Utilizing Rapid Hydrogen Peroxide Generation from 6-Hydroxycatechol to Design Moisture-Activated, Self-Disinfecting Coating.

A coating that can be activated by moisture found in respiratory droplets could be a convenient and effective way to control the spread of airborne pathogens and reduce fomite transmission. Here, the ability of a novel 6-hydroxycatechol-containing polymer to function as a self-disinfecting coating on the surface of polypropylene (PP) fabric was explored. Catechol is the main adhesive molecule found in mussel adhesive proteins. Molecular oxygen found in an aqueous solution can oxidize catechol and generate a known disinfectant, hydrogen peroxide (H2O2), as a byproduct. However, given the limited amount of moisture found in respiratory droplets, there is a need to enhance the rate of catechol autoxidation to generate antipathogenic levels of H2O2. 6-Hydroxycatechol contains an electron donating hydroxyl group on the 6-position of the benzene ring, which makes catechol more susceptible to autoxidation. 6-Hydroxycatechol-coated PP generated over 3000 µM of H2O2 within 1 h when hydrated with a small amount of aqueous solution (100 µL of PBS). The generated H2O2 was three orders of magnitude higher when compared to the amount generated by unmodified catechol. 6-Hydroxycatechol-containing coating demonstrated a more effective antimicrobial effect against both Gram-positive (Staphylococcus aureus and Staphylococcus epidermidis) and Gram-negative (Pseudomonas aeruginosa and Escherichia coli) bacteria when compared to unmodified catechol. Similarly, the self-disinfecting coating reduced the infectivity of both bovine viral diarrhea virus and human coronavirus 229E by as much as a 2.5 log reduction value (a 99.7% reduction in viral load). Coatings containing unmodified catechol did not generate sufficient H2O2 to demonstrate significant virucidal effects. 6-Hydroxycatechol-containing coating can potentially function as a self-disinfecting coating that can be activated by the moisture present in respiratory droplets to generate H2O2 for disinfecting a broad range of pathogens.

Pair of Functional Polyesters That Are Photo-Cross-Linkable and Electrospinnable to Engineer Elastomeric Scaffolds with Tunable Structure and Properties.

A pair of alkyne- and thiol-functionalized polyesters are designed to engineer elastomeric scaffolds with a wide range of tunable material properties (e.g., thermal, degradation, and mechanical properties) for different tissues, given their different host responses, mechanics, and regenerative capacities. The two prepolymers are quickly photo-cross-linkable through thiol-yne click chemistry to form robust elastomers with small permanent deformations. The elastic moduli can be easily tuned between 0.96 ± 0.18 and 7.5 ± 2.0 MPa, and in vitro degradation is mediated from hours up to days by adjusting the prepolymer weight ratios. These elastomers bear free hydroxyl and thiol groups with a water contact angle of less than 85.6 ± 3.58 degrees, indicating a hydrophilic nature. The elastomer is compatible with NIH/3T3 fibroblast cells with cell viability reaching 88 ± 8.7% relative to the TCPS control at 48 h incubation. Differing from prior soft elastomers, a mixture of the two prepolymers without a carrying polymer is electrospinnable and UV-cross-linkable to fabricate elastic fibrous scaffolds for soft tissues. The designed prepolymer pair can thus ease the fabrication of elastic fibrous conduits, leading to potential use as a resorbable synthetic graft. The elastomers could find use in other tissue engineering applications as well.

Chemical Modification of Tiopronin for Dual Management of Cystinuria and Associated Bacterial Infections.

Cystinuria is an inherited autosomal recessive disease of the kidneys of recurring nature that contributes to frequent urinary tract infections due to bacterial growth and biofilm formation surrounding the stone microenvironment. In the past, commonly used strategies for managing cystinuria involved the use of (a) cystine crystal growth inhibitors such as l-cystine dimethyl ester and lipoic acid, and (b) thiol-based small molecules such as N-(2-mercaptopropionyl) glycine, commonly known as tiopronin, that reduce the formation of cystine crystals by reacting with excess cystine and generating more soluble disulfide compounds. However, there is a dearth of simplistic chemical approaches that have focused on the dual treatment of cystinuria and the associated microbial infections. This work strategically exploited a single chemical approach to develop a nitric oxide (NO)-releasing therapeutic compound, S-nitroso-2-mercaptopropionyl glycine (tiopronin-NO), for the dual management of cystine stone formation and the related bacterial infections. The results successfully demonstrated that (a) the antibacterial activity of NO rendered tiopronin-NO effective against the stone microenvironment inhabitants, Escherichia coli and Pseudomonas aeruginosa, and (b) tiopronin-NO retained the ability to undergo disulfide exchange with cystine while being reported to be safe against canine kidney and mouse fibroblast cells. Thus, the synthesis of such a facile molecule aimed at the dual management of cystinuria and related infections is unprecedented in the literature.

Superhydrophobic and Conductive Foams with Antifouling and Oil-Water Separation Properties.

Hybrid organic-inorganic materials are attracting enormous interest in materials science due to the combination of multiple advantageous properties of both organic and inorganic components. Taking advantage of a simple, scalable, solvent-free hard-sacrificial method, we report the successful fabrication of three-dimensional hybrid porous foams by integrating two types of fillers into a poly(dimethylsiloxane) (PDMS) framework. These fillers consist of hydrophobic electrically conductive graphene (GR) nanoplatelets and hydrophobic bactericidal copper (Cu) microparticles. The fillers were utilized to create the hierarchical rough structure with low-surface-energy properties on the PDMS foam surfaces, leading to remarkable superhydrophobicity/superoleophilicity with contact angles of 158 and 0° for water and oil, respectively. The three-dimensional interconnected porous foam structures facilitated high oil adsorption capacity and excellent reusability as well as highly efficient oil/organic solvent-water separation in turbulent, corrosive, and saline environments. Moreover, the introduction of the fillers led to a significant improvement in the electrical conductivity and biofouling resistance (vs whole blood, fibrinogen, platelet cells, and Escherichia coli) of the foams. We envision that the developed composite strategy will pave a facile, scalable, and effective way for fabricating novel multifunctional hybrid materials with ideal properties that may find potential use in a broad range of biomedical, energy, and environmental applications.

Bioinspired ultra-low fouling coatings on medical devices to prevent device-associated infections and thrombosis.

Addressing thrombosis and biofouling of indwelling medical devices within healthcare institutions is an ongoing problem. In this work, two types of ultra-low fouling surfaces (i.e., superhydrophobic and lubricant-infused slippery surfaces) were fabricated to enhance the biocompatibility of commercial medical grade silicone rubber (SR) tubes that are widely used in clinical care. The superhydrophobic (SH) coatings on the tubing substrates were successfully created by dip-coating in superhydrophobic paints consisting of polydimethylsiloxane (PDMS), perfluorosilane-coated hydrophobic zinc oxide (ZnO) and copper (Cu) nanoparticles (NPs) in tetrahydrofuran (THF). The SH surfaces were converted to lubricant-infused slippery (LIS) surfaces through the infusion of silicone oil. The anti-biofouling properties of the coatings were investigated by adsorption of platelets, whole blood coagulation, and biofilm formation in vitro. The results revealed that the LIS tubes possess superior resistance to clot formation and platelet adhesion than uncoated and SH tubes. In addition, bacterial adhesion was investigated over 7 days in a drip-flow bioreactor, where the SH-ZnO-Cu tube and its slippery counterpart significantly reduced bacterial adhesion and biofilm formation of Escherichia coli relative to control tubes (>5 log10 and >3 log10 reduction, respectively). The coatings also demonstrated good compatibility with fibroblast cells. Therefore, the proposed coatings may find potential applications in high-efficiency on-demand prevention of biofilm and thrombosis formation on medical devices to improve their biocompatibility and reduce the risk of complications from medical devices.

Effect of Conductivity on In Situ Deactivation of Catechol-Boronate Complexation-Based Reversible Smart Adhesive.

To reduce the need for elevated electrical potential to deactivate catechol-based smart adhesive and preserve its reversibility, conductive 1-pyrenemethyl methacrylate (PyMA) was incorporated into a catechol and phenylboronic acid-containing adhesive coating immobilized on aluminum (Al) discs. Electrochemical impedance spectroscopy (EIS) indicated that incorporation of 26 mol % of PyMA reduced ionic resistance (Rs) and charge-transfer resistance (Rc) of the coating from over 22 Ω/mm2 to 5.9 and 1.2 Ω/mm2, respectively. A custom-built Johnson-Kendall-Roberts (JKR) contact mechanics test setup was used to evaluate the adhesive property of the coating with in situ applied electricity using a titanium (Ti) sphere both as a test substrate as well as the cathode for application of electricity and the Al disc as the anode. The adhesive coating demonstrated over 95% reduction in the adhesive property when electricity (1-2 V) was applied while the adhesive was in direct contact with the Ti surface. The addition of PyMA enables the deactivation of the adhesive using a voltage as low as 1 V. Both cyclic voltammetry (CV) and attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectra confirmed the formation of catechol-boronate complexation through electrochemical stimulation. Breaking the complex with an acidic buffer (pH 3) recovered the catechol for strong wet adhesion and the coating could be repeatedly deactivated and reactivated using low electrical potential for up to five cycles. Incorporation of both conductive PyMA and boronic acid as the temporary protecting group was required to achieve rapidly switchable adhesive that could be deactivated with low applied voltage.

Highly hydrophobic polytetrafluoroethylene particle immobilization via polydopamine anchor layer on nitric oxide releasing polymer for biomedical applications.

Biomedical surface-associated infections and thrombus formation are two major clinical issues that challenge patient safety and patient the fate of a medical device in the body . Single platform multifunctional surfaces are critical to address both these indwelling medical device-related problems. In this work, bio-inspired approaches are employed to fabricate a polymer composite with a versatile surface that can reduce bacterial infections and platelet adhesion in vitro. In the first bio-inspired approach, the functionality of nitric oxide (NO) produced by endothelial cell lining of blood vessels is mimicked through incorporation of S-nitroso-N-acetylpenicillamine (SNAP) within a CarboSil-2080A™ (CarboSil) polymer composite matrix. The second approach involves utilizing mussel adhesive chemistry, via polydopamine (PDA) to immobilize polytetrafluoroethylene (PTFE) particles on the polymer composite surface. The PTFE coating facilitates a decrease in wettability by making the polymer composite surface highly hydrophobic (contact angle ca. 120°). The surface of the fabricated polymer composite , CarboSil SNAP-PTFE, had a cobblestone-like structured appearance as characterized through scanning electron microscopy (SEM). Water contact angle (WCA) and surface tension measurements indicated no significant coating losses after 24 h under physiological conditions. NO surface flux was measured and analyzed for 5 days using a chemiluminescence-based nitric oxide analyzer and was found to be within the physiological range. CarboSil SNAP-PTFE reduced adhered bacteria (99.3 ± 0.5% for Gram-positive S. aureus and 99.1 ± 0.4% for Gram-negative E. coli) in a 24 h in vitro study. SEM analysis showed the absence of biofilm formation on CarboSil SNAP-PTFE polymer composites, while present on CarboSil in 24 h exposure to S. aureus. Platelet adhesion was reduced by 83.3 ± 4.5%. Overall, the results of this study suggest that a combination of NO-releasing CarboSil with PTFE coating can drastically reduce infection and platelet adhesion.

Fabrication of Bacteria- and Blood-Repellent Superhydrophobic Polyurethane Sponge Materials.

Biofilm and thrombus formation on surfaces results in significant morbidity and mortality worldwide, which highlights the importance of the development of efficacious fouling-prevention approaches. In this work, novel highly robust and superhydrophobic coatings with outstanding multiliquid repellency, bactericidal performance, and extremely low bacterial and blood adhesion are fabricated by a simple two-step dip-coating method. The coatings are prepared combining 1H,1H,2H,2H-perfluorooctyltriethoxysilane (FAS-17)-coated hydrophobic zinc oxide and copper nanoparticles to construct hierarchical micro/nanostructures on commercial polyurethane (PU) sponges followed by polydimethylsiloxane (PDMS) treatment that is used to improve the binding degree between the nanoparticles and the sponge surface. The micro/nanotextured samples can repel various liquids including water, milk, coffee, juice, and blood. Relative to the original PU, the superhydrophobic characteristics of the fabricated sponge cause a significant reduction in the adhesion of bacteria (Staphylococcus aureus) by up to 99.9% over a 4-day period in a continuous drip-flow bioreactor. The sponge is also highly resistant to the adhesion of fibrinogen and activated platelets with ∼76 and 64% reduction, respectively, hence reducing the risk of blood coagulation and thrombus formation. More importantly, the sponge can sustain its superhydrophobicity even after being subjected to different types of harsh mechanical damage such as finger-wiping, knife-scratching, tape-peeling, hand-kneading, hand-rubbing, bending, compress-release (1000 cycles) tests, and 1000 cm sandpaper abrasion under 250 g of loading. Hence, this novel hybrid surface with robustness and the ability to resist blood adhesion and bacterial contamination makes it an attractive candidate for use in diverse application areas.

H2S-Releasing Composite: a Gasotransmitter Platform for Potential Biomedical Applications.

Hydrogen sulfide (H2S) is an endogenous gasotransmitter in the human body involved in various physiological functions including cytoprotection, maintaining homeostasis, and regulation of organ development. Therefore, H2S-releasing polymers that can imitate endogenous H2S release can offer great therapeutic potential. Despite decades of research, the use of H2S donors in medical device applications is mostly unexplored largely due to the challenge of the steady H2S release from a suitable polymeric platform that does not compromise the normal cellular functions of the host. In this work, an exogenous H2S release system was developed by integrating sodium sulfide (Na2S), a common H2S donor, into a medical-grade thermoplastic silicone-polycarbonate-urethane polymer, Carbosil 20 80A (hereon as Carbosil), via a facile solvent evaporation technique. The spatial distribution and nature of Na2S in Carbosil were characterized through X-ray diffraction (XRD) spectroscopy and field emission scanning electron microscopy (FESEM) with energy-dispersive spectroscopy (EDS), indicating an amorphous phase shift upon incorporating Na2S in Carbosil. The composite, Na2S-Carbosil, is responsive in physiological conditions, resulting in sustained H2S release measured for 3 h. In vitro cellular responses of 3T3 mouse fibroblasts, human lung epithelial (HLE), and primary human umbilical vein endothelial cells (HUVEC) were investigated. Fibroblast cells showed cell proliferation in 24 h and complete cell migration in 42 h in vitro. The Na2S-Carbosil composites were cytocompatible toward HUVEC and HLE cells. This study provided important in vitro proof of concept that warrants potential use of these H2S-releasing platforms in engineering biomedical devices, tissue engineering, and drug delivery applications.

Route to sustainable lithium-sulfur batteries with high practical capacity through a fluorine free polysulfide catholyte and self-standing Carbon Nanofiber membranes.

We report on a new strategy to improve the capacity, reduce the manufacturing costs and increase the sustainability of Lithium-Sulfur (LiS) batteries. It is based on a semi-liquid cathode composed of a Li2S8 polysulphide catholyte and a binder-free carbon nanofiber membrane with tailored morphology. The polysulphides in the catholyte have the dual role of active material and providing Li+-conduction, i.e. no traditional Li-salt is used in this cell. The cell is able to deliver an areal capacity as high as 7 mAh cm-2, twice than that of commercial Lithium-ion batteries (LiBs) and 2-4 times higher than that of state-of-the-art LiS cells. In addition, the battery concept has an improved sustainability from a material point of view by being mainly based on sulfur and carbon and being completely fluorine-free, no fluorinated salt or binders are used, and has potential for upscaling and competitive price. The combination of these properties makes the semi-liquid LiS cell here reported a very promising new concept for practical large-scale energy storage applications.

Patient preference for the pre-anesthesia evaluation: Telephone versus in-office assessment.

STUDY OBJECTIVE: Pre-anesthesia evaluation (PAE) is designed to reduce patient and family anxiety, identify pre-existing health issues, avoid surgical delays, minimize costs, and tailor an anesthetic plan. If PAE requires a clinic visit, patients must take time off work and may incur travel and childcare costs. A telephone-based Preoperative Assessment Clinic can minimize patient inconvenience, while maintaining high-quality patient care and improving efficiency. We assessed patient satisfaction with a telephone PAE and determined whether patients preferred a telephone PAE or a conventional clinic visit. DESIGN: Prospective, institutional review board-approved study. SETTING: University hospital. PATIENTS: We conducted an IRB-approved telephone survey of 75 adult, post-operative patients. INTERVENTIONS: Telephone survey. MEASUREMENTS: Patients were asked about their preference for a telephone PAE over an in-person evaluation. Survey questions included assessment of patient satisfaction with their anesthesia evaluation, operation, and anesthetic delivered. Delays and day of surgery cancellations were reviewed. MAIN RESULTS: The majority (97%) of patients stated they preferred a telephone PAE. Patient satisfaction was unaffected by driving distance (30±54 mi), ASA physical status or duration of surgery (169±159 min). Even patients who were not satisfied with their anesthetic (N=5) still preferred the telephone-based PAE. No increase in surgical delays or cancellation was noted. CONCLUSION: The majority of patients in this survey preferred a telephone PAE. Given the large catchment area of our hospital of nine counties, telephone-based interviews add to patient convenience and likely increase compliance with the PAE. Even patients who live in close proximity to our hospital (<5 mi) preferred a telephone assessment. A telephone-based PAE provides high patient satisfaction over a traditional office visit while increasing patient convenience. Larger studies are necessary to ensure that telephone PAEs compare well with in-person examinations.

Nitrogen-Doped Mesoporous Carbon: A Top-Down Strategy to Promote Sulfur Immobilization for Lithium-Sulfur Batteries.

The loss of active sulfur material is a challenge in the application of lithium-sulfur (Li-S) batteries. To immobilize sulfur, a nitrogen-doped mesoporous carbon (PMC) was synthesized with polyaniline (PANi) as the carbon source, which was used for development of Li-S batteries. The nitrogen content and pore system of the PMCs were modulated by varying the pyrolysis temperature to impart good electrochemical properties to the Li-S cells. As a result, the optimal capacity reversibility was obtained with the PMC synthesized at 700 °C that consisted of 12.8 % nitrogen. The enhanced cycle performance of Li-S cells was also validated at high sulfur contents up to 70 % and high C-rates up to 2 C. Furthermore, such sulfur/PMC cathodes could alleviate volume expansion during the discharge process. The results suggest that our synthesized nitrogen-doped PMCs prepared by this top-down strategy are promising materials to immobilize active sulfur in Li-S batteries.

Functionalized Polyacrylonitrile Nanofibrous Membranes for Covalent Immobilization of Glucose Oxidase.

Nanofibrous membrane (NFM) with uniform morphology and large surface area was prepared from 10% solution of polyacrylonitrile (PAN) in N,N-dimethylformamide by electrospinning technique. NFM was chemically modified for use as a support for the immobilization of glucose oxidase. Chemical modification of NFM was carried out by two different methods. In the first method, the cyano groups of PAN were modified to amino groups by a two-step process, while in the second method the carboxylic groups were generated first and then further reacted with hexamethylene diamine to create a reactive spacer arm for the immobilization of enzyme. Scanning electron microscopy studies showed that the surface morphology of NFM was not changed by chemical modification and its mechanical strength was improved. The immobilized glucose oxidase (GOx) retained 54 and 60% of its original activity up to 25 cycles with the PAN NFMs modified by the first and the second method, respectively. The GOx-immobilized NFM from the second method showed promising performance with higher enzyme immobilization, activity retention, and favorable kinetic parameters.

Synthesis and electrochemical properties of polyaniline nanofibers by interfacial polymerization.

Polyaniline nanofibers were prepared by interfacial polymerization with different organic solvents such as chloroform and carbon tetrachloride. Field emission scanning electron microscopy and transmission electron microscopy were used to study the morphological properties of polyaniline nanofibers. Chemical characterization was carried out using Fourier transform infrared spectroscopy, UV-Vis spectroscopy, and X-ray diffraction spectroscopy and surface area was measured using BET isotherm. Polyaniline nanofibers doped with lithium hexafluorophosphate were prepared and their electrochemical properties were evaluated.

Structural characterization and electrochemical properties of Co3O4 anode materials synthesized by a hydrothermal method.

Cobalt oxide [Co3O4] anode materials were synthesized by a simple hydrothermal process, and the reaction conditions were optimized to provide good electrochemical properties. The effect of various synthetic reaction and heat treatment conditions on the structure and electrochemical properties of Co3O4 powder was also studied. Physical characterizations of Co3O4 are investigated by X-ray diffraction, scanning electron microscopy, and Brunauer-Emmett-Teller [BET] method. The BET surface area decreased with values at 131.8 m2/g, 76.1 m2/g, and 55.2 m2/g with the increasing calcination temperature at 200°C, 300°C, and 400°C, respectively. The Co3O4 particle calcinated at 200°C for 3 h has a higher surface area and uniform particle size distribution which may result in better sites to accommodate Li+ and electrical contact and to give a good electrochemical property. The cell composed of Super P as a carbon conductor shows better electrochemical properties than that composed of acetylene black. Among the samples prepared under different reaction conditions, Co3O4 prepared at 200°C for 10 h showed a better cycling performance than the other samples. It gave an initial discharge capacity of 1,330 mAh/g, decreased to 779 mAh/g after 10 cycles, and then showed a steady discharge capacity of 606 mAh/g after 60 cycles.

Kinetics study of invertase covalently linked to a new functional nanogel.

Nanogels are promising materials as supports for enzyme immobilization. A new hydrogel comprising of methacrylic acid (MAAc) and N-vinyl pyrrolidone (N-VP) and ethyleneglycol dimethacrylate (EGDMA) was synthesized and converted to nanogel by an emulsification method. Nanogel was further functionalized by Curtius azide reaction for use as support for the covalent immobilization of invertase (Saccharomyces cerevisiae). As-prepared or invertase-immobilized nanogel was characterized by FTIR, XRD, TEM and nitrogen analysis. The characterization of both free and the immobilized-invertase were performed using a spectrophotometric method at 540 nm. The values of V(max), maximum reaction rate, (0.123 unit/mg), k(m), Michaelis constant (7.429 mol/L) and E(a), energy of activation (3.511 kj/mol) for the immobilized-invertase are comparable with those of the free invertase at optimum conditions (time 70 min, pH 6.0 and temperature 45°C). The covalent immobilization enhanced the pH and thermal stability of invertase. The immobilized biocatalyst was efficiently reused up to eight cycles.