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.     

Academic faculty practices: issues for viability in competitive managed care markets

This study compares the perspectives of eighteen managed care executives and twenty-four faculty practice executives on critical policy issues related to the managed care marketplace. Market sites studied in 1994 included four major metropolitan areas: Minneapolis-St. Paul, Los Angeles, Philadelphia, and Atlanta. These markets were selected as being representative of communities with descending degrees of managed care involvement, but with significant market activity. Study participants from both managed care systems and faculty practices examined five policy issues: (1) the importance of including academic medical centers in current and future health care plans for marketing purposes; (2) the provision of clinical services that are unique to the academic medical center, that is, unavailable elsewhere in the community; (3) the degree of financial supplement that employers might pay for including an academic medical center; (4) future restructuring of organizations to sustain the educational mission of academic faculty within a viable delivery system; (5) satisfaction of managed care providers with graduates of academic medical centers, as measured by the clinical skills of graduate physicians. The study findings showed little support among managed care plans for paying supplements to include faculty practices in a health care network. Most study participants from managed care systems and academic faculty practices identified limited competencies that are unique to academic centers. Moreover, managed care organizations were only willing to undertake limited restructuring at best to include faculty practices within their networks. General concern about the preparation of resident physicians (especially those in primary care disciplines) for practice within contemporary managed care organizations existed among managed care informants. The results of the study indicate that as traditional funding sources for medical education are reduced, schools require greater integration with managed care plans to enable academic medical centers and their faculties to continue promoting clinical enterprise.     

The CD40-CD154 system in anti-infective host defense

Research in the past few years has documented significant advances in our understanding of the CD40-CD40 ligand (CD154) system in diverse immune functions. This system influences many T cell mediated inflammatory immune responses and effector functions, unmasking a previously unexpected role for CD40-CD154 in cell mediated immunity. Manipulation of CD154 in animal models of infection by the use of CD154-deficient mice or anti-CD154 antibodies has shown the importance of this system in the initiation of the inflammatory response, in the activation of antigen-presenting cells and in resistance to infections.     

Tuning of MST neurons to spiral motions

Cells in the dorsal division of the medial superior temporal area (MSTd) have large receptive fields and respond to expansion/contraction, rotation, and translation motions. These same motions are generated as we move through the environment, leading investigators to suggest that area MSTd analyzes the optical flow. One influential idea suggests that navigation is achieved by decomposing the optical flow into the separate and discrete channels mentioned above, that is, expansion/contraction, rotation, and translation. We directly tested whether MSTd neurons perform such a decomposition by examining whether there are cells that are preferentially tuned to intermediate spiral motions, which combine both expansion/contraction and rotation components. The finding that many cells in MSTd are preferentially selective for spiral motions indicates that this simple three-channel decomposition hypothesis for MSTd does not appear to be correct. Instead, there is a continuum of patterns to which MSTd cells are selective. In addition, we find that MSTd cells maintain their selectivity when stimuli are moved to different locations in their large receptive fields. This position invariance indicates that MSTd cells selective for expansion cannot give precise information about the retinal location of the focus of expansion. Thus, individual MSTd neurons cannot code, in a precise fashion, the direction of heading by using the location of the focus of expansion. The only way this navigational information could be accurately derived from MSTd is through the use of a coarse, population encoding. Positional invariance and selectivity for a wide array of stimuli suggest that MSTd neurons encode patterns of motion per se, regardless of whether these motions are generated by moving objects or by motion induced by observer locomotion.     

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.