including 9 Figs and 2184 reference