Mixed-Metal MOF-74 Templated Catalysts for Efficient Carbon Dioxide Capture and Methanation

The vast chemical and structural tunability of metal–organic frameworks (MOFs) are beginning to be harnessed as functional supports for catalytic nanoparticles spanning a range of applications. However, a lack of straightforward methods for producing nanoparticle-encapsulated MOFs as efficient heterogeneous catalysts limits their usage. Herein, a mixed-metal MOF, NiMg-MOF-74, is utilized as a template to disperse small Ni nanoclusters throughout the parent MOF. By exploiting the difference in Ni O and Mg O coordination bond strength, Ni²⁺ is selectively reduced to form highly dispersed Ni nanoclusters constrained by the parent MOF pore diameter, while Mg²⁺ remains coordinated in the framework. By varying the ratio of Ni to Mg in the parent MOF, accessible surface area and crystallinity can be tuned upon thermal treatment, influencing CO₂ adsorption capacity and hydrogenation selectivity. The resulting Ni nanoclusters prove to be an active catalyst for CO₂ methanation and are examined using extended X-ray absorption fine structure and X-ray photoelectron spectroscopy. By preserving a segment of the Mg²⁺-containing MOF framework, the composite system retains a portion of its CO₂ adsorption capacity while continuing to deliver catalytic activity. The approach is thus critical for designing materials that can bridge the gap between carbon capture and CO₂ utilization.     

Moment arms and lengths of human upper limb muscles as functions of joint angles

Modeling of musculoskeletal structures requires accurate data on anatomical parameters such as muscle lengths (MLs), moment arms (MAs) and those describing the upper limb position. Using a geometrical model of planar arm movements with three degrees of freedom, we present, in an analytical form, the available information on the relationship between MAs and MLs and joint angles for thirteen human upper limb muscles. The degrees of freedom included are shoulder flexion/extension, elbow flexion/extension, and either wrist flexion/extension (the forearm in supination) or radial/ulnar deviation (the forearm in mid-pronation). Previously published MA/angle curves were approximated by polynomials. ML/angle curves were obtained by combining the constant values of MLs (defined by the distance between the origin and insertion points for a specific upper limb position) with a variable part obtained by multiplying the MA (joint radius) and the joint angle. The MAs of the prime wrist movers in radial/ulnar deviation were linear functions of the joint angle (R2 > or = 0.9954), while quadratic polynomials accurately described their MAs during wrist flexion/extensions. The relationship between MAs and the elbow angle was described by 2nd, 3rd or 5th-order polynomials (R2 > or = 0.9904), with a lesser quality of fit for the anconeus (R2 = 0.9349). In the full range of angular displacements, the length of wrist, elbow and shoulder muscles can change by 8.5, 55 and 200%, respectively.     

Diagnosis of systemic causes of uveitis; a matter of ophthalmologist and internist

OBJECTIVE: To assess how often the aetiology is established in patients with uveitis, what systemic disease are found and what is the contribution of the internist to the diagnostic process. DESIGN: Retrospective study. SETTING: University Hospital Leiden, the Netherlands. METHOD: From January 1987 to April 1992, 342 patients presented with uveitis. All patients underwent a standard ophthalmological examination. Referral to an internist and individualised laboratory screening followed in patients with recurrent, chronic, bilateral or panuveitis. Recorded were: ophthalmological data, results of laboratory screening, results of analysis by the internist, final diagnosis and presence of systemic disease. RESULTS: 149 (44%) patients were examined by the internist, 18 (5.2%) were seen by another specialist. In 169 (49%) patients a specific diagnosis was made. 74 (22%) had a systemic disease, 74 a primary ocular disease. In 28 (8%) a systemic disease was presumed (5% were HLA-B27 positive, 3% had abnormal laboratory results); 5 (1%) patients had endophthalmitis as a complication of a septic process. CONCLUSION: In approximately 1/3 of the patients with uveitis a systemic disease was found. Examination by the internist tailored to the individual patient is essential in the evaluation of uveitis patients.     

The Clausius inequality corrected for heat transfer involving radiation

The objective of this paper is to prove that the Clausius inequality must be re-stated to have general applicability for heat transfer involving radiative fluxes. The integrand (đQ/T) of the Clausius expression applies to heat conduction and convection, but does not hold for most radiative transfer scenarios, with the exception of reversible infinitesimal net blackbody radiation transfer. In other cases involving radiative transfer, the equality holds for a cycle even though irreversible heat addition by radiative transfer occurs. This is without the erroneous presumption of entropy destruction anywhere in the cycle. Thus, the Clausius inequality indicates reversibility for a cycle that includes an irreversible process. Further, in some radiative cases the quantity đQ/T, where T is the boundary temperature, is not the entropy transfer at the system boundary, and in fact, primarily represents entropy production within the system. It is also clear that in another case considered, the quantity đQ/T had no physical meaning whatsoever. Consequently, the Clausius expression has been re-stated so that it is applicable to cycles with processes involving any form of heat transfer. A new integrand (đQ_cc/T + đS_Net,Rad) is presented, allowing the Clausius inequality to generally apply to all heat transfer scenarios. The work in this paper emphasizes the need to re-state other fundamental equations allowing applicability to all heat transfer processes, and draws attention to the unique character of radiative entropy calculations.     

Effect of process distillation on mutagenicity and cell-transformation activity of solvent-refined,coal-derived liquids

Blended SRC-II process streams, representing a full boiling range distillate material, were fractionally distilled into non-overlapping 50 °F cuts with boiling points between 300 and 850 °F. Another set of 18 distillate cuts were obtained with boiling points ranging between 138 and 1055 °F. Distillate cuts were assayed for mutagenic activity using the histidine reversion assay with Salmonella typhimurium strains TA98, TA100, TA1535 and TA1537, as well as for mammalian-cell transformation activity in the Syrian hamster embryo test, and DNA damage in the prophage induction assay. Samples were also separated into chemical class fractions by alumina column chromatography and analysed by high resolution gas chromatography so that the chemical composition of the cuts could be related to their relative activity in the different assays. In the mammalian cell transformation and microbial mutagenicity assays, significant activity was found almost exclusively in distillate cuts with components boiling > 700 °F, with the highest activity in the transformation assay observed for cuts > 800 °F. All of the distillate cuts showed increased levels of DNA damage as expressed by lambda prophage induction in Escherichia coli 8177. However, the greatest activity was associated with distillate cuts with boiling points in the 800 °F + range. Chemical analysis of the 50 °F distillate cuts showed a variety of polycyclic aromatic hydrocarbons (PAH) and amino-PAH compounds to be present in the distillate cuts boiling > 700 °F and essentially absent from cuts boiling < 700 °F. The sample set of non-overlapping (50 °F) cuts were reblended according to the proportions of each cut found in the original blend material. These reblended composites were then assayed to compare their activity with that predicted from the activities of the component distillate cuts. The reblending experiments indicated the microbial mutagenicity response was essentially additive. Mammalian cell transformation activities were non-additive, indicating a compositional effect on the expression of transforming agents in the complex mixture.     

Entities,identities, identifiers and credentials — what does it all mean?

This paper looks at the concepts of entities, identities, identifiers and credentials, their definitions, and how they combine to authenticate an identity to an account, or function, within a service. Credentials can be divided into several different types on the basis of their use, origin and characteristics. In particular, types such as composite, dynamic and derived credentials will be considered, and their applicability within an identity management system. Each credential must be managed through its entire life cycle from initial registration, general use and suspension, to deletion. The notion of public (i.e. freely distributable) and private (i.e. known only to you) aspects of a credential is explored. The bindings, by trusted third parties, of identifiers and public credentials into permits and instruments of proof is explained along with the convenience, but greater exposure, of local information. Several scenarios are analysed in terms of how different types of credentials are employed during the authentication process.     

Ni catalyst promotion of a Cis-selective Pd catalyst for canola oil hydrogenation

A Ni catalyst was added to a cis-selective Pd catalyst in an attempt to further improve the Pd catalyst's cis-selectivity and activity for canola oil hydrogenation. The system was tested under reaction conditions known to be suitable for cis-selective hydrogenation with the Pd catalyst (50 ppm Pd, 70 °C, and 5.2 MPa). Although inactive on its own under these conditions, the addition of 100 ppm Ni increased the hydrogenation activity (from 2.12 to 2.49 10⁻² min⁻¹). Further addition of Ni up to 1000 ppm resulted in no further improvements in activity. The trans isomer contents of the oils hydrogenated with Pd and the Pd/Ni systems were similar. The level of conjugated dienes decreased rapidly during hydrogenation with both Pd alone and with the Pd/Ni combination and no changes in conjugation were detected in the presence of the Ni catalyst alone. The increased activity of the Pd/Ni system over Pd alone was attributed to adsorption of catalyst poisons from the oil by Ni.     

Prevention and Mitigation Strategies to Address Recent Brittle Fractures in Steel Bridges

Brittle fracture results in unplanned loss of service, very costly repairs, concern regarding the future safety of the structure, and potential loss of life. These types of failures are most critical when there is no evidence of fatigue cracking leading up to the fracture and the fracture origin is concealed from view. Hence, the failure occurs without warning and the details are, essentially, noninspectable. In these cases, it appears desirable to take a proactive approach and introduce preventative retrofits to reduce the potential for future crack development. These efforts will help ensure that the likelihood of unexpected fractures is minimized. This paper examines the behavior of two bridge structures in which brittle fractures have developed in recent times, discusses the causes of the failures, and offers suggested design strategies for prevention and retrofit mitigation techniques. In situations where considerable uncertainty exists in the prediction of accumulated damage or in the ability to reliably inspect critical details, preemptive retrofit strategies appear to be highly desirable.