Functionalization of cotton fiber by partial etherification and self-assembly of polyoxometalate encapsulated in Cu3(BTC)2 metal-organic framework.

A combination of a Keggin-type polyoxometalate (POM), [CuPW11O39](5-), with a Cu3(BTC)2 metal-organic framework (MOF-199/HKUST-1; where BTC is benzene-1,3,5-tricarboxylate), was successfully self-assembled on a cellulose substrate (cotton) with a room-temperature process. Cotton fibers were functionalized by partial etherification. Cu3(BTC)2 metal-organic framework and polyoxometalate encapsulated in Cu3(BTC)2 metal-organic framework were self-assembled on the carboxymethylate ion sites initiated with copper nitrate using ethanol and water as solvents. Octahedral crystals were observed on both MOF-cotton and POM-MOF-cotton; both contained copper while the POM-MOF-cotton also contained tungsten. Occupancy of POM in MOF cages was calculated to be about 13%. Moisture content remained at 3 to 4 wt % similar to that of untreated cotton. Reactivity to both hydrogen sulfide and methyl parathion was higher for POM-MOF-cotton due to the Keggin polyoxometalate and the extra-framework cations Cu(2+) ions compensating the charges of the encapsulated Keggins. The POM-MOF material was found to effectively remove 0.089 mg of methyl parathion per mg of MOF from a hexane solution while MOF-cotton removed only 0.054 mg of methyl parathion per mg of MOF.

Effect of plasma etching on destructive adsorption properties of polypropylene fibers containing magnesium oxide nanoparticles.

Dermal absorption of pesticides poses a danger for agricultural workers. Use of personal protection equipment (PPE) is required to provide protection; some of the current PPE involves impermeable barriers. In these barrier materials, the same mechanism that prevents the penetration of toxic chemicals also blocks the passage of water vapor and air from flowing through the material, making the garments uncomfortable. Fibers that degrade organophosphate pesticides, such as methyl parathion, were developed by incorporating metal oxides. These modified fibers can be incorporated into conventional fabric structures that allow water vapor to pass through, thereby maintaining comfort. Fibers with self-decontamination functionality were developed by incorporating magnesium oxide (MgO) nanoparticles into a polypropylene (PP) melt-extruded fiber. These fibers were then treated with plasma etching to expose increased surface area of the MgO nanoparticles. Three steps were involved in this research project: (1) determining the reactivity of MgO and methyl parathion, (2) making melt-spun MgO/PP fibers, and (3) testing the reactivity of MgO/PP composite fibers and methyl parathion. It was confirmed that MgO stoichiometrically degrades methyl parathion by way of destructive adsorption. The etching of the PP fibers containing MgO nanoparticles increased the chemical accessibility of MgO reactive sites, therefore making them more effective in degrading methyl parathion. These fibers can enhance the protection provided by PPE to agricultural and horticultural workers and military personnel.

Metal ion-mediated nitric oxide generation from polyurethanes via covalently linked copper(II)-cyclen moieties.

Polyurethanes are widely used in the manufacturing of biomedical catheters and other blood-contacting devices; however, thrombus formation still occurs, which renders these catheters ineffective unless systemic anticlotting agents are used. Nitric oxide (NO) is a well-known inhibitor of platelet activity. In the current study, two commercially available medical polyurethanes (Pellethane and Tecophilic) were derivatized to possess NO-generating Cu(II)-cyclen moieties pendant to the polymer backbone. A new three-step synthetic approach is used, that is simpler than a recently reported method to prepare Cu(II)-cyclen-polyurethane materials. Both derivatized polyurethanes were found to produce NO at levels at or above those of endothelial cells. A comparison between the modified commercial polyurethanes (hydrophobic vs. hydrophilic) is presented, including the synthetic scheme, extensive characterization, and coating application. These derivatized polymers may serve as useful coatings to prevent clotting on the surface of catheters and other blood-contacting biomedical devices.