Adsorption of Rare Earth Elements onto DNA-Functionalized Mesoporous Carbon.

The recovery and separation of rare earth elements (REEs) are of national importance owing to the specific usages, high demand, and low supply of these elements. In this research, we have investigated the adsorption of rare earth elements onto DNA-functionalized mesoporous carbons with a BET surface area of 605 m2/g and a median mesopore width of 48 Å. Three types of single-stranded DNA, one with 100 base units of thymine, another with 20 units of thymine, and the third, a 2000 unit long DNA from salmon milt were grafted on the carboxylated mesoporous carbon surface. All of the DNA-functionalized mesoporous carbons demonstrated higher adsorption of REEs compared to pristine mesoporous carbon and DNA grafted with 100 units of thymine demonstrated slightly higher adsorbed amounts compared to others. Pure neodymium (Nd(III)) adsorption in the aqueous phase demonstrated an adsorbed amount of 110.4 mg/g with respect to the initial concentration of 500 mg/g. A pH variation study with pure Nd(III) demonstrated that the adsorbed amount is higher at elevated pH compared to that at lower pH, thereby suggesting possible recovery at lower pH. Adsorption of a mixture of 16 REEs, including Sc, Lu, Tm, Yb, Er, Ho, Tb, Dy, Y, Eu, Gd, Sm, Ce, Nd, Pr, and La revealed that the adsorbed amount increased with an increase in the atomic weight and metallic radii of elements within the lanthanides. The calculation of the distribution coefficients for all of the equilibrium adsorption amounts suggested that adsorption is more effective in the lower concentration region. The Nd L3-edge X-ray absorption near edge structure (XANES) confirmed a 3+ oxidation state of Nd in the adsorbed phase. The extended X-ray absorption fine structure (EXAFS) confirmed the local atomic structure relaxation of Nd complexes in the adsorbed phase and shortening of the Nd-O bond distance by about 0.03-0.04 Å, which may be associated with their local complexation at the carbon surface.

Enhanced PEDOT adhesion on solid substrates with electrografted P(EDOT-NH2).

Conjugated polymers, such as poly(3,4-ethylene dioxythiophene) (PEDOT), have emerged as promising materials for interfacing biomedical devices with tissue because of their relatively soft mechanical properties, versatile organic chemistry, and inherent ability to conduct both ions and electrons. However, their limited adhesion to substrates is a concern for in vivo applications. We report an electrografting method to create covalently bonded PEDOT on solid substrates. An amine-functionalized EDOT derivative (2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanamine (EDOT-NH2), was synthesized and then electrografted onto conducting substrates including platinum, iridium, and indium tin oxide. The electrografting process was performed under slightly basic conditions with an overpotential of ~2 to 3 V. A nonconjugated, cross-linked, and well-adherent P(EDOT-NH2)-based polymer coating was obtained. We found that the P(EDOT-NH2) polymer coating did not block the charge transport through the interface. Subsequent PEDOT electrochemical deposition onto P(EDOT-NH2)-modified electrodes showed comparable electroactivity to pristine PEDOT coating. With P(EDOT-NH2) as an anchoring layer, PEDOT coating showed greatly enhanced adhesion. The modified coating could withstand extensive ultrasonication (1 hour) without significant cracking or delamination, whereas PEDOT typically delaminated after seconds of sonication. Therefore, this is an effective means to selectively modify microelectrodes with highly adherent and highly conductive polymer coatings as direct neural interfaces.

Stiffness, strength and adhesion characterization of electrochemically deposited conjugated polymer films.

Conjugated polymers such as poly(3,4-ethylenedioxythiphene) (PEDOT) are of interest for a variety of applications including interfaces between electronic biomedical devices and living tissue. The mechanical properties, strength, and adhesion of these materials to solid substrates are all vital for long-term applications. We have been developing methods to quantify the mechanical properties of conjugated polymer thin films. In this paper, the stiffness, strength and the interfacial shear strength (adhesion) of electrochemically deposited PEDOT and PEDOT-co-1,3,5-tri[2-(3,4-ethylene dioxythienyl)]-benzene (EPh) were studied. The estimated Young's modulus of the PEDOT films was 2.6±1.4GPa, and the strain to failure was around 2%. The tensile strength was measured to be 56±27MPa. The effective interfacial shear strength was estimated with a shear-lag model by measuring the crack spacing as a function of film thickness. For PEDOT on gold/palladium-coated hydrocarbon film substrates an interfacial shear strength of 0.7±0.3MPa was determined. The addition of 5mole% of a tri-functional EDOT crosslinker (EPh) increased the tensile strength of the films to 283±67MPa, while the strain to failure remained about the same (2%). The effective interfacial shear strength was increased to 2.4±0.6MPa. STATEMENT OF SIGNIFICANCE: This paper describes methods for estimating the ultimate mechanical properties of electrochemically deposited conjugated polymer (here PEDOT and PEDOT copolymers) films. Of particular interest and novelty is our implementation of a cracking test to quantify the shear strength of the PEDOT thin films on these solid substrates. There is considerable interest in these materials as interfaces between biomedical devices and living tissue, however potential mechanisms and modes of failure are areas of continuing concern, and establishing methods to quantify the strengths of these interfaces are therefore of particular current interest. We are confident that these results will be useful to the broader biological materials community and are worthy of broader dissemination.

Poly[3,4-ethylene dioxythiophene (EDOT) -co- 1,3,5-tri[2-(3,4-ethylene dioxythienyl)]-benzene (EPh)] copolymers (PEDOT-co-EPh): optical, electrochemical and mechanical properties.

PEDOT-co-EPh copolymers with systematic variations in composition were prepared by electrochemical polymerization from mixed monomer solutions in acetonitrile. The EPh monomer is a trifunctional crosslinking agent with three EDOTs around a central benzene ring. With increasing EPh content, the color of the copolymers changed from blue to yellow to red due to decreased absorption in the near infrared (IR) spectrum and increased absorption in the visible spectrum. The surface morphology changed from rough and nanofibrillar to more smooth with rounded bumps. The electrical transport properties dramatically decreased with increasing EPh content, resulting in coatings that either substantially lowered the impedance of the electrode (at the lowest EPh content), leave the impedance nearly unchanged (near 1% EPh), or significantly increase the impedance (at 1% and above). The mechanical properties of the films were substantially improved with EPh content, with the 0.5% EPh films showing an estimated 5x improvement in modulus measured by AFM nanoindentation. The PEDOT-co-EPh copolymer films were all shown to be non-cytotoxic toward and promote the neurite outgrowth of PC12 cells. Given these results, we expect that the films of most interest for neural interface applications will be those with improved mechanical properties that maintain the improved charge transport performance (with 1% EPh and below).

Significant enhancement of PEDOT thin film adhesion to inorganic solid substrates with EDOT-acid.

With its high conductivity, tunable surface morphology, relatively soft mechanical response, high chemical stability, and excellent biocompatibility, poly(3,4-ethylenedioxythiophene) (PEDOT) has become a promising coating material for a variety of electronic biomedical devices. However, the relatively poor adhesion of PEDOT to inorganic metallic and semiconducting substrates still poses challenges for long-term applications. Here, we report that 2,3-dihydrothieno(3,4-b)(1,4)dioxine-2-carboxylic acid (EDOT-acid) significantly improves the adhesion between PEDOT thin films and inorganic solid electrodes. EDOT-acid molecules were chemically bonded onto activated oxide substrates via the chemisorption of the carboxylic groups. PEDOT was then polymerized onto the EDOT-acid modified substrates, forming covalently bonded coatings. The adsorption of EDOT-acid onto the electrode surfaces was characterized by cyclic voltammetry (CV), contact angle measurements, atomic force microscopy, and X-ray photoelectron spectroscopy. The electrical properties of the subsequently coated PEDOT films were studied by electrochemical impedance spectroscopy and CV. An aggressive ultrasonication test confirmed the significantly improved adhesion and mechanical stability of the PEDOT films on electrodes with EDOT-acid treatment over those without treatment.

Synthesis and characterization of bicontinuous cubic poly(3,4-ethylene dioxythiophene) gyroid (PEDOT GYR) gels.

We describe the synthesis and characterization of bicontinuous cubic poly(3,4-ethylenedioxythiophene) (PEDOT) conducting polymer gels prepared within lyotropic cubic poly(oxyethylene)10 nonylphenol ether (NP-10) templates with Ia3[combining macron]d (gyroid, GYR) symmetry. The chemical polymerization of EDOT monomer in the hydrophobic channels of the NP-10 GYR phase was initiated by AgNO3, a mild oxidant that is activated when exposed to ultraviolet (UV) radiation. The morphology and physical properties of the resulting PEDOT gels were examined as a function of temperature and frequency using optical and electron microscopy, small-angle X-ray scattering (SAXS), dynamic mechanical spectroscopy, and electrochemical impedance spectroscopy (EIS). Microscopy and SAXS results showed that the PEDOT gels remained ordered and stable after the UV-initiated chemical polymerization, confirming the successful templated-synthesis of PEDOT in bicontinuous GYR nanostructures. In comparison to unpolymerized 3,4-ethylenedioxythiophene (EDOT) gel phases, the PEDOT structures had a higher storage modulus, presumably due to the formation of semi-rigid PEDOT-rich nanochannels. Additionally, the storage modulus (G') for PEDOT gels decreased only modestly with increasing temperature, from ∼1.2 × 10(5) Pa (10 °C) to ∼7 × 10(4) Pa (40 °C), whereas G' for the NP-10 and EDOT gels decreased dramatically, from ∼5.0 × 10(4) Pa (10 °C) to ∼1.5 × 10(2) Pa (40 °C). EIS revealed that the impedance of the PEDOT gels was smaller than the impedance of EDOT gels at both high frequencies (PEDOT ∼10(2) Ω and EDOT 2-3 × 10(4) Ω at 10(5) Hz) and low frequencies (PEDOT 10(3)-10(5) Ω and EDOT ∼5 × 10(5) Ω at 10(-1) Hz). These results indicated that PEDOT gels were highly ordered, mechanically stable and electrically conductive, and thus should be of interest for applications for which such properties are important, including low impedance and compliant coatings for biomedical electrodes.

In vivo polymerization of poly(3,4-ethylenedioxythiophene) in the living rat hippocampus does not cause a significant loss of performance in a delayed alternation task.

After extended implantation times, traditional intracortical neural probes exhibit a foreign-body reaction characterized by a reactive glial sheath that has been associated with increased system impedance and signal deterioration. Previously, we have proposed that the local in vivo polymerization of an electronically and ionically conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), might help to rebuild charge transport pathways across the glial scar between the device and surrounding parenchyma (Richardson-Burns et al 2007 J. Neural Eng. 4 L6-13). The EDOT monomer can be delivered via a microcannula/electrode system into the brain tissue of living animals followed by direct electrochemical polymerization, using the electrode itself as a source of oxidative current. In this study, we investigated the long-term effect of local in vivo PEDOT deposition on hippocampal neural function and histology. Rodent subjects were trained on a hippocampus-dependent task, delayed alternation (DA), and implanted with the microcannula/electrode system in the hippocampus. The animals were divided into four groups with different delay times between the initial surgery and the electrochemical polymerization: (1) control (no polymerization), (2) immediate (polymerization within 5 min of device implantation), (3) early (polymerization within 3-4 weeks after implantation) and (4) late (polymerization 7-8 weeks after polymerization). System impedance at 1 kHz was recorded and the tissue reactions were evaluated by immunohistochemistry. We found that under our deposition conditions, PEDOT typically grew at the tip of the electrode, forming an ∼500 µm cloud in the tissue. This is much larger than the typical width of the glial scar (∼150 µm). After polymerization, the impedance amplitude near the neurologically important frequency of 1 kHz dropped for all the groups; however, there was a time window of 3-4 weeks for an optimal decrease in impedance. For all surgery-polymerization time intervals, the polymerization did not cause significant deficits in performance of the DA task, suggesting that hippocampal function was not impaired by PEDOT deposition. However, GFAP+ and ED-1+ cells were also found at the deposition two weeks after the polymerization, suggesting potential secondary scarring. Therefore, less extensive deposition or milder deposition conditions may be desirable to minimize this scarring while maintaining decreased system impedance.

Chitosan adsorption on hydroxyapatite and its role in preventing acid erosion.

Polymer adsorption onto an artificial saliva (AS) layer is investigated using quartz-crystal microbalance with dissipation (QCM-D) and chitosan as the model polymer. QCM-D is utilized in an innovative manner to monitor in situ adsorption of chitosan (CH) onto a hydroxyapatite (HA) coated crystal and to examine the ability of the adsorbed layer to "protect" the HA upon sequential exposure to acidic solutions. After deposition of a thin AS layer (16 nm), the total thickness on the HA substrate increases to 37 nm upon exposure to CH at pH 5.5 for 10 min. Correspondingly, the surface charge changes from negative (i.e., AS) to positive, consistent with the adsorption the polycationic CH onto or into the AS layer. Upon exposure to an oxidizing agent, the chitosan cross-links and collapses as noted by a decrease in thickness to 10 nm and an increase in the shear modulus by an order of magnitude. Atomic force microscopy (AFM) is used to determine the surface morphology and RMS roughness of the coated and HA surfaces after citric acid challenges. Both physisorbed and cross-linked chitosan are demonstrated to limit and prevent the erosion of HA, respectively.

Human macrophage adhesion on polysaccharide patterned surfaces.

Despite many advances in designing biocompatible materials, inflammation remains a problem in medical devices and implants. We report two methods, microcontact printing and photodegradation by UV exposure, to pattern dextran and hyaluronic acid on glass, as well as demonstrate their utility for use as an anti-inflammatory biomaterial. The dextran/glass patterned surface can be further modified by grafting hyaluronic acid to glass, creating a binary polysaccharide patterned surface. We used two geometries, 90 µm squares and 22 µm stripes, to study the human macrophage (THP-1) adhesion on the patterned surfaces containing dextran, hyaluronic acid and the binary pattern. The results indicate that a majority of the macrophages are non-adherent on hyaluronic acid for three day culture. The ranking of surfaces according to macrophage adhesion is 3-aminopropyl triethoxysilane-modified glass culture dish, dextranized surfaces, glass, and hyaluronic acid-modified surfaces. On the binary pattern of dextran and hyaluronic acid, macrophages preferentially attach and adhere to the dextranized area. Patterned surfaces provide an excellent platform for mimicking the complexity of the glycocalyx and investigating the interface between this surface and cells. This binary polysaccharide pattern also offers a new route to address anti-inflammatory potential of surface coatings on biomaterials in a high through-put fashion.