Solvent-switchable continuous-breathing behaviour in a diamondoid metal–organic framework and its influence on CO2 versus CH4 selectivity

Understanding the behaviour of flexible metal–organic frameworks (MOFs)—porous crystalline materials that undergo a structural change upon exposure to an external stimulus—underpins their design as responsive materials for specific applications, such as gas separation, molecular sensing, catalysis and drug delivery. Reversible transformations of a MOF between open- and closed-pore forms—a behaviour known as ‘breathing’—typically occur through well-defined crystallographic transitions. By contrast, continuous breathing is rare, and detailed characterization has remained very limited. Here we report a continuous-breathing mechanism that was studied by single-crystal diffraction in a MOF with a diamondoid network, (Me2NH2)[In(ABDC)2] (ABDC, 2-aminobenzene-1,4-dicarboxylate). Desolvation of the MOF in two different solvents leads to two polymorphic activated forms with very different pore openings, markedly different gas-adsorption capacities and different CO2 versus CH4 selectivities. Partial desolvation introduces a gating pressure associated with CO2 adsorption, which shows that the framework can also undergo a combination of stepped and continuous breathing

Non-negative mixed finite element formulations for a tensorial diffusion equation

We consider the tensorial diffusion equation, and address the discrete maximum-minimum principle of mixed finite element formulations. In particular, we address non-negative solutions (which is a special case of the maximum-minimum principle) of mixed finite element formulations. The discrete maximum-minimum principle is the discrete version of the maximum-minimum principle. In this paper we present two non-negative mixed finite element formulations for tensorial diffusion equations based on constrained optimization techniques (in particular, quadratic programming). These proposed mixed formulations produce non-negative numerical solutions on arbitrary meshes for low-order (i.e., linear, bilinear and trilinear) finite elements. The first formulation is based on the Raviart-Thomas spaces, and is obtained by adding a non-negative constraint to the variational statement of the Raviart-Thomas formulation. The second non-negative formulation based on the variational multiscale formulation. For the former formulation we comment on the affect of adding the non-negative constraint on the local mass balance property of the Raviart-Thomas formulation. We also study the performance of the active set strategy for solving the resulting constrained optimization problems. The overall performance of the proposed formulation is illustrated on three canonical test problems.Comment: 40 pages using amsart style file, and 15 figure

Multi-stimulus linear negative expansion of a breathing M(O2CR)4-node MOF

The metal–organic framework (Me2NH2)2[Cd(NO2BDC)2] (SHF-81) comprises flattened tetrahedral Cd(O2CR)42− nodes, in which Cd(II) centres are linked via NO2BDC2− ligands (2-nitrobenzene-1,4-dicarboxylate) to give a doubly interpenetrated anionic network, with charge balanced by two Me2NH2+ cations per Cd centre resident in the pores. The study establishes that this is a twinned α-quartz-type structure (trigonal, space group P3x21, x = 1 or 2), although very close to the higher symmetry β-quartz arrangement (hexagonal, P6x22, x = 2 or 4) in its as-synthesised solvated form [Cd(NO2BDC)2]·2DMF·0.5H2O (SHF-81-DMF). The activated MOF exhibits very little N2 uptake at 77 K, but shows significant CO2 uptake at 273–298 K with an isosteric enthalpy of adsorption (ΔHads) at zero coverage of −27.4 kJ mol−1 determined for the MOF directly activated from SHF-81-DMF. A series of in situ diffraction experiments, both single-crystal X-ray diffraction (SCXRD) and powder X-ray diffraction (PXRD), reveal that the MOF is flexible and exhibits breathing behaviour with observed changes as large as 12% in the a- and b-axes (|Δa|, |Δb| 0; Δc 0). The largest change in dimensions is observed during activation/desolvation from SHF-81-DMF to SHF-81 (Δa, Δb 0; ΔV < 0). Collectively the nine in situ diffraction experiments conducted suggest the breathing behaviour is continuous, although individual desolvation and adsorption experiments do not rule out the possibility of a gating or step at intermediate geometries that is coupled with continuous dynamic behaviour towards the extremities of the breathing amplitude

Mechanisms of surface charge modification of carbonates in aqueous electrolyte solutions

The influence of different types of salts (NaCl, CaCl 2 , MgCl 2 , NaHCO 3 , and Na 2 SO 4 ) on the surface characteristics of unconditioned calcite and dolomite particles, and conditioned with stearic acid, was investigated. This study used zeta potential measurements to gain fundamental understanding of physico-chemical mechanisms involved in surface charge modification of carbonate minerals in the presence of diluted salt solutions. By increasing the salt concentration of divalent cationic salt solution (CaCl 2 and MgCl 2 ), the zeta potential of calcite particles was altered, resulting in charge reversal from negative to positive, while dolomite particles maintained positive zeta potential. This is due to the adsorption of potential-determining cations (Ca 2+ and Mg 2+ ), and consequent changes in the structure of the diffuse layer, predominantly driven by coulombic interactions. On the other hand, chemical adsorption of potential-determining anions (HCO −3 and SO 2−4 ) maintained the negative zeta potential of carbonate surfaces and increased its magnitude up to 10 mM, before decreasing at higher salt concentrations. Physisorption of stearic acid molecules on the calcite and dolomite surfaces changed the zeta potential to more negative values in all solutions. It is argued that divalent cations (Ca 2+ and Mg 2+ ) would result in positive and neutral complexes with stearic acid molecules, which may result in strongly bound stearic acid films, whereas ions resulting in negative mineral surface charges (SO 2−4 and HCO −3 ) will cause stearic acid films to be loosely bound to the carbonate mineral surfaces. The suggested mechanism for surface charge modification of carbonates, in the presence of different ions, is changes in both distribution of ions in the diffuse layer and its structure as a result of ion adsorption to the crystal lattice by having a positive contribution to the disjoining pressures when changing electrolyte concentration. This work extends the current knowledge base for dynamic water injection design by determining the effect of salt concentration on surface electrostatics

Non-linear adsorption characteristics of modified pine wood sawdust optimised for adsorption of Cd(II) from aqueous systems

A chemically-modified adsorbent (SDTMA), produced from the treatment of pinewood sawdust with maleic acid, was tested in batch adsorption experiments to remove Cd(II) ions from aqueous solution. SDTMA was characterised for the pH of zero point charge (pHZPC), spectroscopic evaluation of the surface functionalisation, structural and morphological features. Factors affecting adsorption behaviour, such as adsorbent dose, pH of solution, contact time and Cd(II) ion concentration were investigated. Results obtained show that adsorption rate to be comparatively fast, with equilibrium achieved after ~35 min. Subsequent analysis, showed Langmuirian behaviour and a monolayer adsorption capacity of 180.4 mg g-1, at pH 6; while data derived from two-parameter (Langmuir, Freundlich, Temkin and Dubinin-Radushkevich (D-R)) and three-parameter (Redlich-Peterson (R-P), Toth Khan and Sips) isotherm models was evaluated using non-linear regression methods, with error analysis, to determine the most appropriate model and allow prediction of optimum parameters. The Sips isotherm model proved the most appropriate in describing the experimental data obtained in the study. Additionally, the rate of adsorption was analysed using a range of kinetic models (pseudo-first-order, pseudo-second-order, intra-particle diffusion, Bangham and Elovich) in their non-linear forms to provide insight into the adsorption mechanism and showing pseudo-second order behaviour is observed. In conclusion, the SDTMA adsorbent material produced in this study offers high potential for the removal of Cd(II) ions from aqueous solution due to the carboxylic functionalities incorporated into the material, which is optimised by solution pH and adsorbent dose

Qualitative impact assessment of land management interventions on ecosystem services (“QEIA”). Report-3.7: cultural services

This project assessed the impacts of 741 potential land management actions, suitable for agricultural land in England, on the Farming & Countryside Programme’s Environmental Objectives (and therefore Environment Act targets and climate commitments) through 53 relevant environmental and cultural service indicators. The project used a combination of expert opinion and rapid evidence reviews, which included 1000+ pages of evidence in 10 separate reports with reference to over 2400 published studies, and an Integrated Assessment comprising expert-derived qualitative impact scores. The project has ensured that ELM schemes are evidence-based, offer good value for money, and contribute to SoS priorities for farming

Evidence for charge localization in the ferromagnetic phase of La_(1-x)Ca_(x)MnO_3 from High real-space-resolution x-ray diffraction

High real-space-resolution atomic pair distribution functions of La_(1-x)Ca_(x)MnO_3 (x=0.12, 0.25 and 0.33) have been measured using high-energy x-ray powder diffraction to study the size and shape of the MnO_6 octahedron as a function of temperature and doping. In the paramagnetic insulating phase we find evidence for three distinct bond-lengths (~ 1.88, 1.95 and 2.15A) which we ascribe to Mn^{4+}-O, Mn^{3+}-O short and Mn^{3+}-O long bonds respectively. In the ferromagnetic metallic (FM) phase, for x=0.33 and T=20K, we find a single Mn-O bond-length; however, as the metal-insulator transition is approached either by increasing T or decreasing x, intensity progressively appears around r=2.15 and in the region 1.8 - 1.9A suggesting the appearance of Mn^{3+}-O long bonds and short Mn^{4+}-O bonds. This is strong evidence that charge localized and delocalized phases coexist close to the metal-insulator transition in the FM phase.Comment: 8 pages, 8 postscript figures, submitted to Phys. Rev.

Non-traumatic injury profile of amateur cyclists

BACKGROUND : Non-traumatic bicycle injuries are common. However, research available on non-traumatic injuries in amateur cyclists is more than a decade old, and most of the research on this topic has been done in Europe and America on professional cyclists in multi-day cycling events. An understanding of the common injuries may lead to appropriate prevention intervention. OBJECTIVE : To determine the incidence of overuse injuries in amateur cyclists preparing for participation in a 1-day cycle challenge. METHODS : A questionnaire was emailed to participants of the 2012 Momentum 94.7 Cycle Challenge, which amateur participants ≥18 years old were invited to complete. Data on demographics, training habits and the participants’ injury profile in the preceding year were collected. RESULTS : Of the 3 300 respondents, 75% were male and 59% were between 30 and 50 years old. Non-traumatic injury, pain or neurological symptoms were reported by 88% of the respondents. The percentages of all respondents who experienced problems in the following anatomical areas were as follows: neck 34%, back 41%, hand/wrist 41%, buttock/perineum 41%, hip 7%, knee 33% and foot/ankle 24%. Knee pain was responsible for the need to stop training for the largest percentage of respondents. Neurological complaints were common in respondents who experienced neck, back, hand/wrist, buttock/perineum and foot/ankle problems. CONCLUSION : Non-traumatic injuries in amateur cyclists are common, with back, hand/wrist and buttock/perineal symptoms the most frequent problems. Knee problems caused the greatest need to stop training and seek medical help.http://www.journals.co.za/sama/m_sajsm.htmlhb201

Palynological evidence for environmental and climatic change in the lower Guadiana valley, Portugal, during the last 13 000 years

Pollen analysis of a 48 m AMS radiocarbon-dated sediment sequence from the Guadiana estuary provides the first record of Lateglacial and Holocene vegetation history in the Algarve province of Portugal. This paper focuses on the record of terrestrial pollen taxa, which document a series of forest expansions and declines during the period 13 000 cal. BP to 1600 cal. BP and provide insights into climate evolution in southwestern Iberia. The main vegetation phases identified in the Guadiana valley are (1) Lateglacial interstadial (Allerød) forest with Quercus and Pinus under a temperate, moist, continental climate; (2) a Younger Dryas forest decline (Quercus) and expansion of pinewoods, xeric scrub and open ground habitats (with Juniperus, Artemisia, Ephedra distachya type, Centaurea scabiosa type) under arid and cold conditions; (3) an early Holocene forest/scrub/open-ground vegetation mosaic developing under a warm, dry and continental climate; (4) a maximum of Quercus forest and thermomediterranean evergreen taxa (Olea, Phillyrea, Pistacia) reflecting a warm, moist oceanic climate between c. 9000 cal. BP and c. 5000 cal. BP; and (5) the expansion of shrublands with Cistaceae and Ericaceae under a drier climatic regime and increasing anthropogenic activity since c. 5000 cal. BP. Holocene episodes of maximum climatic aridity are identified in the record of xerophytic taxa (Juniperus, Artemisia, Ephedra distachya type) centred around 10 200 cal. BP, 7800 cal. BP, 4800 cal. BP, 3100 cal. BP and 1700 cal. BP. Regional comparisons suggest a correlation of arid phases across southern Iberia and northwest Africa, which can be related to abrupt North Atlantic coolings (Bond events).Research Council studentship for WJF (NERC/S/A/2001/06109), with the support of Trinity College and the Department of Geography, University of Cambridg