Nonleaching Biocidal N-Halamine-Functionalized Polyamine-, Guanidine-, and Hydantoin-Based Coatings.

Fibrous materials with inherent antimicrobial properties can help in real-time deactivation of microorganisms, enabling multiple uses while reducing secondary infections. Coatings with antiviral polymers enhance the surface functionality for existing and potential future pandemics. Herein, we demonstrated a straightforward route toward biocidal surface creation using polymers with nucleophilic biguanide, guanidine, and hydantoin groups that are covalently attached onto a solid support. Biocidal poly(N-vinylguanidine) (PVG) and poly(allylamine-co-4-aminopyridine-co-5-(4-hydroxybenzylidene)hydantoin) (PAH) were introduced for coating applications along with commercially available polyvinylamine (PVAm) and poly(hexamethylene biguanide) (PHMB). Nonleaching coatings were created by first fabricating bifunctional siloxane or isocyanate precursor coatings on the cotton, nylon-cotton, and glass fiber fabric, followed by the polymer attachment. The developed grafting methods ensured the stability of the coating and the reuse of the material while maintaining the biocidal properties. Halogenation of polymer-coated fabric was conducted by aqueous solutions of sodium hypochlorite or in situ generation of hypobromous acid (HOBr), resulting in surfaces coated by N-halamines with high contents of active > N-Cl or > N-Br groups. The polymer-coated fabrics were stable in multiple laundry cycles and maintained hydrophilic character after coating and halogenation. Halogenated polymer-coated fabrics completely inactivated human respiratory coronavirus based on a contact-killing mechanism and were shown to be reusable after recharging with bromine or chlorine.

Multifunctional polymeric guanidine and hydantoin halamines with broad biocidal activity.

Prolonged and excessive use of biocides during the coronavirus disease era calls for incorporating new antiviral polymers that enhance the surface design and functionality for existing and potential future pandemics. Herein, we investigated previously unexplored polyamines with nucleophilic biguanide, guanidine, and hydantoin groups that all can be halogenated leading to high contents of oxidizing halogen that enables enhancement of the biocidal activity. Primary amino groups can be used to attach poly(N-vinylguanidine) (PVG) and poly(allylamine-co-4-aminopyridine-co-5-(4-hydroxybenzylidene)hydantoin) (PAH) as well as a broad-spectrum commercial biocide poly(hexamethylene biguanide) (PHMB) onto a solid support. Halogenation of polymer suspensions was conducted through in situ generation of excess hypobromous acid (HBrO) from bromine and sodium hydroxide or by sodium hypochlorite in aqueous solutions, resulting in N-halamines with high contents of active > N-Br or > N-Cl groups. The virucidal activity of the polymers against human respiratory coronavirus HCoV-229E increased dramatically with their halogenation. Brominated PHMB-Br showed activation activity value > 5 even at 1 mg/L, and complete virus inhibition was observed with either PHMB-Br or PAH-Br at 10 mg/mL. Brominated PVG-Br and PAH-Br possessed fungicidal activity against C. albicans, while PHMB was fungistatic. PHMB, PHMB-Br and PAH polymers demonstrated excellent bactericidal activity against the methicillin-resistant S. aureus and vancomycin-resistant E. faecium. Brominated polymers (PHMB-Br, PVG-Br, PAH-Br) were not toxic to the HeLa monolayers, indicating acceptable biocompatibility to cultured human cells. With these features, the N-halamine polymers of the present study are a worthwhile addition to the arsenal of biocides and are promising candidates for development of non-leaching coatings.

Capture and electrochemical conversion of CO2 in molten alkali metal borate-carbonate blends.

A family of blended compositions of molten mixed lithium and sodium borate (Li1.5Na1.5BO3) and eutectic lithium-potassium carbonate (Li1.24K0.76CO3) salts has been introduced as reversible carbon dioxide absorbents and as media for CO2 electrolysis for carbon conversion. Material properties, temperature effects and kinetics of CO2 uptake were examined. Li, Na borate can absorb up to 7.3 mmol g-1 CO2 at 600 °C. The blended borate-carbonate compositions are molten in the 550-600 °C temperature range, with viscosity adjustable to within a 10-1000 Pa s window depending on the borate/carbonate ratio. The blends can withstand cyclic temperature and CO2 pressure swings without significant deterioration of their CO2 uptake capabilities. Addition of eutectic carbonate into mixed Li, Na borate salts lowers overall CO2 uptake due to the lower solubility of CO2 in carbonate. However, addition of the eutectic lowers the temperature of the pressure swing operation and dramatically accelerates the CO2 uptake during the initial stage of the absorption, potentially enabling a faster cycling. Electroreduction of CO2 and carbon deposition on a galvanized steel cathode was more effective with increasing carbonate fraction in the molten alkali borate/carbonate blend. Blended borate/carbonate compositions with 50-60% borate content possessed sufficiently high loading capacity for CO2 and simultaneously enabled maximum carbon product yield and Coulombic efficiency. Most of the recovered carbon product was shown to be in the form of multiwalled carbon nanotube.

Oxidation of betrixaban to yield N-nitrosodimethylamine by water disinfectants.

Degradation of betrixaban, an oral anticoagulant recently approved by the U.S. Food and Drug Administration (FDA), and its N-nitrosodimethylamine (NDMA) formation potential were studied mechanistically in the presence of monochloramine (NH2Cl), free chlorine, and ozone. Upon monochloramination, the formation of NDMA exceeded 1% at basic pH and was significant at circumneutral pH as well. The kinetic studies revealed that the reaction between betrixaban and monochloramine followed pseudo-first-order reaction kinetics. Increasing monochloramine concentration, its reaction time, and pH all significantly enhanced the NDMA formation yield, which also increased three-fold in the presence of bromide during monochloraminantion. The presence of nitrite inhibited the formation of NDMA under the same conditions. This study revealed a new potent and significant precursor of NDMA, indicating that monochloramination of waters containing betrixaban can lead to the formation of NDMA and other disinfection by-products such as dichloroacetonitrile (DCAN) and dimethylformamide (DMF). Moreover, chlorination of betrixaban by hypochlorite also yielded NDMA, albeit at two orders of magnitude lower yield than chloramination, while no NDMA formation was observed from ozonation of betrixaban.

Polydiacetylene functionalized with charged termini for device-free colorimetric detection of malathion.

We introduce 10,12-Pentacosadiynoic acid conjugated with pyridine-2-aldoxime (pralidoxime, PAM) as a positively charged amphiphilic molecule capable of forming a polymer with polydiacetylene (PDA-PAM) via 1,4-addition photopolymerization of self-assembled PAM-modified monomers. Colloidally stabilized vesicles formed by PDA-PAM and unmodified pentacosadiynoic acid via electrostatic interactions in a basic aqueous medium exhibit a colorimetric transition in the presence of malathion. The malathion detection limit, through color change observed by the naked eye, is in the mM range (liquid suspension) or at nmol/cm2 levels (solid membrane); the response to exposure to malathion was rapid, within seconds. Density functional theory (DFT) calculations on the PDA-PAM system before and after binding with the target molecule (malathion) demonstrate that the large blue absorption shift of 0.42 eV observed in the malathion-bound configuration of the polymer is due to the dissociation of the positive charge center on the pralidoxime functional group from the negative charge center on the carboxylic terminus.

Postsynthetic Functionalization of Mg-MOF-74 with Tetraethylenepentamine: Structural Characterization and Enhanced CO2 Adsorption.

Postsynthetic functionalization of magnesium 2,5-dihydroxyterephthalate (Mg-MOF-74) with tetraethylenepentamine (TEPA) resulted in improved CO2 adsorption performance under dry and humid conditions. XPS, elemental analysis, and neutron powder diffraction studies indicated that TEPA was incorporated throughout the MOF particle, although it coordinated preferentially with the unsaturated metal sites located in the immediate proximity to the surface. Neutron and X-ray powder diffraction analyses showed that the MOF structure was preserved after amine incorporation, with slight changes in the lattice parameters. The adsorption capacity of the functionalized amino-Mg-MOF-74 (TEPA-MOF) for CO2 was as high as 26.9 wt % versus 23.4 wt % for the original MOF due to the extra binding sites provided by the multiunit amines. The degree of functionalization with the amines was found to be important in enhancing CO2 adsorption, as the optimal surface coverage improved performance and stability under both pure CO2 and CO2/H2O coadsorption, and with partially saturated surface coverage, optimal CO2 capacity could be achieved under both wet and dry conditions by a synergistic binding of CO2 to the amines as well as metal centers.

Self-Decontaminating Fibrous Materials Reactive toward Chemical Threats.

Polymers that possess highly nucleophilic pyrrolidinopyridine (Pyr) and primary amino (vinylamine, VAm) groups were prepared by free-radical copolymerization of N,N-diallylpyridin-4-amine (DAAP) and N-vinylformamide (NVF) followed by acidic hydrolysis of NVF into VAm. The resulting poly(DAAP-co-VAm-co-NVF) copolymers were water-soluble and reacted with water-dispersible polyurethane possessing a high content of unreacted isocyanate groups. Spray-coating of the nylon-cotton (NYCO), rayon, and poly(p-phenylene terephthalamide) (Kevlar 119) fibers pretreated with phosphoric acid resulted in covalent bonding of the polyurethane with the hydroxyl groups on the fiber surface. A second spray-coating of aqueous solutions of poly(DAAP-co-VAm-co-NVF) on the polyurethane-coated fiber enabled formation of urea linkages between unreacted isocyanate groups of the polyurethane layer and the amino groups of poly(DAAP-co-VAm-co-NVF). Fibers with poly(DAAP-co-VAm-co-NVF) attached were compared with fibers modified by adsorption of water-insoluble poly(butadiene-co-pyrrolidinopyridine) (polyBPP) in terms of the stability against polymer leaching in aqueous washing applications. While the fibers modified by attachment of poly(DAAP-co-VAm-co-NVF) exhibited negligible polymer leaching, over 65% of adsorbed polyBPP detached and leached from the fibers within 7 days. Rayon fibers modified by poly(DAAP-co-VAm-co-NVF) were tested for sorption of dimethyl methylphosphonate (DMMP) in the presence of moisture using dynamic vapor sorption technique. Capability of the fibers modified with poly(DAAP-co-VAm-co-NVF) to facilitate hydrolysis of the sorbed DMMP in the presence of moisture was uncovered. The self-decontaminating property of the modified fibers against chemical threats was tested using a CWA simulant diisopropylfluorophosphate (DFP) in aqueous media at pH 8.7. Fibers modified with poly(DAAP-co-VAm-co-NVF) facilitated hydrolysis of DFP with the half-lives up to an order of magnitude shorter than that of the unmodified fibers. The presented polymers and method of multilayer coating can lead to a development of self-decontaminating textiles and other materials.

Sensing and inactivation of Bacillus anthracis Sterne by polymer-bromine complexes.

We report on the performance of brominated poly(N-vinylpyrrolidone) (PVP-Br), brominated poly(ethylene glycol) (PEG-Br), and brominated poly(allylamine-co-4-aminopyridine) (PAAm-APy-Br) for their ability to decontaminate Bacillus anthracis Sterne spores in solution while also allowing for the sensing of the spores. The polymers were brominated by bromine using carbon tetrachloride or potassium tribromide as solvents, with bromine loadings ranging from 1.6 to 4.2 mEq/g of polymer. B. anthracis Sterne spores were exposed to increasing concentrations of brominated polymers for 5 min, while the kinetics of the sporicidal activity was assessed. All brominated polymers demonstrated spore log-kills of 8 within 5 min of exposure at 12 mg/mL aqueous polymer concentration. Sensing of spores was accomplished by measuring the release of dipicolinic acid (DPA) from the spore using time-resolved fluorescence. Parent, non-brominated polymers did not cause any release of DPA and the spores remained viable. In contrast, spores exposed to the brominated polymers were inactivated and the release of DPA was observed within minutes of exposure. Also, this release of DPA continued for a long time after spore inactivation as in a controlled release process. The DPA release was more pronounced for spores exposed to brominated PVP and brominated PEG-8000 compared to brominated PAAm-APy and brominated PEG-400. Using time-resolved fluorescence, we detected as low as 2500 B. anthracis spores, with PEG-8000 being more sensitive to low spore numbers. Our results suggest that the brominated polymers may be used effectively as decontamination agents against bacterial spores while also providing the sensing capability.

Magnetic Surfactants and Polymers with Gadolinium Counterions for Protein Separations.

New magnetic surfactants, (cationic hexadecyltrimethlyammonium bromotrichlorogadolinate (CTAG), decyltrimethylammonium bromotrichlorogadolinate (DTAG), and a magnetic polymer (poly(3-acrylamidopropyl)trimethylammonium tetrachlorogadolinate (APTAG)) have been synthesized by the simple mixing of the corresponding surfactants and polymer with gadolinium metal ions. A magnetic anionic surfactant, gadolinium tri(1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate) (Gd(AOT)3), was synthesized via metathesis. Both routes enable facile preparation of magnetically responsive magnetic polymers and surfactants without the need to rely on nanocomposites or organic frameworks with polyradicals. Electrical conductivity, surface tensiometry, SQUID magnetometry, and small-angle neutron scattering (SANS) demonstrate surface activity and self-aggregation behavior of the magnetic surfactants similar to their magnetically inert parent analogues but with added magnetic properties. The binding of the magnetic surfactants to proteins enables efficient separations under low-strength (0.33 T) magnetic fields in a new, nanoparticle-free approach to magnetophoretic protein separations and extractions. Importantly, the toxicity of the magnetic surfactants and polymers is, in some cases, lower than that of their halide analogues.

Nucleophilic Polymers and Gels in Hydrolytic Degradation of Chemical Warfare Agents.

Water- and solvent-soluble polymeric materials based on polyalkylamines modified with nucleophilic groups are introduced as catalysts of chemical warfare agent (CWA) hydrolysis. A comparative study conducted at constant pH and based on the criteria of the synthetic route simplicity, aqueous solubility, and rate of hydrolysis of CWA mimic, diisopropylfluorophosphate (DFP), indicated that 4-aminopyridine-substituted polyallylamine (PAAm-APy) and polyvinylamine substituted with 4-aminopyridine (PVAm-APy) were advantageous over 4-pyridinealdoxime-modified PVAm and PAAm, poly(butadiene-co-pyrrolidinopyridine), and PAAm modified with bipyridine and its complex with Cu(II). The synthesis of PVAm-APy and PAAm-APy involved generation of a betaine derivative of acrylamide and its covalent attachment onto the polyalkylamine chain followed by basic hydrolysis. Hydrogel particles of PAAm-APy and PVAm-APy cross-linked by epichlorohydrin exhibited pH-dependent swelling and ionization patterns that affected the rate constants of DFP nucleophilic hydrolysis. Deprotonation of the aminopyridine and amine groups increased the rates of the nucleophilic hydrolysis. The second-order rate of nucleophilic hydrolysis was 5.5- to 10-fold higher with the nucleophile-modified gels compared to those obtained by cross-linking of unmodified PAAm, throughout the pH range. Testing of VX and soman (GD) was conducted in 2.5-3.7 wt % PVAm-APy suspensions or gels swollen in water or DMSO/water mixtures. The half-lives of GD in aqueous PVAm-APy were 12 and 770 min at pH 8.5 and 5, respectively. Addition of VX into 3.5-3.7 wt % suspensions of PVAm-APy in DMSO-d6 and D2O at initial VX concentration of 0.2 vol % resulted in 100% VX degradation in less than 20 min. The unmodified PVAm and PAAm were 2 orders of magnitude less active than PVAm-APy and PAAm-APy, with VX half-lives in the range of 24 h. Furthermore, the PVAm-APy and PAAm-APy gels facilitated the dehydrochlorination reaction of sulfur mustard (HD) and its analogue 2-chloroethyl ethylsulfide (CEES). The ability of the reported aminopyridine-modified polyalkylamine materials to degrade the most persistent of CWAs, coupled with aqueous solubility, and the presence of numerous amino groups that provide convenient "handles" for covalent attachment on polymeric and inorganic supports yields promise for applications such as protective fabric and textile treatment and components of decontaminating materials.

Heteropolyacid-functionalized aluminum 2-aminoterephthalate metal-organic frameworks as reactive aldehyde sorbents and catalysts.

Porous materials based on aluminum(III) 2-aminoterephthalate metal organic frameworks (MOFs NH2MIL101(Al) and NH2MIL53(Al)) and their composites with phosphotungstic acid (PTA) were studied as sorbents of saturated vapors of acetaldehyde, acrolein, and butyraldehyde. MOF functionalization by PTA impregnation from aqueous/methanol solutions resulted in MOF with the original crystal topology with the presence of an ordered PTA phase in the MOF/PTA composite. The MOF/PTA composites contained 29-32 wt % PTA and were stable against loss of PTA through leaching to the aqueous/organic solvent solutions. The MOF and MOF/PTA materials exhibited equilibrium uptake of acetaldehyde from its saturated vapor phase exceeding 50 and 600 wt %, respectively, at 25 °C. The acetaldehyde vapor uptake occurs through the vapor condensation, pore-filling mechanism with simultaneous conversion of acetaldehyde to crotonaldehyde and higher-molecular-weight compounds resulting from repeated aldol condensation. The products of aldehyde condensation and polymerization were identified by MALDI-TOF and electrospray mass spectrometry. The kinetics of the MOF- and MOF/PTA-catalyzed aldol condensation of acetaldehyde were studied in water-acetonitrile mixtures. The aldol condensation kinetics in MOF suspensions were rapid and pseudo-first-order. The apparent second-order rate constants for the aldol condensation catalyzed by MOF/PTA were estimated to be 5 × 10(-4) to 1.5 × 10(-3) M(-1)s(-1), which are higher than those reported in the case of homogeneous catalysis by amino acids or sulfuric acid. MOF and MOF/PTA materials are efficient heterogeneous catalysts for the aldehyde self-condensation in aqueous-organic media.

Organophophorous ester degradation by chromium(III) terephthalate metal-organic framework (MIL-101) chelated to N,N-dimethylaminopyridine and related aminopyridines.

Porous materials based on chromium(III) terephthalate metal organic frameworks (MOF) MIL-101(Cr) and their complexes with dialkylaminopyridines (DAAP) were synthesized via a DAAP-MOF complexation, and tested for hydrolytic degradation of organophosphorous esters such as diethyl 4-nitrophenyl phosphate (paraoxon). Elemental analysis, TGA, XRD, FT-IR, TEM, SEM, and nitrogen adsorption measurements indicated that the DAAP units were incorporated into MIL-101 pores by complexation, keeping the parent framework intact. The DAAP-MOF enabled facile paraoxon hydrolysis in water/acetonitrile mixtures under ambient conditions (100% conversion after 24 h at pH 10). The MOF-DAAP complexes showed synergistic effects, being 7-fold and 47-fold more active than the parent MIL-101 or DAAP materials, respectively. The high hydrolysis reaction turnover was realized by simultaneous action of the Lewis acid Cr(III) center of the MOF as well as the electron-rich nucleophile, DAAP. This study demonstrates a simple and efficient method of generating catalytically active MOF materials for environmental detoxification as well as defensive applications.

Interplay of electron hopping and bounded diffusion during charge transport in redox polymer electrodes.

Redox polymer electrodes (RPEs) have been prepared both by attachment of random copolymers of hydroxybutyl methacrylate and vinylferrocene (poly(HBMA-co-VF)) to carbon substrates by grafting either "to" or "from" the substrate surfaces, and by impregnation of porous carbon substrates with redox polymer gels of similar composition. An observed linear dependence of peak current on the square root of the applied voltage scan rate in cyclic voltammetry (CV) led to the conclusion that the rate controlling step in the redox process was the diffusive transfer of electrons through the redox polymer layer. The variation in the peak current with increasing concentration of the redox species in the polymer indicated that the electron transport transitioned from bounded diffusion to electron hopping. A modified form of the Blauch-Saveant equation for apparent diffusivity of electrons through a polymer film indicated that bounded diffusion was the dominant mechanism of electron transport in RPEs with un-cross-linked polymer chains at low concentrations of the redox species, but, as the concentration of the redox species increased, electron hopping became more dominant, and was the primary mode of electron diffusion above a certain concentration level of redox species. In the cross-linked polymer gels, bounded diffusion was limited because of the restricted mobility of the polymer chains. Electron hopping was the primary mode of electron diffusion in such systems at all concentrations of the redox species.

Intracellular Delivery of siRNA by Polycationic Superparamagnetic Nanoparticles.

The siRNA transfection efficiency of nanoparticles (NPs), composed of a superparamagnetic iron oxide core modified with polycationic polymers (poly(hexamethylene biguanide) or branched polyethyleneimine), were studied in CHO-K1 and HeLa cell lines. Both NPs demonstrated to be good siRNA transfection vehicles, but unmodified branched polyethyleneimine (25 kD) was superior on both cell lines. However, application of an external magnetic field during transfection (magnetofection) increased the efficiency of the superparamagnetic NPs. Furthermore, our results reveal that these NPs are less toxic towards CHO-K1 cell lines than the unmodified polycationic-branched polyethyleneimine (PEI). In general, the external magnetic field did not alter the cell's viability nor it disrupted the cell membranes, except for the poly(hexamethylene biguanide)-modified NP, where it was observed that in CHO-K1 cells application of the external magnetic field promoted membrane damage. This paper presents new polycationic superparamagnetic NPs as promising transfection vehicles for siRNA and demonstrates the advantages of magnetofection.

Alkylaminopyridine-modified aluminum aminoterephthalate metal-organic frameworks as components of reactive self-detoxifying materials.

Aluminum aminoterephthalate MOF particulate materials (NH(2)-MIL-101(Al) and NH(2)-MIL-53(Al)), studied here as components of self-detoxifying surfaces, retained their reactivity following their covalent attachment to protective surfaces utilizing a newly developed strategy in which the MOF particles were deposited on a reactive adhesive composed of polyisobutylene/toluene diisocyanate (PIB/TDI) blends. Following MOF attachment and curing, the MOF primary amino groups were functionalized with highly nucleophilic 4-methylaminopyridine (4-MAP) by disuccinimidyl suberate-activated conjugation. The resulting MOF-4-MAP modified PIB/TDI elastomeric films were mechanically flexible and capable of degrading diisopropyl fluorophosphate (DFP), a chemical threat simulant.

Antiviral properties of polymeric aziridine- and biguanide-modified core-shell magnetic nanoparticles.

Polycationic superparamagnetic nanoparticles (∼150-250 nm) were evaluated as virucidal agents. The particles possess a core-shell structure, with cores consisting of magnetite clusters and shells of functional silica covalently bound to poly(hexamethylene biguanide) (PHMBG), polyethyleneimine (PEI), or PEI terminated with aziridine moieties. Aziridine was conjugated to the PEI shell through cationic ring-opening polymerization. The nanometric core-shell particles functionalized with biguanide or aziridine moieties are able to bind and inactivate bacteriophage MS2, herpes simplex virus HSV-1, nonenveloped infectious pancreatic necrosis virus (IPNV), and enveloped viral hemorrhagic septicaemia virus (VHSV). The virus-particle complexes can be efficiently removed from the aqueous milieu by simple magnetocollection.

Aldehyde-alcohol reactions catalyzed under mild conditions by chromium(III) terephthalate metal organic framework (MIL-101) and phosphotungstic acid composites.

Porous materials based on chromium(III) terephthalate metal organic frameworks (MIL-101) and their composites with phosphotungstic acid (PTA) were studied as heterogeneous acid catalysts in aldehyde-alcohol reactions exemplified by acetaldehyde-phenol (A-P) condensation and dimethylacetal formation from benzaldehyde and methanol (B-M reaction). The MIL-101 was synthesized solvothermically in water, and the MIL101/PTA composite materials were obtained by either impregnation of the already prepared MIL-101 porous matrix with phosphotungstic acid solution or by solvothermic treatment of aqueous mixtures of Cr(NO(3))(3), and terephthalic and phosphotungstic acids. The MIL101/PTA materials appeared to be effective catalysts for both A-P and B-M reactions occurring at room temperature, with half-lives ranging from 0.5 h (A-P) to 1.5-2 h (B-M) and turnover numbers over 600 for A-P and over 2900 for the B-M reaction, respectively. A synergistic effect of the strong acidic moieties (PTA) addition to mildly acidic Brønsted and Lewis acid cites of the MIL-101 was observed with the MIL101/PTA composites. The ability of the PTA and MIL101/PTA materials to strongly absorb and condense acetaldehyde vapors was discovered, with the MIL101/PTA absorbing over 10-fold its dry weight of acetaldehyde condensate at room temperature. The acetaldehyde was converted rapidly to crotonaldehyde and higher-molecular-weight compounds while in contact with MIL-101 and MIL101/PTA materials. The stability of the MIL-101 and MIL101/PTA catalysts was assessed within four cycles of the 1-day alcohol-aldehyde reactions in terms of the overall catalyst recovery, PTA or Cr content, and reaction rate constants in each cycle. The loss of the catalyst over 4 cycles was approximately 10 wt % for all tested catalysts due to the incomplete recovery and minute dissolution of the components. The reaction rates in all cycles remained unchanged and the catalyst losses stopped after the third cycle. The developed MIL101/PTA composites appear to be feasible for industrial catalytic applications.

Electrospun polyurethane fibers for absorption of volatile organic compounds from air.

Electrospun polyurethane fibers for removal of volatile organic compounds (VOC) from air with rapid VOC absorption and desorption have been developed. Polyurethanes based on 4,4-methylenebis(phenylisocyanate) (MDI) and aliphatic isophorone diisocyanate as the hard segments and butanediol and tetramethylene glycol as the soft segments were electrospun from their solutions in N,N-dimethylformamide to form micrometer-sized fibers. Although activated carbon possessed a many-fold higher surface area than the polyurethane fiber meshes, the sorption capacity of the polyurethane fibers was found to be similar to that of activated carbon specifically designed for vapor adsorption. Furthermore, in contrast to VOC sorption on activated carbon, where complete regeneration of the adsorbent was not possible, the polyurethane fibers demonstrated a completely reversible absorption and desorption, with desorption obtained by a simple purging with nitrogen at room temperature. The fibers possessed a high affinity toward toluene and chloroform, but aliphatic hexane lacked the necessary strong attractive interactions with the polyurethane chains and therefore was less strongly absorbed. The selectivity of the polyurethane fibers toward different vapors, along with the ease of regeneration, makes them attractive materials for VOC filtration.

Electrospray as a tool for drug micro- and nanoparticle patterning.

Carbamazepine (CBZ) microparticles of different sizes and shapes, including spheres, q-tips, elongated spheres, and tear-shaped particles, were formed by electrospraying solutions of different CBZ concentrations. The particle characteristics were determined by the interplay between jet formation, droplet breakup, solvent evaporation, and eventual particle solidification. The average particle size increased with increasing CBZ concentration, with particles of different shapes being observed for different CBZ concentrations. The cascade of sizes and shapes observed was interpreted in terms of Rayleigh instability theory as applied to charged jets and droplets, with the final sizes depending upon the time needed to evaporate the solvent sufficiently for CBZ to solidify; the lower the initial concentration of CBZ, the smaller the final droplets/particles that are formed.

Redox-responsive gels with tunable hydrophobicity for controlled solubilization and release of organics.

The hydrophobicity of the chemical environment within a redox-responsive polymer gel synthesized by copolymerization of hydroxybutyl methacrylate (HBMA) and vinylferrocene (VF) can be controlled by tuning the oxidation state of the redox-responsive moiety, ferrocene. When ferrocene is in the uncharged reduced state, the gel is hydrophobic and selectively extracts butanol from aqueous solution. Upon oxidation to ferricenium ions, charge is induced at the ferrocene sites making the gel hydrophilic, with a reduced capacity for butanol relative to water. Equilibrium distribution coefficients and separation factors provide quantitative evidence for this changing preference for butanol depending on oxidation state. The selection of the monomer constituting the polymer backbone, HBMA, was based on an initial screening using the Hansen solubility parameters of commercially available monomers. The effect of the various constituents of the gel on the gel's butanol extraction ability has been ascertained experimentally.