Gold nanoparticles-conjugation of irisin enhances therapeutic effect by improving cardiac function and attenuating inflammation in sepsis.

Irisin is considered to be a promising therapeutic approach for cardiac depression and inflammatory disorders. The short half-life of irisin impeded its use and drug efficacy in the treatment. This study aimed to examine if pegylated gold nanoparticles-conjugated to irisin would improve therapeutic effects in cecal ligation and puncture (CLP)-induced sepsis in mice. Recombinant irisin were conjugated to a pegylated gold nanoparticle, which was given to mice exposed to CLP. The cecal ligation procedure and sham on mice were operated and assigned to one of following five groups: (I) CLP group: The mouse models underwent the CLP surgical procedure and received only vehicle saline treatment (n = 5); (II) CLP + soluble Irisin: The mouse underwent the CLP and received an intramuscular injection (i.m) (TA) injection of 1 ug of soluble irisin into each tibialis anterior (TA) leg (n = 5); (III) CLP + Gold nanoparticle-conjugated to Irisin: The mouse models underwent the CLP and received an i.m (TA) injection of 1 µg of Gold nanoparticle-irisin via intramuscular injection (TA) into each leg (n = 5); (IV) CLP + Gold nanoparticles- conjugated to IgG: The mouse underwent the CLP and received an i.m (TA) injection of gold nanoparticles conjugated to IgG (n = 5). (V) Sham: The mouse underwent the surgical operation without conducting the CLP (n = 10). The post-operated animals were observed for one week, and survival rates were estimated. Echocardiography was performed to measure cardiac function at 12 h following CLP. TUNEL was employed to detect apoptosis in both cardiac and skeletal muscles; histology was conducted to assess tissue injury in muscles. Enzyme linked immunosorbent assay (ELISA) was conducted to examine release of interleukin 6 (IL6) and the tumor necrosis factor (TNF) alpha. Compared to the CLP control, soluble irisin treatment improved cardiac function recovery, as indicated by the fractional shortening (FS) and ejection fraction (EF). Irisin treatment exhibited reduced IL6 and TNF-alpha release in association with less apoptosis, lower muscle injury index and improved survival post-CLP. However, compared to soluble irisin treatment, gold nanoparticles-conjugated to irisin showed a significant improvement in cardiac function, suppression of apoptosis, reduced IL6 and TNF-alpha releases, decreased muscle injury and an improved survival rate of post-CLP. This study reveals that gold nanoparticles-conjugated irisin can serve to improve irisin's therapeutic effects over a longer course of treatment.

Influence of Residual Nonaqueous-Phase Liquids (NAPLs) on the Transport and Retention of Perfluoroalkyl Substances.

Per- and polyfluoralkyl substances (PFAS) are known to accumulate at interfaces, and the presence of nonaqueous-phase liquids (NAPLs) could influence the PFAS fate in the subsurface. Experimental and mathematical modeling studies were conducted to investigate the effect of a representative NAPL, tetrachloroethene (PCE), on the transport behavior of PFAS in a quartz sand. Perfluorooctanesulfonate (PFOS), perfluorononanoic acid (PFNA), a 1:1 mixture of PFOS and PFNA, and a mixture of six PFAS (PFOS, PFNA, perfluorooctanoic acid (PFOA), perfluoroheptanoic acid (PFHpA), perfluorohexanesulfonate (PFHxS), and perfluorobutanesulfonate (PFBS)) were used to assess PFAS interactions with PCE-NAPL. Batch studies indicated that PFAS partitioning into PCE-NAPL (Knw < 0.1) and adsorption on 60-80 mesh Ottawa sand (Kd < 6 × 10-5 L/g) were minimal. Column studies demonstrated that the presence of residual PCE-NAPL (∼16% saturation) delayed the breakthrough of PFOS and PFNA, with minimal effects on the mobility of PFBS, PFHpA, PFHxS, and PFOA. Breakthrough curves (BTCs) obtained for PFNA and PFOS alone and in mixtures were nearly identical, indicating the absence of competitive adsorption effects. A mathematical model that accounts for NAPL-water interfacial sorption accurately reproduced PFAS BTCs, providing a tool to predict PFAS fate and transport in co-contaminated subsurface environments.

Graphene oxide nanosheets augment silk fibroin aerogels for enhanced water stability and oil adsorption.

Nanocomposite aerogels exhibit high porosity and large interfacial surface areas, enabling enhanced chemical transport and reactivity. Such mesoporous architectures can be prepared by freeze-casting naturally-derived biopolymers such as silk fibroin, but often form mechanically weak structures that degrade in water, which limits their performance under ambient conditions. Adding 2D material fillers such as graphene oxide (GO) or transition metal carbides (e.g. MXene) could potentially reinforce these aerogels via stronger intermolecular interactions with the polymeric binder. Here, we show that freeze-casting of GO nanosheets with silk fibroin results in a highly water-stable, mechanically robust aerogel, with considerably enhanced properties relative to silk-only or silk-MXene aerogels. These silk-GO aerogels exhibit high contact angles with water and are highly water stable. Moreover, aerogels can adsorb up 25-35 times their mass in oil, and can be used robustly for selective oil separation from water. This increased stability may occur due to strengthened intermolecular interactions such as hydrogen bonding, despite the random coil and α-helix conformation of silk fibroin, which is typically more soluble in water. Finally, we show these aerogels can be prepared at scale by freeze-casting on a copper mesh. Ultimately, we envision that these multicomponent aerogels could be widely utilized for molecular separations and environmental sensing, as well as for thermal insulation and electrical conductivity.

Controlled Release of Molecular Intercalants from Two-Dimensional Nanosheet Films.

Solution co-deposition of two-dimensional (2D) nanosheets with chemical solutes yields nanosheet-molecular heterostructures. A feature of these macroscopic layered hybrids is their ability to release the intercalated molecular agent to express chemical functionality on their surfaces or in their near surroundings. Systematic design methods are needed to control this molecular release to match the demand for rate and lifetime in specific applications. We hypothesize that release kinetics are controlled by transport processes within the layered solids, which primarily involve confined molecular diffusion through nanochannels formed by intersheet van der Waals gaps. Here a variety of graphene oxide (GO)/molecular hybrids are fabricated and subject to transient experiments to characterize release kinetics, locations, and mechanisms. The measured release rate profiles can be successfully described by a numerical model of internal transport processes, and the results used to extract effective Z-directional diffusion coefficients for various film types. The diffusion coefficients are found to be 8 orders of magnitude lower than those in free solution due to nanochannel confinement and serpentine path effects, and this retardation underlies the ability of 2D materials to control and extend release over useful time scales. In-plane texturing of the heterostructured films by compressive wrinkling or crumpling is shown to be a useful design tool to control the release rate for a given film type and molecular intercalant. The potential of this approach is demonstrated through case studies on the controlled release of chemical virucidal agents.

A graphene-based hydrogel monolith with tailored surface chemistry for PFAS passive sampling.

Aquatic contamination by per- and polyfluorinated alkyl substances (PFAS) has attracted global attention due to their environmental and health concerns. Current health advisories and surface water regulatory limits require PFAS detection in the parts per trillion (ppt) range. One way to achieve those low detection limits is to use a reliable passive sampling-based monitoring tool for PFAS, as exists for numerous nonpolar persistent organic pollutants. Here we introduce a new graphene-based hydrogel monolith and describe its synthesis, chemical functionalization, property characterization, and testing as a PFAS equilibrium passive sampler. The graphene monoliths were self-assembled by hydrothermal treatment from graphene oxide (GO) aqueous dispersions to produce free standing cylinders of ~563 mm3 volume consisting of ~4 wt-% thin-walled porous graphene and ~96 wt-% water. The uptake of 23 PFAS was measured on the as-produced monoliths, and equilibrium partition coefficients (KSW), were derived for longer chain (C≥8) perfluoroalkyl acids (PFAA) and neutral precursors such as sulfonamides (log KSW range 1.9 - 3.6). To increase the KSW for shorter chain PFAA, the monoliths were chemically modified by a new diazonium-based grafting reaction that introduces positive surface charge without damage to the graphenic backbone. Introduction of benzylamine moieties through the diazonium intermediate switches zeta potential at pH 7 from -45mV (as-produced graphene) to + 5mV. This modification increased the sorption of short and middle chain PFAA by ten-fold (e.g. log KSW for PFBA increased from 1.3 to 2.2), thereby improving the functionality of the passive sampler device for a wider range of PFAS. Field deployments demonstrated that the graphene monoliths were capable of detecting key PFAS in the Delaware River.