Role of the metal cation in the dehydration of the microporous metal–organic frameworks CPO-27-M

The dehydration of the CPO-27-M (M-MOF-74, M = Zn, Co, Ni, Mg, Mn, Cu) metal-organic framework series has been investigated comprehensively using in situ variable temperature powder X-ray diffraction (VT-PXRD) and thermal analysis (TG) coupled with mass spectrometry (MS). Significant differences in the order of water desorption from different adsorption sites on heating are found with varying metal cation in the otherwise isostructural material. For all CPO-27-M (except M = Cu), water is bonded significantly more strongly to the accessible open metal sites, and these water molecules are only desorbed at higher temperatures than the other water molecules. CPO-27-Cu is an exception, where all water molecules desorb simultaneously and at much lower temperatures (below 340 K). MS and TG data show that all CPO-27-M start to release traces of CO2 already at 300–350 K, and thus long before bulk thermal decomposition is observed. Only for CPO-27-Co, the CO2 release is essentially constant on its baseline between 450 and 700 K, and it is the only CPO-27-M member that shows a stable plateau in the TG in this region. Additional rehydration studies on CPO-27-Co show that the MOF incorporates any water molecules present until the pores are fully loaded. CPO-27-Co consequently behaves as an efficient trap for any water present

Middle to late Pleistocene palaeoecological reconstructions and palaeotemperature estimates for cold/cool stage deposits at Whittlesey, eastern England

Fossiliferous beds in a complex sequence of late Middle to Late Pleistocene deposits at Whittlesey, eastern England, provided a rare opportunity for a multidisciplinary study of the palaeoecology of cool/cold stage deposits from different glacial stages. The fossiliferous sediments investigated form part of the River Nene 1st Terrace. Three of the four fossil assemblages investigated pre-date the last interglacial stage (Ipswichian/Eemian/marine oxygen isotope stage (MIS) 5e), whereas the other dates to part of the MIS 3 interstadial complex (Middle Devensian/Weichselian). Pollen, plant macrofossil, molluscan, coleopteran, ostracod, foraminifera and vertebrate data are available to a greater or lesser extent for each cool/cold stage assemblage, and they broadly present the same ecological picture for each one: a continuum from low-energy permanent to non-permanent aquatic habitats through marshland with associated waterside taxa, together with flood influxes of fluvial, riparian and ruderal taxa. Although each fossil assemblage records cool/cold climatic conditions, to a greater or lesser extent, these conditions are more apparent in the insect and ostracod faunas. In comparison with results published for the Last Glacial Maximum (LGM) stadial in The Netherlands, palaeotemperature estimates based on ranges of mutual agreement between independent coleopteran and ostracod methods for the three pre-Ipswichian/Eemian assemblages indicate minimum mean July air temperatures that are from +1° to +3 °C warmer, but January values that embrace the −8 °C estimate for the LGM. There is, however, a disparity between the coleopteran and ostracod palaeotemperature estimates for the Middle Devensian/Weichselian fossil assemblage, which are based on two different sample stratigraphic levels; the lower, coleopteran assemblage is indicative of very cool, continental climates, whereas the stratigraphically slightly higher ostracod assemblage suggests a climatic amelioration. Lack of numerical age-estimates prevents a robust stratigraphical interpretation, but the youngest pre-Ipswichian/Eemian fossil assemblage could date to the MIS 7–6 transition, at a time when cooling possibly preceded glacially driven sea-level fall. It is apparent from the rich coleopteran data that some continental cold-indicator taxa also appeared in pre-Ipswichian/Eemian cold stages and therefore assignment of continental cold-indicator taxa to particular Devensian/Weichselian intervals should be undertaken with care

Predisposing factors to dental caries in children with cleft lip and palate: A review and strategies for early prevention

Objective: To review predisposing factors contributing to dental caries in patients with cleft lip, cleft palate, or both (CUP). Design: Patients with CUP have a higher susceptibility to caries compared with the population group without clefts. A review of the literature was undertaken to determine factors that could account for the compromised oral hygiene and the high caries prevalence in patients with CUP. Results: After a literature review, modern strategies for the prevention of early childhood caries were developed and should be considered for integration into the overall management protocol of patients with CUP. Conclusions: Preventive dental care is ever more so important in patients with CUP compared with patients without clefts

Effect ofl larger pore size on the sorption properties of isoreticular metal–organic frameworks with high number of open metal sites

Four isostructural CPO‐54‐M metal‐organic frameworks based on the larger organic linker 1,5‐dihydroxynaphthalene‐2,6‐dicarboxylic acid and divalent cations (M=Mn, Mg, Ni, Co) are shown to be isoreticular to the CPO‐27 (MOF‐74) materials. Desolvated CPO‐54‐Mn contains a very high concentration of open metal sites, which has a pronounced effect on the gas adsorption of N2, H2, CO2 and CO. Initial isosteric heats of adsorption are significantly higher than for MOFs without open metal sites and are slightly higher than for CPO‐27. The plateau of high heat of adsorption decreases earlier in CPO‐54‐Mn as a function of loading per mole than in CPO‐27‐Mn. Cluster and periodic density functional theory based calculations of the adsorbate structures and energetics show that the larger adsorption energy at low loadings, when only open metal sites are occupied, is mainly due to larger contribution of dispersive interactions for the materials with the larger, more electron rich bridging ligand

Effect of Larger Pore Size on the Sorption Properties of Isoreticular Metal–Organic Frameworks with High Number of Open Metal Sites

Four isostructural CPO‐54‐M metal‐organic frameworks based on the larger organic linker 1,5‐dihydroxynaphthalene‐2,6‐dicarboxylic acid and divalent cations (M=Mn, Mg, Ni, Co) are shown to be isoreticular to the CPO‐27 (MOF‐74) materials. Desolvated CPO‐54‐Mn contains a very high concentration of open metal sites, which has a pronounced effect on the gas adsorption of N2, H2, CO2 and CO. Initial isosteric heats of adsorption are significantly higher than for MOFs without open metal sites and are slightly higher than for CPO‐27. The plateau of high heat of adsorption decreases earlier in CPO‐54‐Mn as a function of loading per mole than in CPO‐27‐Mn. Cluster and periodic density functional theory based calculations of the adsorbate structures and energetics show that the larger adsorption energy at low loadings, when only open metal sites are occupied, is mainly due to larger contribution of dispersive interactions for the materials with the larger, more electron rich bridging ligand

Role of the metal cation in the dehydration of the microporous metal–organic frameworks CPO-27-M

The dehydration of the CPO-27-M (M-MOF-74, M = Zn, Co, Ni, Mg, Mn, Cu) metal-organic framework series has been investigated comprehensively using in situ variable temperature powder X-ray diffraction (VT-PXRD) and thermal analysis (TG) coupled with mass spectrometry (MS). Significant differences in the order of water desorption from different adsorption sites on heating are found with varying metal cation in the otherwise isostructural material. For all CPO-27-M (except M = Cu), water is bonded significantly more strongly to the accessible open metal sites, and these water molecules are only desorbed at higher temperatures than the other water molecules. CPO-27-Cu is an exception, where all water molecules desorb simultaneously and at much lower temperatures (below 340 K). MS and TG data show that all CPO-27-M start to release traces of CO2 already at 300–350 K, and thus long before bulk thermal decomposition is observed. Only for CPO-27-Co, the CO2 release is essentially constant on its baseline between 450 and 700 K, and it is the only CPO-27-M member that shows a stable plateau in the TG in this region. Additional rehydration studies on CPO-27-Co show that the MOF incorporates any water molecules present until the pores are fully loaded. CPO-27-Co consequently behaves as an efficient trap for any water present