Toward Long-Term Accurate and Continuous Monitoring of Nitrate in Wastewater Using Poly(tetrafluoroethylene) (PTFE)-Solid-State Ion-Selective Electrodes (S-ISEs).

Long-term accurate and continuous monitoring of nitrate (NO3-) concentration in wastewater and groundwater is critical for determining treatment efficiency and tracking contaminant transport. Current nitrate monitoring technologies, including colorimetric, chromatographic, biometric, and electrochemical sensors, are not feasible for continuous monitoring. This study addressed this challenge by modifying NO3- solid-state ion-selective electrodes (S-ISEs) with poly(tetrafluoroethylene) (PTFE, (C2F4)n). The PTFE-loaded S-ISE membrane polymer matrix reduces water layer formation between the membrane and electrode/solid contact, while paradoxically, the even more hydrophobic PTFE-loaded S-ISE membrane prevents bacterial attachment despite the opposite approach of hydrophilic modifications in other antifouling sensor designs. Specifically, an optimal ratio of 5% PTFE in the S-ISE polymer matrix was determined by a series of characterization tests in real wastewater. Five percent of PTFE alleviated biofouling to the sensor surface by enhancing the negative charge (-4.5 to -45.8 mV) and lowering surface roughness (Ra: 0.56 ± 0.02 nm). It simultaneously mitigated water layer formation between the membrane and electrode by increasing hydrophobicity (contact angle: 104°) and membrane adhesion and thus minimized the reading (mV) drift in the baseline sensitivity ("data drifting"). Long-term accuracy and durability of 5% PTFE-loaded NO3- S-ISEs were well demonstrated in real wastewater over 20 days, an improvement over commercial sensor longevity.

Effect of hydroxyapatite concentration on high-modulus composite for biodegradable bone-fixation devices.

There are over 3 million bone fractures in the United States annually; over 30% of which require internal mechanical fixation devices to aid in the healing process. The current standard material used is a metal plate that is implanted onto the bone. However, metal fixation devices have many disadvantages, namely stress shielding and metal ion leaching. This study aims to fix these problems of metal implants by making a completely biodegradable material that will have a high modulus and exhibit great toughness. To accomplish this, long-fiber poly-l-lactic acid (PLLA) was utilized in combination with a matrix composed of polycaprolactone (PCL) and hydroxyapatite (HA) nano-rods. Through single fibril tensile tests, it was found that the PLLA fibers have a Young's modulus of 8.09 GPa. Synthesized HA nanorods have dimensions in the nanometer range with an aspect ratio over 6. By dip coating PLLA fibers in a suspension of PCL and HA and hot pressing the resulting coated fibers, dense fiber-reinforced samples were made having a flexural modulus up to 9.2 GPa and a flexural strength up to 187 MPa. The flexural modulus of cortical bone ranges from 7 to 25 GPa, so the modulus of the composite material falls into the range of bone. The typical flextural strength of bone is 130 MPa, and the samples here greatly exceed that with a strength of 187 MPa. After mechanical testing to failure the samples retained their shape, showing toughness with no catastrophic failure, indicating the possibility for use as a fixation material. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1963-1971, 2017.

Influence of surface treatment and biomimetic hydroxyapatite coating on the mechanical properties of hydroxyapatite/poly(L-lactic acid) fibers.

Poly(L-lactic acid) (PLLA) micro-fibers have been coated with hydroxyapatite (HA) using a quick biomimetic method to form a precursor for bone repair composites. To increase the coating content within a coating time as short as 1-2.5 h, PLLA fibers have been treated by soaking in NaOH or NaOCl solutions at mild conditions. Although different surface hydrolysis and coating methods have been used to prepare bioceramic/polymer composites, it is for the first time that the influences of the surface treatment and HA coating process on the mechanical properties of the polymer and HA/polymer composite fibers were investigated systemically.

Self-reinforced composites of hydroxyapatite-coated PLLA fibers: fabrication and mechanical characterization.

Self-reinforced composites (SRCs) are materials where both the matrix and fiber-reinforcing phase are made up of the same polymer. Improved bonding can be achieved with self-reinforced composites compared to traditional dual-polymer, fiber-reinforced composites owing to the identical chemistry of the components in SRCs. Bonding between the fiber and matrix phase is an important factor in applications where mechanical stability is required, such as in the field of bone repair. In this study, we prepared bioabsorbable poly(L-lactic acid)/hydroxyapatite (PLLA/HA) self-reinforced composites via a three-step process that includes surface etching of the fiber, the deposition of the HA coating onto the PLLA fibers through immersion in simulated body fluid (SBF), and hot compaction molding. Although coated with a layer of HA, self-reinforced composites were successfully generated by hot compaction. The effects of compaction time (15 and 30 min), compaction temperature (140, 150, 155, 160, 165, and 170 °C), and HA wt% (0, 5, 10, and 15 wt%) on flexural mechanical properties were studied. Mechanical test results indicated that in unfilled (no HA) PLLA SRCs, compaction time and temperature increased the flexural modulus of the composites tested. Based on the results obtained for unfilled composites, a single compaction time and temperature condition of 15 min and 170 °C were selected to study the effect of HA loading on the composite mechanical properties. HA was successfully loaded onto the fibers at 0, 5, 10, and 15 wt% before hot compaction and was found to significantly increase flexural modulus (P=0.0001). Modulus values ranged from 8.3 GPa±0.5 (0 wt% HA) to 9.7 GPa±0.6 (15 wt% HA). Microscopy results suggest that the HA in these composites forms a nodular-like structure along the fibers, which allows polymer-polymer contact yet prevents longitudinal shear. The procedure used successfully generated composites with flexural moduli near the lower range of bone that may have a possible clinical use for load-bearing bone-fixation devices.

Biodegradable composites with aligned hydroxyapatite nanoneedles.

We prepared an anisotropic bone graft composite to mimic the hierarchical structure of the natural bone in which aligned hydroxyapatite (HA) nanocrystals deposit along collagen fibers. To approach the modulus and strength of the bone, we incorporated synthesized HA nanoneedles and melt drawn poly(L-lactic acid) fibers in our composite as reinforcing components. Their preferred orientation was induced via a modified pultrusion process. The HA orientation distribution was examined using wide angle X-ray diffraction. Micromechanical Halpin-Tsai model predictions considering the amount, shape, and orientation distribution of HA were compared, favorably, with the experimental observations.

Hydrogel functionalization with DNA aptamers for sustained PDGF-BB release.

We demonstrate that hydrogel functionalization with DNA aptamers can be applied for developing a novel sustained-release system.

Alkali etching of a poly(lactide) fiber.

Alkali etching of a poly(l-lactic acid) fiber was studied by exposing the fiber surface to sodium hydroxide solutions. The factors examined included the etching time (0-1.5 h), alkali concentration (0.25-3 mol/L), and etching temperature (25-80 degrees C). The extent of etching was determined gravimetrically. Both weight loss and mechanical testing results suggest that alkali etching is strictly a surface hydrolysis reaction, as opposed to a bulk reaction, and thus the weight loss rate decreases with a shrinking fiber radius. A slight increase in the fiber crystallinity observed from thermal analysis was interpreted as a result of surface-limited etching on a sheath-core fiber microstructure. The dependence of the rate on the alkali concentration is nonlinear, suggesting that the fiber weight loss rate is subject to both chemical hydrolysis and transport limitations. The dependence of the rate on the temperature follows the Arrhenius equation. The fiber weight after etching can thus be predicted by an overall expression combining all factors: time, temperature, concentration, and fiber diameter.

Solvent-specific gel-like transition via complexation of polyelectrolyte and nanoparticles suspended in - mixtures: a rheological study.

Polyelectrolytes are routinely used in many applications including hydrogels and aqueous particle suspensions. Although the rheology of charge-stabilized colloidal particle systems involving polyelectrolyte in a single solvent has been studied both theoretically and experimentally, the influence of a second solvent has received considerably less attention. We report here on the system comprising ellipsoidal nano-hydroxyapatite particles suspended in water-glycerol mixtures containing dissolved polyelectrolyte "dispersant." The nano-hydroxyapatite content ranged from 0 to 20 vol%, while the concentration of the neutralized poly(acrylic acid) dispersant was varied between 0 to 0.08 wt% in the suspension (0 to 0.108% with respect to the HA component). In contrast to earlier reports on similar suspensions, an increase in apparent viscosity by three orders of magnitude with increasing polyelectrolyte content was observed. At the highest concentrations of polyelectrolyte, the suspensions exhibited solid-like behavior as indicated by the presence of a yield behavior and a shear storage modulus one order of magnitude larger than the loss modulus. These observations led to the hypothesis that the polyelectrolyte contributed to the formation of polymer-rich water bridges between the particles, although no macrophase separation was found in the absence of the particles.

Fabrication of novel calcium phosphate/poly(lactic acid) fiber composites.

Composites using high-modulus polylactic acid (PLA) fibers coated with calcium phosphate (CaP) were prepared using a cyclic precipitation technique. Scanning electron microscopy revealed that small nuclei of CaP formed after the first soaking cycle, while large quantities of CaP particles were observed after the sixth cycle. The amount of CaP deposited on the PLA yarn increased with deposition time in Ca(2+) and PO(4) (3-) solutions and number of cycles, and decreased with stirring rate during washing cycles. It was observed that around 35 wt % of CaP was deposited on the yarn surface after six cycles of cyclic-soaking. Based on the results, a heterogeneous nucleation and growth mechanism was proposed for the CaP deposition on the surface of hydrolyzed polyester. Composites comprising the coated fibers in a poly(caprolactone) matrix exhibited flexural moduli within the range of that of the cortical bone.

Biodegradable HA-PLA 3-D porous scaffolds: effect of nano-sized filler content on scaffold properties.

Scaffolds comprising poly(lactic acid) and nano-hydroxyapatite (HA) were prepared using the solvent-casting/salt-leaching technique. NaCl was used as the leaching agent. Nano-sized HA was synthesized by a hydrothermal method at 170 degrees C and autogenous pressure. High-resolution TEM imaging revealed that the HA particles were ellipsoidal-shaped with needle-like morphologies. The particles had an average size of approximately 25 nm in width and 150 nm in length with aspect ratios ranging from 6 to 8. As the HA content increased in the scaffold from 0 to 50 wt%, the compression modulus of the scaffolds increased from 4.72+/-1.2 to 9.87+/-1.8 MPa, while the yield strength from 0.29+/-0.03 to 0.44+/-0.01 MPa. Such polymeric scaffolds should be suitable materials for non-load sharing tissue-engineering applications.