RESUMO
Widespread access to greener energy is required in order to mitigate the effects of climate change. A significant barrier to cleaner natural gas usage lies in the safety/efficiency limitations of storage technology. Despite highly porous metal-organic frameworks (MOFs) demonstrating record-breaking gas-storage capacities, their conventionally powdered morphology renders them non-viable. Traditional powder shaping utilising high pressure or chemical binders collapses porosity or creates low-density structures with reduced volumetric adsorption capacity. Here, we report the engineering of one of the most stable MOFs, Zr-UiO-66, without applying pressure or binders. The process yields centimetre-sized monoliths, displaying high microporosity and bulk density. We report the inclusion of variable, narrow mesopore volumes to the monoliths' macrostructure and use this to optimise the pore-size distribution for gas uptake. The optimised mixed meso/microporous monoliths demonstrate Type II adsorption isotherms to achieve benchmark volumetric working capacities for methane and carbon dioxide. This represents a critical advance in the design of air-stable, conformed MOFs for commercial gas storage.
RESUMO
The sequential reaction of ZnMe2 with a 2-pyridylamine (HN(2-C5H4N)R, R = Ph: 1; 3,5-Xy (=3,5-xylyl): 2; 2,6-Xy: 3; Bz (=benzyl): 4; Me: 5), tBuLi and thereafter with oxygen affords various lithium zincate species, the solid-state structures of which reveal a diversity of oxo-capture modes. Amine 1 reacts to give both dimeric THF [Li(Me)OZn[N(2-C5H4N)Ph]2] (6), wherein oxygen has inserted into the Zn-C bond of a [MeZn[N(2-C5H4N)-Ph]2] ion, and the trigonal Li2Zn complex, bis(OtBu)-capped (THF x Li)2-[[(mu3-O)tBu]2Zn[N(2-C5H4N)Ph]2] (7). The structural analogue of 6 (8) results from the employment of 2, while the use of more sterically congested 3 yields a pseudo-cubane dimer [(THF x [Li(tBu)OZn(OtBu)Me]]2] (9) notable for the retention of labile Zn-C(Me). Amines 4 and 5 afford the oxo-encapsulation products [mu4-O)Zn4[(2-C5H4N)-NBz]6] (10b), and [tBu(mu3-O)-Li3(mu6-O)Zn3[(2-C5H4N)NMe]6] (11), respectively, with concomitant oxo-insertion into a Li-C interaction resulting in capping of the fac-isomeric (mu6-O)M3M'3 distorted octahedral core of the latter complex by a tert-butoxide group.
RESUMO
BACKGROUND: Patients with chronic low back pain present physicians with diagnostic and therapeutic problems. Physical treatments tend to have low success rates and it is postulated that this may be because low back pain can be a manifestation of abnormal illness behaviour. METHODS: A structured prospective study determined the prevalence of somatization in a sample of 131 adult patients with chronic low back pain using the Illness Behaviour Questionnaire (IBQ) and the Modified Somatic Perception Questionnaire (MSPQ). The scores on these psychological questionnaires were compared with the blind interpretation of pain distribution drawings and with the results of a mechanical classification of the patient's symptoms and signs. RESULTS: Fifty-four per cent of patients had four or more (out of five) abnormal illness indicators. The MSPQ values for the group were significantly above the control values in the literature. Thirty-two per cent of pain diagrams were thought to be incompatible with an organic cause when assessed by an orthopaedic surgeon and sixty-two per cent when assessed by a psychiatrist. CONCLUSIONS: Psychosocial factors are dominant in the presentation of chronic low back pain in adults and the disorder is not primarily a musculoskeletal one.