Mixed-Metal MOF-74 Templated Catalysts for Efficient Carbon Dioxide Capture and Methanation

The vast chemical and structural tunability of metal–organic frameworks (MOFs) are beginning to be harnessed as functional supports for catalytic nanoparticles spanning a range of applications. However, a lack of straightforward methods for producing nanoparticle-encapsulated MOFs as efficient heterogeneous catalysts limits their usage. Herein, a mixed-metal MOF, NiMg-MOF-74, is utilized as a template to disperse small Ni nanoclusters throughout the parent MOF. By exploiting the difference in Ni O and Mg O coordination bond strength, Ni²⁺ is selectively reduced to form highly dispersed Ni nanoclusters constrained by the parent MOF pore diameter, while Mg²⁺ remains coordinated in the framework. By varying the ratio of Ni to Mg in the parent MOF, accessible surface area and crystallinity can be tuned upon thermal treatment, influencing CO₂ adsorption capacity and hydrogenation selectivity. The resulting Ni nanoclusters prove to be an active catalyst for CO₂ methanation and are examined using extended X-ray absorption fine structure and X-ray photoelectron spectroscopy. By preserving a segment of the Mg²⁺-containing MOF framework, the composite system retains a portion of its CO₂ adsorption capacity while continuing to deliver catalytic activity. The approach is thus critical for designing materials that can bridge the gap between carbon capture and CO₂ utilization.     

Retinal neurostimulator for a multifocal vision prosthesis.

A neurostimulator application-specific integrated circuit (ASIC) with scalable circuitry that can stimulate 14 channels, has been developed for an epi-retinal vision prosthesis. This ASIC was designed to allow seven identical units to be connected to control up to 98 channels, with the ability to stimulate 14 electrodes simultaneously. The neurostimulator forms part of a vision prosthesis, designed to restore vision to patients who have lost their sight due to retinal diseases such as retinitis pigmentosa and macular degeneration. For charge balance, the neurostimulator was designed to stimulate with current sources and sinks operating together, and with the ability to drive a hexagonal mosaic of electrodes to reduce the electrical crosstalk that occurs when multiple bipolar stimulation sites are active simultaneously. A hexagonal mosaic of electrodes surrounds each stimulation site and has been shown to effectively isolate each site, increasing the ability to inject localized independent charge into multiple regions simultaneously.     

Ahch, the mouse homologue of DAX1: cloning, characterization and synteny with GyK, the glycerol kinase locus

We cloned the murine full-length cDNA encoding Ahch, the mouse homologue of DAX1 (DSS-AHC Region on Human X Chromosome, Gene1) which is the gene responsible for human X-linked adrenal hypoplasia congenita (AHC) and hypogonadotropic hypogonadism (HH). Sequence analysis revealed that the murine and human cDNAs have 65% aa identity and 75% aa similarity overall. The cysteine residues in the putative DNA binding domain, which may interact with Zn2+ ions to form zinc fingers, are 100% conserved between the two species, indicating that the novel zinc-finger structures in DAX1 may be functional. In addition, mouse interspecific backcrosses show that the Ahch gene is closely linked to the glycerol kinase locus, GyK, on the mouse X chromosome, indicating that the order of the loci is conserved in this syntenic region between mouse and human.     

Visual learning and classification of human epithelial type 2 cell images through spontaneous activity patterns

Identifying the presence of anti-nuclear antibody (ANA) in human epithelial type 2 (HEp-2) cells via the indirect immunofluorescence (IIF) protocol is commonly used to diagnose various connective tissue diseases in clinical pathology tests. As it is a labour and time intensive diagnostic process, several computer aided diagnostic (CAD) systems have been proposed. However, the existing CAD systems suffer from numerous shortcomings due to the selection of features, which is commonly based on expert experience. Such a choice of features may not work well when the CAD systems are retasked to another dataset. To address this, in our previous work, we proposed a novel approach that learns a set of filters from HEp-2 cell images. It is inspired by the receptive fields in the mammalian's vision system, since the receptive fields can be thought as a set of filters for similar shapes. We obtain robust filters for HEp-2 cell classification by employing the independent component analysis (ICA) framework. Although, this approach may be held back due to one particular problem; ICA learning requires a sufficiently large volume of training data which is not always available. In this paper, we demonstrate a biologically inspired solution to address this issue via the use of spontaneous activity patterns (SAP). The spontaneous activity patterns, which are related to the spontaneous neural activities initialised by the chemical release in the brain, are found as the typical stimuli for the visual cell development of newborn animals. In the classification system for HEp-2 cells, we propose to model SAP as a set of small image patches containing randomly positioned Gaussian spots. The SAP image patches are generated and mixed with the training images in order to learn filters via the ICA framework. The obtained filters are adopted to extract the set of responses from a HEp-2 cell image. We then employ regions from this set of responses and stack them into “cubic regions”, and apply a classification based on the correlation information of the features. We show that applying the additional SAP leads to a better classification performance on HEp-2 cell images compared to using only the existing patterns for training ICA filters. The improvement on classification is particularly significant when there are not enough specimen images available in the training set, as SAP adds more variations to the existing data that makes the learned ICA model more robust. We show that the proposed approach consistently outperforms three recently proposed CAD systems on two publicly available datasets: ICPR HEp-2 contest and SNPHEp-2.     

Analysis of wide-angle X-ray diffraction patterns of aligned glassy polymers with particular references to polystyrene

Improvement of WAXD patterns from aligned glassy polymers by a numerical desmearing technique is reported. This gives a fibre type diffraction pattern that can be more easily interpreted than radial or cylindrical distribution functions. Application to atactic and quenched isotactic polystyrene shows that the molecular conformations that are found are in agreement with those deduced from i.r. and n.m.r. spectroscopy. For isotactic polystyrene there is significant agreement between the fibre pattern of the aligned glassy polymer and that of the drawn crystalline polymer.     

Radial distribution functions of non-crystalline polymers and their application to the structural analysis of PMMA

The use of Radial Distribution Functions (RDFs) in the determination of the structure of non-crystalline polymers is briefly reviewed. Particular aspects of the procedure for preparing RDFs from X-ray scattering are discussed in detail; namely the employment of an energy dispersive detector to remove the Compton component of the scattered X-rays and the application of the method of sampled transforms. A RDF is presented for atactic polymethylmethacrylate (PMMA) and its precision and reliability are discussed. It is analysed by comparison with RDFs calculated from computer-generated atom co-ordinates for isolated lengths of PMMA chains in different conformations. Methods are introduced by which the calculated RDFs are smeared to account for random disorder in the real chain and normalized so that, despite the finite range of the model, they can be immediately compared with the difference RDF which is directly obtained by transforming the data. Comparison between experimental and calculated RDFs shows that reasonable agreement is only obtained for a very limited range of conformations corresponding to sequences of backbone bond rotation angles of (10, 10, –10, –10) and the bond angles alternately 110 and 128. The form of the RDF appears very sensitive to important aspects of the molecular structure. The results both confirm and refine an earlier proposal from this laboratory which was based on comparisons between experimental and calculated functions in reciprocal space.     

Utilizing the Explicit Finite Element Method for Studying Granular Flows

Granular flows are systems of complex dry particulates whose behavior is difficult to predict during sliding contact. Existing computational tools used to simulate granular flows are particle dynamics, cellular automata (CA), and continuum modeling. In the present investigation, another numerical tool—the explicit finite element method (FEM)—is analyzed as a potential technique for simulating granular flow. For this purpose, explicit dynamic finite element models of parallel shear cells were developed. These models contained 52 particles and consisted of granules that are both round and multi-shaped (diamond, triangle, and rectangle). Each parallel shear cell consisted of a smooth stationary top wall and a rough bottom surface that was given a prescribed velocity of U = 0.7 in/sec (1.78 cm/s). The coefficient of friction (COF) between the particle–particle and particle–wall collisions was varied between 0.0 and 0.75. Utilizing the output of the simulations, results are presented for the shear behavior, particle kinetic energy, and particle stresses within the shear cell as a function of time. As a means of validating the explicit technique for granular flow, a 75 particle, zero roughness, couette shear cell model (solid fraction of 0.50) is subsequently presented for which direct comparisons are made to the results published by Lun. [Lun, C.K. et al.: Phys. Fluids 8, 2868–2883 (1996)] Overall, the results indicate that the explicit FEM is a powerful tool for simulating granular flow phenomena in sliding contacts. In fact, the explicit method demonstrated several advantages over existing numerical techniques while providing equivalent accuracy to the molecular dynamics (MD) approach. These advantages included being able to monitor the collision (sub-surface and surface) stresses and kinetic energies of individual particles over time, the ability to analyze any particle shape, and the ability to capture force chains during granular flow.     

The effect of variations in objective focal length on electron microscope performance.

Standard specimens were examined in a transmission electron microscope with a top entry stage. Using a range of objective focal lengths, measurements of contrast, resolution and magnification range were made. Focal lengths up to 14 mm were examined. The contrast was found to increase with increasing focal length, being twelve and a half times greater at 14 mm focal length than at the normal high resolution mode of 2 mm focal length. Resolution, determined by the fresnel fringe method decreased from 0-3 nm to 3-5 nm. The photographic image mangnification was reduced from X 1000-X500,000 at 2 mm focal length to X100-X50,000 at 14 mm focal length.     

Viscoelastic properties of branched polyacrylate melts

The viscoelastic properties of poly(n‐butyl acrylate), poly(ethyl acrylate) and poly(methyl acrylate) melts have been studied using samples that varied in both molar mass and the mol% branched repeat units, these properties having been previously determined by gel permeation chromatography and ¹³C NMR spectroscopy, respectively. Poly(n‐butyl acrylate) was studied most extensively using seven samples; one sample of poly(n‐butyl acrylate), two samples of poly(ethyl acrylate) and one sample of poly(methyl acrylate) were used to study the effect of side‐group size. Storage and loss moduli were measured over a range of frequency (1 × 10^?3 to 1 × 10² rad s^?1) at temperatures from T_g + 20 °C to T_g + 155 °C and then shifted to form master curves at T_g + 74 °C through use of standard superposition procedures. The plateau regions were not distinct due to the broad molar mass distributions of the polyacrylates. Hence, the upper and lower limits of shear storage modulus from the nominal ‘plateau’ region of the curves for the seven poly(n‐butyl acrylate) samples were used to calculate the chain molar mass between entanglements, M_e, which gave the range 13.0 kg mol^?1 < M_e < 65.0 kg mol^?1. The Graessley–Edwards dimensionless interaction density and dimensionless contour length concentration were calculated for poly(n‐butyl acrylate) using the mean value of plateau modulus (1.2 × 10⁵ Pa) and three different methods for estimation of the Kuhn length; the data fitted closely to the Graessley–Edwards universal plot. The Williams–Landel–Ferry C₁ and C₂ parameters were determined for each of the polyacrylates; the data for the poly(n‐butyl acrylate) samples indicate an overall reduction in C₁ and C₂ as the degree of branching increases. Although the values of C₁ and C₂ were different for poly(n‐butyl acrylate), poly(ethyl acrylate) and poly(methyl acrylate), there is no trend for variation with structure. Thus the viscoelastic properties of the polyacrylate melts are similar to those for other polymer melts and, for the samples investigated, the effect of molar mass appears to dominate the effect of branching. © 2001 Society of Chemical Industry