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5,407 result(s) for "O’Keeffe, Michael"
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The Chemistry and Applications of Metal-Organic Frameworks
Metal-organic frameworks are porous materials that can exhibit very high surface areas that have potential for applications such as gas storage and separation, as well as catalysis. Furukawa et al. ( 1230444 ) review the structures devised so far and discuss the design strategies that allow families of materials to be synthesized and modified with similar framework topology but vary in pore size and type of functional groups present on the linkers. Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.
Cavity-enhanced microwave readout of a solid-state spin sensor
Overcoming poor readout is an increasingly urgent challenge for devices based on solid-state spin defects, particularly given their rapid adoption in quantum sensing, quantum information, and tests of fundamental physics. However, in spite of experimental progress in specific systems, solid-state spin sensors still lack a universal, high-fidelity readout technique. Here we demonstrate high-fidelity, room-temperature readout of an ensemble of nitrogen-vacancy centers via strong coupling to a dielectric microwave cavity, building on similar techniques commonly applied in cryogenic circuit cavity quantum electrodynamics. This strong collective interaction allows the spin ensemble’s microwave transition to be probed directly, thereby overcoming the optical photon shot noise limitations of conventional fluorescence readout. Applying this technique to magnetometry, we show magnetic sensitivity approaching the Johnson–Nyquist noise limit of the system. Our results pave a clear path to achieve unity readout fidelity of solid-state spin sensors through increased ensemble size, reduced spin-resonance linewidth, or improved cavity quality factor. Conventional optical readout limits the sensitivity of solid state spin sensors due to photon shot noise and poor contrast. Here, the authors demonstrate room-temperature microwave detection of an ensemble of NV centers embedded in a microwave cavity, which offers high-fidelity readout without time overhead.
Bottom-up construction of a superstructure in a porous uranium-organic crystal
Bottom-up construction of highly intricate structures from simple building blocks remains one of the most difficult challenges in chemistry. We report a structurally complex, mesoporous uranium-based metal-organic framework (MOF) made from simple starting components. The structure comprises 10 uranium nodes and seven tricarboxylate ligands (both crystallographically nonequivalent), resulting in a 173.3-angstrom cubic unit cell enclosing 816 uranium nodes and 816 organic linkers—the largest unit cell found to date for any nonbiological material. The cuboctahedra organize into pentagonal and hexagonal prismatic secondary structures, which then form tetrahedral and diamond quaternary topologies with unprecedented complexity. This packing results in the formation of colossal icosidodecahedral and rectified hexakaidecahedral cavities with internal diameters of 5.0 nanometers and 6.2 nanometers, respectively—ultimately giving rise to the lowest-density MOF reported to date.
Terminology of metal–organic frameworks and coordination polymers (IUPAC Recommendations 2013)
A set of terms, definitions, and recommendations is provided for use in the classification of coordination polymers, networks, and metal–organic frameworks (MOFs). A hierarchical terminology is recommended in which the most general term is coordination polymer. Coordination networks are a subset of coordination polymers and MOFs a further subset of coordination networks. One of the criteria an MOF needs to fulfill is that it contains potential voids, but no physical measurements of porosity or other properties are demanded per se. The use of topology and topology descriptors to enhance the description of crystal structures of MOFs and 3D-coordination polymers is furthermore strongly recommended.
Colossal cages in zeolitic imidazolate frameworks as selective carbon dioxide reservoirs
Get cagey with the CO 2 Zeolitic imidazolate frameworks, or ZIFs, are porous crystalline materials in which organic imidazolate links connect to transition metals to form a tetrahedral framework. Many different ZIF structures can be created by simply adjusting the link–link interactions. Wang et al . used this tactic to produce two new materials with structures of a scale and complexity rarely seen before. The resulting cages contain up to 264 vertices within the pore network, and are constructed from as many as 7,524 atoms. The cages can selectively capture and store carbon dioxide with high efficiency and this, combined with stability and ease of fabrication, makes giant ZIFs promising candidates for technologies aimed at reducing carbon dioxide emissions. Zeolitic imidazolate frameworks (ZIFs) are porous crystalline materials where organic imidazolate links connect to transition metals to form a tetrahedral framework. Intriguingly, many different ZIF structures can be created by simply adjusting the link-link interactions. Links that result in two new materials with structures of a scale and complexity rarely seen before have now been designed: huge and complex cages within the pore network contain up to 264 vertices, and are constructed from as many as 7,524 atoms. Zeolitic imidazolate frameworks (ZIFs) are porous crystalline materials with tetrahedral networks that resemble those of zeolites: transition metals (Zn, Co) replace tetrahedrally coordinated atoms (for example, Si), and imidazolate links replace oxygen bridges 1 . A striking feature of these materials is that the structure adopted by a given ZIF is determined by link–link interactions, rather than by the structure directing agents used in zeolite synthesis 2 . As a result, systematic variations of linker substituents have yielded many different ZIFs that exhibit known or predicted zeolite topologies. The materials are chemically and thermally stable, yet have the long-sought-after design flexibility offered by functionalized organic links and a high density of transition metal ions 1 , 2 , 3 , 4 , 5 , 6 , 7 . Here we report the synthesis and characterization of two porous ZIFs—ZIF-95 and ZIF-100—with structures of a scale and complexity previously unknown in zeolites 8 , 9 , 10 . The materials have complex cages that contain up to 264 vertices, and are constructed from as many as 7,524 atoms. As expected from the adsorption selectivity recently documented for other members of this materials family 3 , both ZIFs selectively capture carbon dioxide from several different gas mixtures at room temperature, with ZIF-100 capable of storing 28 litres per litre of material at standard temperature and pressure. These characteristics, combined with their high thermal and chemical stability and ease of fabrication, make ZIFs promising candidate materials for strategies aimed at ameliorating increasing atmospheric carbon dioxide levels.
Large-Pore Apertures in a Series of Metal-Organic Frameworks
We report a strategy to expand the pore aperture of metal-organic frameworks (MOFs) into a previously unattained size regime (>32 angstroms). Specifically, the systematic expansion of a well-known MOF structure, MOF-74, from its original link of one phenylene ring (I) to two, three, four, five, six, seven, nine, and eleven (II to XI, respectively), afforded an isoreticular series of MOF-74 structures (termed IRMOF-74-l to XI) with pore apertures ranging from 14 to 98 angstroms. All members of this series have non-interpenetrating structures and exhibit robust architectures, as evidenced by their permanent porosity and high thermal stability (up to 300°C). The pore apertures of an oligoethylene glycol-functionalized IRMOF-74-VII and IRMOF-74-IX are large enough for natural proteins to enter the pores.
Ultrahigh Porosity in Metal-Organic Frameworks
Crystalline solids with extended non-interpenetrating three-dimensional crystal structures were synthesized that support well-defined pores with internal diameters of up to 48 angstroms. The Zn 4 O(CO₂) 6 unit was joined with either one or two kinds of organic link, 4,4', 4\"-[benzene-l, 3,5-triyl-tris (ethyne-2, l-diyl)] tribenzoate (BTE), 4'4',4\"-[benzene-1,3,5-triyl-tris(benzene-4,1-diyl)] tribenzoate (BBC), 4,4',44\"-benzene-1,3,5-triyl-tribenzoate (BTB)/2,6-naphthalenedicarboxylate (NDC), and BTE/biphenyl-4,4'-dicarboxylate (BPDC), to give four metal-organic frameworks (MOFs), MOF-180, -200, -205, and -210, respectively. Members of this series of MOFs show exceptional porosities and gas (hydrogen, methane, and carbon dioxide) uptake capacities. For example, MOF-210 has Brunauer-Emmett-Teller and Langmuir surface areas of 6240 and 10,400 square meters per gram, respectively, and a total carbon dioxide storage capacity of 2870 milligrams per gram. The volume-specific internal surface area of MOF-210 (2060 square meters per cubic centimeter) is equivalent to the outer surface of nanoparticles (3-nanometer cubes) and near the ultimate adsorption limit for solid materials.
Migration of Myeloid Cells during Inflammation Is Differentially Regulated by the Cell Surface Receptors Slamf1 and Slamf8
Previous studies have demonstrated that the cell surface receptor Slamf1 (CD150) is requisite for optimal NADPH-oxidase (Nox2) dependent reactive oxygen species (ROS) production by phagocytes in response to Gram- bacteria. By contrast, Slamf8 (CD353) is a negative regulator of ROS in response to Gram+ and Gram- bacteria. Employing in vivo migration after skin sensitization, induction of peritonitis, and repopulation of the small intestine demonstrates that in vivo migration of Slamf1-/- dendritic cells and macrophages is reduced, as compared to wt mice. By contrast, in vivo migration of Slamf8-/- dendritic cells, macrophages and neutrophils is accelerated. These opposing effects of Slamf1 and Slamf8 are cell-intrinsic as judged by in vitro migration in transwell chambers in response to CCL19, CCL21 or CSF-1. Importantly, inhibiting ROS production of Slamf8-/- macrophages by diphenyleneiodonium chloride blocks this in vitro migration. We conclude that Slamf1 and Slamf8 govern ROS-dependent innate immune responses of myeloid cells, thus modulating migration of these cells during inflammation in an opposing manner.
Hamiltonian engineering with constrained optimization for quantum sensing and control
While quantum devices rely on interactions between constituent subsystems and with their environment to operate, native interactions alone often fail to deliver targeted performance. Coherent pulsed control provides the ability to tailor effective interactions, known as Hamiltonian engineering. We propose a Hamiltonian engineering method that maximizes desired interactions while mitigating deleterious ones by conducting a pulse sequence search using constrained optimization. The optimization formulation incorporates pulse sequence length and cardinality penalties consistent with linear or integer programming. We apply the general technique to magnetometry with solid state spin ensembles in which inhomogeneous interactions between sensing spins limit coherence. Defining figures of merit for broadband Ramsey magnetometry, we present novel pulse sequences which outperform known techniques for homonuclear spin decoupling in both spin-1/2 and spin-1 systems. When applied to nitrogen vacancy (NV) centers in diamond, this scheme partially preserves the Zeeman interaction while zeroing dipolar coupling between negatively charged NV− centers. Such a scheme is of interest for NV− magnetometers which have reached the NV−-NV− coupling limit. We discuss experimental implementation in NV ensembles, as well as applicability of the current approach to more general spin bath decoupling and superconducting qubit control.
Exceptional Chemical and Thermal Stability of Zeolitic Imidazolate Frameworks
Twelve zeolitic imidazolate frameworks (ZIFs; termed ZIF-1 to -12) have been synthesized as crystals by copolymerization of either Zn(II) (ZIF-1 to -4, -6 to -8, and -10 to -11) or Co(II) (ZIF-9 and -12) with imidazolate-type links. The ZIF crystal structures are based on the nets of seven distinct aluminosilicate zeolites: tetrahedral Si(AI) and the bridging O are replaced with transition metal ion and imidazolate link, respectively. In addition, one example of mixed-coordination imidazolate of Zn(II) and In(III) (ZIF-5) based on the garnet net is reported. Study of the gas adsorption and thermal and chemical stability of two prototypical members, ZIF-8 and -11, demonstrated their permanent porosity (Langmuir surface area = 1,810 m²/g), high thermal stability (up to 550°C), and remarkable chemical resistance to boiling alkaline water and organic solvents.