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-<i>co</i>-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-<i>d</i>₆ 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

Alkylaminopyridine-Modified Aluminum Aminoterephthalate Metal-Organic Frameworks As Components of Reactive Self-Detoxifying Materials

Aluminum aminoterephthalate MOF particulate materials (NH₂-MIL-101­(Al) and NH₂-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

Thermoelectric Enhancement by Compositing Carbon Nanotubes into Iodine-Doped Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]

Free-standing iodine-doped composite samples of poly­[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) with carbon nanotubes (NTs) showed thermoelectric (TE) power factors (PFs) up to 33 μW·m^–1·K^–2 after optimizing multiple factors, including: (1) sample fabrication solvent, (2) doping time, (3) average MEH-PPV molecular weight, (4) NT fraction in the composite, and (5) use of single-wall versus multi-wall nanotubes (SWNT and MWNT, respectively). Composite fabrication from halogenated solvents gave the best TE performance after iodine doping times of 2–4 h; performance drops substantially in ∼20 h doped samples. TE performance dropped after at least 24 h of removal from iodine vapor but was fully restored upon re-exposure to the dopant. Longer-chain MEH-PPV gave not only mechanically stronger films but also higher PFs in doped SWNT composites. MWNT composites gave low PFs, attributed to poor NT dispersion. Scanning electron microscopy showed increasingly extensive network formation as NT fraction increased in the composites; this phase separation provides charge transport pathways that improve thermoelectric PFs. The results support a strategy of producing phase-separated materials having both electrical conduction enhanced regions and Seebeck thermopower retaining regions to maximize organic TE response

All-Organic, Stimuli-Responsive Polymer Composites with Electrospun Fiber Fillers

Stimuli-responsive materials are desired for a wide range of applications. Here, we report the design and fabrication of all-organic, stimuli-responsive polymer composites using electrospun nanofibers as the filler. The incorporation of 4 wt % of filler into the polymer matrix increased the tensile storage modulus by 2 orders of magnitude. Upon exposure to water, the filler fibers plasticize and no longer provide mechanical reinforcement. The tensile storage modulus subsequently diminishes 2 orders of magnitude to the value of the neat matrix polymer