When will you have a new mobile phone? An empirical answer from big data

When and why people change their mobile phones are important issues in mobile communications industry, because it will impact greatly on the marketing strategy and revenue estimation for both mobile operators and manufactures. It is a promising way to take use of big data to analyze and predict the phone changing event. In this paper, based on mobile user big data, first through statistical analysis, we find that three important probability distributions, i.e., power-law, log-normal, and geometric distribution, play an important role in the user behaviors. Second, the relationships between eight selected attributes and phone changing are built, for example, young people have greater intention to change their phones if they are using the phones belonging to the low occupancy phones or feature phones. Third, we verified the performance of four prediction models on phone changing event under three scenarios. Information gain ratio was used to implement attribute selection and then sampling method, cost-sensitive together with standard classifiers were used to solve imbalanced phone changing event. Experiment results show our proposed enhanced backpropagation neural network in the undersampling scenario can attain better prediction performance

Management of Refractory/Aggressive Pituitary Adenomas Review of Current Treatment Options

Tumors of central nervous system (CNS) account for a small portion of tumors of human body, which includes tumors occurring in the parenchyma of brain and spinal cord as well as their coverings. This chapter covers some new development in some major brain tumors in both pediatric and adult populations, as well as some uncommon but diagnostic and management challenging tumors

Exceptional capture of methane at low pressure by an iron‐based metal‐organic framework

The selective capture of methane (CH4) at low concentrations and its separation from N2 are extremely challenging owing to the weak host-guest interactions between CH4 molecules and any sorbent material. Here, we report the exceptional adsorption of CH4 at low pressure and efficient separation of CH4/N2 by MFM-300(Fe). MFM-300(Fe) shows a very high uptake for CH4 of 0.85 mmol g−1 at 1 mbar and 298 K and a record CH4/N2 selectivity of 45 for porous solids, representing a new benchmark for CH4 capture and CH4/N2 separation. The excellent separation of CH4/N2 by MFM-300(Fe) has been confirmed by dynamic breakthrough experiments. In situ neutron powder diffraction, and solid-state nuclear magnetic resonance and diffuse reflectance infrared Fourier transform spectroscopies, coupled with modelling, reveal a unique and strong binding of CH4 molecules involving Fe-OH···CH4 and C···phenyl ring interactions within the pores of MFM-300(Fe), thus promoting the exceptional adsorption of CH4 at low pressure

Synthesis of metal-organic frameworks by continuous flow

A continuous flow process for the synthesis of a metal-organic framework using only water as the reaction medium and requiring only short residence times is described. This affords a new route to scale-up of materials incorporating many of the principles of green chemistry. The process is demonstrated by the synthesis MIL-53(Al) via continuous flow reaction requiring only 5-6 minutes with a space time yield of 1300 kg m-3 d-1. We have demonstrated the synthesis of 500 g of MIL-53(Al) using this process, which can be scaled-up further by simply feeding further solutions of metal salt and ligand through the reactor. The product has a higher surface area and a better colour than a commercially produced sample of this MOF. In addition, a new and effective method for the extraction of terephthalic acid from within the pores of MIL-53(Al) using supercritical ethanol has been developed, representing a new methodology for activation and removal of substrates from porous hosts

Studies on metal-organic frameworks of Cu(II) with isophthalate linkers for hydrogen storage

Hydrogen (H2) is a promising alternative energy carrier due to its environmental benefits, high energy density and its abundance. However, development of a practical storage system to enable the “Hydrogen Economy” remains a huge challenge. Metal-organic frameworks (MOFs) are an important class of crystalline coordination polymers constructed by bridging metal centers with organic linkers, and show promise for H2 storage due to their high surface area and tuneable properties. We summarize our research on novel porous materials with enhanced H2 storage properties, and describe frameworks derived from 3,5-substituted dicarboxylates (isophthalates) that serve as versatile molecular building blocks for the construction of a range of interesting coordination polymers with Cu(II) ions. A series of materials has been synthesised by connecting linear tetracarboxylate linkers to {Cu(II)2} paddlewheel moieties. These (4,4)-connected frameworks adopt the fof-topology in which the Kagomé lattice layers formed by {Cu(II)2} paddlewheels and isophthalates are pillared by the bridging ligands. These materials exhibit high structural stability and permanent porosity, and the pore size, geometry and functionality can be modulated by variation of the organic linker to control the overall H2 adsorption properties. NOTT-103 shows the highest H2 storage capacity of 77.8 mg g−1 at 77 K, 60 bar among the fof-type frameworks. H2 adsorption at low, medium and high pressures correlates with the isosteric heat of adsorption, surface area and pore volume, respectively. Tri-branched C3-symmetric hexacarboxylate ligands with Cu(II) give highly porous (3,24)-connected frameworks incorporating {Cu(II)2} paddlewheels. These ubt-type frameworks comprise three types of polyhedral cage: a cuboctahedron, truncated tetrahedron and a truncated octahedron which are fused in the solid state in the ratio 1:2:1, respectively. Increasing the length of the hexacarboxylate struts directly tunes the porosity of the resultant material from micro- to mesoporosity. These materials show exceptionally high H2 uptakes owing to their high surface area and pore volume. NOTT-112, the first reported member of this family reported, adsorbs 111 mg g−1 of H2 at 77 K , 77 bar. More recently, enhanced H2 adsorption in these ubt-type frameworks has been achieved using combinations of polyphenyl groups linked by alkynes to give an overall gravimetric gas capacity for NU-100 of 164 mg g−1 at 77 K, 70 bar. However, due to its very low density NU-100 shows a lower volumetric capacity of 45.7 g L-1 compared with 55.9 g L-1 for NOTT-112, which adsorbs 2.3 wt% H2 at 1 bar, 77K. This significant adsorption of H2 at low pressures is attributed to the arrangement of the {Cu24(isophthalate)24} cuboctahedral cages within the polyhedral structure. Free metal coordination positions are the first binding sites for D2, and in these ubt-type frameworks there are two types of Cu(II) centres, one with its vacant site pointing into the cuboctahedral cage and another pointing externally. D2 molecules bind first at the former position, and then at the external open metal sites. However, other adsorption sites between the cusp of three phenyl groups and a Type I pore window in the framework are also occupied. Ligand and complex design feature strongly in enhancing and maximising H2 storage, and, although current materials operate at 77 K, research continues to explore routes to high capacity H2 storage materials that can function at higher temperatures

Modulation of uptake and reactivity of nitrogen dioxide in metal‐organic framework materials

We report the modulation of reactivity of nitrogen dioxide (NO2) in a charged metal–organic framework (MOF) material, MFM‐305‐CH3 in which unbound N‐centres are methylated and the cationic charge counter‐balanced by Cl− ions in the pores. Uptake of NO2 into MFM‐305‐CH3 leads to reaction between NO2 and Cl− to give nitrosyl chloride (NOCl) and NO3− anions. A high dynamic uptake of 6.58 mmol g−1 at 298 K is observed for MFM‐305‐CH3 as measured using a flow of 500 ppm NO2 in He. In contrast, the analogous neutral material, MFM‐305, shows a much lower uptake of 2.38 mmol g−1. The binding domains and reactivity of adsorbed NO2 molecules within MFM‐305‐CH3 and MFM‐305 have been probed using in situ synchrotron X‐ray diffraction, inelastic neutron scattering and by electron paramagnetic resonance, high‐field solid‐state nuclear magnetic resonance and UV/Vis spectroscopies. The design of charged porous sorbents provides a new platform to control the reactivity of corrosive air pollutants

Catalytic decomposition of NO2 over a copper-decorated metal-organic framework by non-thermal plasma

Efficient catalytic conversion of NO2 to non-harmful species remains an important target for research. State-of-the-art deNOx processes are based upon ammonia (NH3)-assisted selective catalytic reduction (NH3-SCR) over Cu-exchanged zeolites at elevated temperatures. Here, we describe a highly efficient non-thermal plasma (NTP) deNOx process catalyzed by a Cu-embedded metal-organic framework, Cu/MFM-300(Al), at room temperature. Under NTP activation at 25°C, Cu/MFM-300(Al) enables direct decomposition of NO2 into N2, NO, N2O, and O2 without the use of NH3 or other reducing agents. NO2 conversion of 96% with a N2 selectivity of 82% at a turnover frequency of 2.9 h−1 is achieved, comparable to leading NH3-SCR catalysts that use NH3 operating at 250°C–550°C. The mechanism for the rate-determining step (NO→N2) is elucidated by in operando diffuse reflectance infrared Fourier transform spectroscopy, and electron paramagnetic resonance spectroscopy confirms the formation of Cu2+⋯NO nitrosylic adducts on Cu/MFM-300(Al), which facilitates NO dissociation and results in the notable N2 selectivity

Atomically dispersed copper sites in a metal-organic framework for reduction of nitrogen dioxide

Metal–organic framework (MOF) materials provide an excellent platform to fabricate single-atom catalysts due to their structural diversity, intrinsic porosity, and designable functionality. However, the unambiguous identification of atomically dispersed metal sites and the elucidation of their role in catalysis are challenging due to limited methods of characterization and lack of direct structural information. Here, we report a comprehensive investigation of the structure and the role of atomically dispersed copper sites in UiO-66 for the catalytic reduction of NO2 at ambient temperature. The atomic dispersion of copper sites on UiO-66 is confirmed by high-angle annular dark-field scanning transmission electron microscopy, electron paramagnetic resonance spectroscopy, and inelastic neutron scattering, and their location is identified by neutron powder diffraction and solid-state nuclear magnetic resonance spectroscopy. The Cu/UiO-66 catalyst exhibits superior catalytic performance for the reduction of NO2 at 25 °C without the use of reductants. A selectivity of 88% for the formation of N2 at a 97% conversion of NO2 with a lifetime of >50 h and an unprecedented turnover frequency of 6.1 h–1 is achieved under nonthermal plasma activation. In situ and operando infrared, solid-state NMR, and EPR spectroscopy reveal the critical role of copper sites in the adsorption and activation of NO2 molecules, with the formation of {Cu(I)···NO} and {Cu···NO2} adducts promoting the conversion of NO2 to N2. This study will inspire the further design and study of new efficient single-atom catalysts for NO2 abatement via detailed unravelling of their role in catalysis