Non-stick syringe needles: Beneficial effects of thin film metallic glass coating.

This paper reports on the use of Zr-based (Zr53Cu33Al9Ta5) thin film metallic glass (TFMG) for the coating of syringe needles and compares the results with those obtained using titanium nitride and pure titanium coatings. TFMG coatings were shown to reduce insertion forces by ∼66% and retraction forces by ∼72%, when tested using polyurethane rubber block. The benefits of TFMG-coated needles were also observed when tested using muscle tissue from pigs. In nano-scratch tests, the TFMG coatings achieved a coefficient of friction (COF) of just ∼0.05, which is about one order of magnitude lower than those of other coatings. Finite-element modeling also indicates a significant reduction in injection and retraction forces. The COF can be attributed to the absence of grain boundaries in the TFMG coating as well as a smooth surface morphology and low surface free energy.

A fine pointed glucose oxidase immobilized electrode for low-invasive amperometric glucose monitoring.

A low invasive type glucose sensor, which has a sensing region at the tip of a fine pointed electrode, was developed for continuous glucose monitoring. Platinum-iridium alloy electrode with a surface area of 0.045mm(2) was settled at the middle of pointed PEEK (Polyetheretherketone) tubing and was employed as sensing electrode. Electrodeposition of glucose oxidase in the presence of surfactant, Triton X-100, was performed for high-density enzyme immobilization followed by the electropolymerization of o-phenylenediamine for the formation of functional entrapping and permselective polymer membrane. Ag/AgCl film was coated on the surface of PEEK tubing as reference electrode. Amperometric responses of the prepared sensors to glucose were measured at a potential of 0.60V (vs. Ag/AgCl). The prepared electrode showed the sensitivity of 2.55µA/cm(2) mM with high linearity of 0.9986, within the glucose concentration range up to 21mM. The detection limit (S/N=3) was determined to be 0.11mM. The glucose sensor properties were evaluated in phosphate buffer solution and in vivo monitoring by the implantation of the sensors in rabbit, while conventional needle type sensors as a reference were used. The results showed that change in output current of the proposed sensor fluctuated similar with one in output current of the conventional needle type sensors, which was also in similar accordance with actual blood sugar level measured by commercially glucose meter. One-point calibration method was used to calibrate the sensor output current.

Fabrication of Amperometric Glucose Sensor Using Glucose Oxidase-Cellulose Nanofiber Aqueous Solution.

Cellulose nanofiber aqueous solution, which remained virtually transparent for more than one week, was prepared by using the clear upper layer of diluted cellulose nanofiber solution produced by wet jet milling. Glucose oxidase (GOx) was easily dissolved in this solution and GOx-immobilized electrode was easily fabricated by simple repetitious drops of GOx-cellulose solution on the surface of a platinum-iridium electrode. Glucose sensor properties of the obtained electrodes were examined in phosphate buffer solution of pH 7.4 at 40°C. The obtained electrode provided a glucose sensor response with significantly high response speed and good linear relationship between glucose concentration and response current. After an initial decrease of response sensitivity for a few days, relatively constant sensitivity was obtained for about 20 days. Nevertheless, the influence of electroactive compounds such as ascorbic acid, uric acid and acetoaminophen were not negletable.

Highly selective needle-type glucose sensors prepared by the immobilization of glucose oxidase on γ-polyglutamic acid film.

Fine needle-type glucose sensors with an outer diameter of less that 0.2 mm were fabricated using a low-cost biodegradable γ-polyglutamic acid (PGA) not only as a glucose oxidase (GOx) immobilizing material, but also as a permselective inner membrane. PGA film was prepared on a cellulose acetate-coated Pt-Ir wire electrode, and GOx was covalently immobilized on its surface using water-soluble carbodiimide. The obtained electrode was practically not affected by the existence of electroactive compounds, and provided long-term stability for approximately one month. It also functioned in horse serum with a good linear relationship between the current and glucose concentrations within the range of 2.8 to 22.4 mM.

[Study of the removal of Pb2+ from aqueous solution by poly-gamma-glutamic acid coated magnetic nanoparticles].

In this study, a novel low cost magnetic adsorbent material prepared by poly-gamma-glutamic acid (gamma-PGA) coating Fe3o4 magnetic particles, which was called coated magnetic namoparticles (PG-M) was developed for the removal of Pb2+ from water by Dr. Yasuzawa. The particle size of PG-M was about 120-320 nm, and there was no significant difference in Fe3O4 and PG-M particle size, Fe3O4 was only as the support of PG-M core and did not directly involve in the reaction. The shape of PG-M was irregular cubic structure. The experiments were applied to quantify adsorptive time, pH, competitive ion and organics on the removal effect of Pb2+. The results showed that PG-M was effective in removal of Pb2+; the equilibrium amount of adsorptive was as high as 93.3 mg/g and the optimized condition of pH value for metal ions removal was 7.0, while contact time was about 45 min. The removal efficiency of Pb2+ was not significantly influenced by Na+ while was reduced with the increasing concentration of Ca2+. The removal of Pb2+ was enhanced with the presence of organic matter (humic acid, HA) when the concentration of HA was below 5 mg/L, and decreased when the concentration of HA exceeded 5 mg/L. Langmuir isotherms fitted the experimental data better compared to Freundlich isotherms. Pseudo second order model well described the sorption kinetics of Pb2+. The used PG-M can be desorbed by 0.1 mol/L HCl and became reusable. PG-M is nontoxic and eco-friendly, which have a good prospect in water treatment.

Synthesis and electropolymerization of phosphorylcholine-containing pyrroles and their hemocompatible properties.

A series of N-substituted pyrroles having phosphorylcholine with different methylene chain lengths between pyrrole group and phosphorylcholine group were synthesized and their electropolymerizations were performed in aqueous solution. The methylene chains were trimethylene (n = 3), pentamethylene (n = 5), nonamethylene (n = 9), and undecamethylene (n = 11), for 3-(1-pyrrolyl)propyl-2-(trimethylammonium)ethyl phosphate (5a), 5-(1-pyrrolyl)pentyl-2-(trimethylammonium)ethyl phosphate (5b), 9-(1-pyrrolyl)nonyl-2-(trimethylammonium)ethyl phosphate (5c), and 11-(1-pyrrolyl)undecyl-2-(trimethylammonium)ethyl phosphate (5d), respectively. Although electropolymerized films were produced from all pyrrole derivatives, thick and black polymer films were prepared from 5a, 5b and 5c. The pyrrole derivative with long methylene-chain 5d provided only colorless or slightly blackish thin film. Hemocompatibilities of the polymers from 5a, 5b and 5c were evaluated by platelet rich plasma (PRP) contacting studies and scanning electron microscopy (SEM) observations. The results indicated that these polymers have excellent hemocompatibility.

Fabrication of an implantable fine needle-type glucose sensor using gamma-polyglutamic acid.

Implantable fine needle-type glucose sensors with an outer diameter of less that 0.2 mm were fabricated using a low-cost and non-animal origin polyamide, gamma-polyglutamic acid (PGA) as a glucose oxidase (GOx) immobilizing material. Two types of PGA, gamma-polyglutamic acid (PGAH) and gamma-polyglutamic acid sodium salt (PGANa), were employed to prepare GOx immobilized film by the covalent attachment of GOx using water-soluble carbodiimide (EDC). Nafion/cellulose acetate composite film and polyurethane/polydimethylsiloxane composite film were employed as a permselective inner film and a biocompatible outer film, respectively. The procedure of enzyme-immobilized film fabrication affected the stability of the sensor; that is, GOx immobilized film prepared by pouring a mixture solution of GOx and EDC on a PGA precoated surface showed higher sensor stability than that prepared by pouring a mixture solution of GOx, PGA and EDC. Although, obvious differences in the sensor properties were not observed between the use of PGANa and PGAH, the electrode prepared with PGAH had a lower swelling degree. The glucose sensors prepared with both PGANa and PGAH were practically not affected by the existence of electroactive compounds, such as uric acid, and provided long-term stability for approximately 5 weeks. These sensors also showed good performance in horse serum.

Characterization of a glucose sensor prepared by electropolymerization of pyrroles containing a tris-bipyridine osmium complex.

A glucose sensor was developed by electrocopolymerization using pyrroles containing a tris-bipyridine (bpy) osmium complex (Os-py), pyrrole (py), pyrrole propanoic acid (PPA) and glucose oxidase (GOx) to improve the key performance characteristics, such as the sensitivity, selectivity, and long-term stability. Tris-bipyridine osmium pyrrole complexes with four different methylene moieties were utilized to correlate the methylene length with the glucose sensor performance. The electrocatalytic response of glucose was clearly observed at electrodes modified with Os-py, except for the electrode immobilized with the Os-py complex containing the shortest methylene moiety. The current response to glucose increased up to a concentration of 100 mmol dm(-3). The electrocatalytic response to glucose at the [Os(bpy)(2)(py(6)-bpy)](2+/3+)/py/PPA/GOx electrode was stable for more than 100 days. Dissolved oxygen and potential interference compounds (ascorbic acid, uric acid, and acetaminophen) minimally perturbed the current response to glucose at the [Os(DM-bpy)(2)(py(6)-bpy)](2+/3+)/py/PPA/GOx electrode. Based on these results, a longer methylene moiety appears to improve the performance characteristics of a glucose sensor fabricated via the electropolymerization of tris-bipyridine osmium pyrrole complexes.

Selection of novel structural zinc sites from a random peptide library.

Zinc ion (Zn(2+)) can be coordinated with four or three amino acid residues to stabilize a protein's structure or to form a catalytic active center. We used phage display selection of a dodecamer random peptide library with Zn(2+) to identify structural zinc sites. The binding specificity for Zn(2+) of selected sequences was confirmed using enzyme-linked immunosorbent and competitive inhibition assays. Circular dichroism spectra indicated that the interaction with Zn(2+) induced a change in conformation, which means the peptide acts as a structural zinc site. Furthermore, a search of protein databases revealed that two selected sequences corresponded to parts of natural zinc sites of copper/zinc superoxide dismutase and zinc-containing ferredoxin. We demonstrated that Zn(2+)-binding sequences selected from the random combinatorial library would be candidates for artificial structural zinc sites.