Among the large family of metal-organic frameworks (MOFs), Zr-based MOFs, which exhibit rich structure types, outstanding stability, intriguing properties and functions, are foreseen as one of the most promising MOF materials for practical applications. Although this specific type of MOF is still in its early stage of development, significant progress has been made in recent years. Herein, advances in Zr-MOFs since 2008 are summarized and reviewed from three aspects: design and synthesis, structure, and applications. Four synthesis strategies implemented in building and/or modifying Zr-MOFs as well as their scale-up preparation under green and industrially feasible conditions are illustrated first. Zr-MOFs with various structural types are then classified and discussed in terms of different Zr-based secondary building units and organic ligands. Finally, applications of Zr-MOFs in catalysis, molecule adsorption and separation, drug delivery, and fluorescence sensing, and as porous carriers are highlighted. Such a review based on a specific type of MOF is expected to provide guidance for the in-depth investigation of MOFs towards practical applications.
Metal-organic frameworks (MOFs) are a category of porous materials that offer unparalleled control over their surface areas (demonstrated as higher than for any other material), pore characteristics, and functionalization. This allows them to be customized for exceptional performance in a wide variety of applications, most commonly including gas storage and separation, drug delivery, luminescence, or heterogeneous catalysis. In order to optimize biomimicry, controlled separations and storage of small molecules, and detailed testing of structure-property relationships, one major goal of MOF research is "rational design" or "pore engineering", or precise control of the placement of multiple functional groups in pores of chosen sizes and shapes. MOF crystal growth can be controlled through judicious design of stepwise synthetic routes, which can also allow functionalization of MOFs in ways that were previously synthetically inaccessible. Organic chemists have developed a library of powerful techniques over the last century, allowing the total synthesis and detailed customization of complex molecules. Our hypothesis is that total synthesis is also possible for customized porous materials, through the development of similar multistep techniques. This will enable the rational design of MOFs, which is a major goal of many researchers in the field. We have begun developing a library of stepwise synthetic techniques for MOFs, allowing the synthesis of ultrastable MOFs with multiple crystallographically ordered and customizable functional groups at controlled locations within the pores. In order to design MOFs with precise control over pore size and shape, stability, and the placement of multiple different functional groups within the pores at tunable distances from one another, we have concentrated on methods which allow us to circumvent the lack of control inherent to one-pot MOF crystallization. Kinetically tuned dimensional augmentation (KTDA) is an approach using preformed metal clusters as starting materials and monotopic carboxylates as equilibrium shifting agents to make single crystals of ultrastable MOFs. Postsynthetic metathesis and oxidation (PSMO) takes advantage of the fast ligand exchange rate of a metal ion at the low oxidation state as well as the kinetic inertness of the same metal at high oxidation state to make ultrastable and highly crystalline MOFs. Multiple similar strategies have been successful for the metathesis of Fe-based MOFs to Cr. Several highly crystalline Ti-MOFs have also been prepared. Kinetically controlled linker installation and cluster metalation methods utilize a stable MOF with inherent coordinatively unsaturated sites as matrix and postsynthetically install linkers or grow clusters on the matrix, so that a robust MOF with precisely placed functionalities is realized. This method has diverse applications especially when specific functional groups or metals having synergistic effects are desired in the proper proximity. Exceptional porosity and stability are required for many potenti...
The origin of cancer health disparities and mortality in Arkansas is multifactorial. In response to a cooperative agreement with the National Cancer Institute's Center to Reduce Cancer Health Disparities, the Arkansas Special Populations Access Network (ASPAN) was developed to reduce these disparities. ASPAN's partnership with local primary care physicians of the Arkansas Medical, Dental, and Pharmaceutical Association through the Cancer Education Awareness Program is the focus of this article. A quasi‐experimental intervention, the Community Cancer Education Awareness Program, was employed that included 1) physician education to increase awareness of risk factors and cancer screening; and 2) patient education to increase screening, and 3) patient‐generated screening questionnaires to prompt discussion of cancer risk and screening recommendations between patients and physicians. Two urban and 2 rural clinics were targeted during a 12‐month period with interval intervention assessments. Baseline review of records (n = 200) from patients ≥40 were utilized to assess the rate of breast, prostate, and colorectal screenings among clinics. For the patient education intervention, patients (n = 120) were interviewed via a 34‐item assessment. Physician awareness of cancer risk factors and screening recommendations significantly increased. Statistically significant increases were seen for prostate (P = .028), breast (P = .036), and colorectal (P < .001) cancer screening across all 4 clinics. Patients' increased likelihood of cancer screenings was associated with knowledge about consumption of animal fat (P < .001), dietary fiber (P < .013), and mammograms (P < .001). Utilizing the physician as the central change agent, the ASPAN provider network successfully enhanced cancer screening awareness of minority physicians and their patients. Cancer 2006. © 2006 American Cancer Society.
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