ZnO nanotubes and nanorods grown on gold thin film were used to create pH sensor devices. The developed ZnO nanotube and nanorod pH sensors display good reproducibility, repeatability and long-term stability and exhibit a pH-dependent electrochemical potential difference versus an Ag/AgCl reference electrode over a large dynamic pH range. We found the ZnO nanotubes provide sensitivity as high as twice that of the ZnO nanorods, which can be ascribed to the fact that small dimensional ZnO nanotubes have a higher level of surface and subsurface oxygen vacancies and provide a larger effective surface area with higher surface-to-volume ratio as compared to ZnO nanorods, thus affording the ZnO nanotube pH sensor a higher sensitivity. Experimental results indicate ZnO nanotubes can be used in pH sensor applications with improved performance. Moreover, the ZnO nanotube arrays may find potential application as a novel material for measurements of intracellular biochemical species within single living cells.

Abstract:In this study, a potentiometric intracellular glucose biosensor was fabricated by immobilization of glucose oxidase on nanoflake ZnO. Nanoflake ZnO with a wall thickness around 200 nm was grown on the tip of a borosilicate glass capillary and used as a selective intracellular glucose biosensor for the measurement of glucose concentrations in human adipocytes and frog oocytes. The results showed a fast response within 4 s and a logarithmic linear glucose-dependent electrochemical potential difference over a wide range of glucose concentration (500 nM-10 mM). Our measurements of intracellular glucose were consistent with the values of intracellular glucose concentrations reported in the literature. The monitoring capability of the sensor was demonstrated by following the increase in the intracellular glucose concentration induced by insulin in frog oocytes. In addition, the nanoflake ZnO material provided 1.8 times higher sensitivity than previously used ZnO nanorods under the same conditions. Moreover, the fabrication method in our experiment is simple and the resulting nanosensor showed good performance in sensitivity, stability, selectivity, reproducibility, and anti-interference. All these results demonstrate that the nanoflake ZnO can provide a promising material for reliable measurements of intracellular glucose concentrations within single living cells. Key Words:Glucose oxidase (GOD), Intracellular, Potentiometric biosensor, Nanoflake ZnO, Nafion membrane Among all glucose biosensors, enzyme-based electrochemical glucose biosensors have been in the main focus of biosensor research because of their simplicity, relatively low cost, and high sensitivity [14][15][16]. The intrinsic advantages of electrochemical biosensors are their robustness, easy miniaturization, excellent detection limits, also with small sample volumes, and ability to be used in 3 turbid biofluids. In enzyme-based electrochemical biosensors, enzyme immobilization is regarded to be one of the most important issues. Since proper immobilization of enzymes on a suitable matrix and their stability are important factors in the fabrication of biosensors, the search of support materials that provide large surface area for higher enzyme loading and a compatible microenvironment that helps enzyme bioactivity is thus of great importance.Recently, zinc oxide (ZnO) nanostructures have attracted considerable interest in the applications of biosensors due to many advantages, including non-toxicity, bio-safety, excellent biological compatibility, high electron-transfer rates, enhanced analytical performance, increased sensitivity, and easy preparation [17][18][19][20][21][22]. In addition, it is important to note that ZnO is relatively stable around biological pH-values, which makes ZnO compatible with biological fluids and species [23].Furthermore, the high isoelectric point (IEP) of ZnO (IEP 9.5) makes it a good matrix for immobilizing low IEP acidic proteins or DNA by electrostatic interactions with high binding stability [24][25][26]. This wi...

The tip of a borosilicate glass capillary with functionalized hexagonal ZnO nanorods was used to make a sensitive electrochemical intracellular Ca2+ sensor. To adjust the sensor for Ca2+ measurements with sufficient selectivity and stability, polyvinylchloride membrane containing Ca2+ ionophores were coated on the surface. The membrane covered ZnO nanorods exhibited a Ca2+-dependent electrochemical potential difference versus an Ag/AgCl reference electrode. The potential difference was linear over a large concentration range (100 nM–10 mM). The measurements of Ca2+ concentrations using our ZnO nanorods sensor in human fat cells or in frog egg cells were consistent with values of Ca2+ concentrations reported in the literature. This nanoelectrode device paves the way to measurements of intracellular biochemical species in specific locations within single living cells.

Buckling and elastic stability study of vertical well aligned ZnO nanorods grown on Si substrate and ZnO nanotubes etched from the same nanorods was done quantitatively by nanoindentation technique. The critical load, modulus of elasticity, and flexibility of the ZnO nanorods and nanotubes were observed and we compared these properties for the two nanostructures. It was observed that critical load of nanorods (2890 μN) was approximately five times larger than the critical load of the nanotubes (687 μN). It was also observed that ZnO nanotubes were approximately five times more flexible (0.32 nm/μN) than the nanorods (0.064 nm/μN). We also calculated the buckling energies of the ZnO nanotubes and nanorods from the force displacement curves. The ratio of the buckling energies was also close to unity due to the increase/decrease of five times for one parameter (critical load) and increase/decrease of five times for the other parameter (displacement) of the two samples. We calculated critical load, critical stress, strain, and Young modulus of elasticity of single ZnO nanorod and nanotube. The high flexibility of the nanotubes and high elasticity of the ZnO nanorods can be used to enhance the efficiency of piezoelectric nanodevices. We used the Euler buckling model and shell cylindrical model for the analysis of the mechanical properties of ZnO nanotubes and nanorods.

Mechanical instability and buckling characterization of vertically aligned single-crystal ZnO nanorods grown on different substrates including Si, SiC and sapphire (α-Al(2)O(3)) was done quantitatively by the nanoindentation technique. The nanorods were grown on these substrates by the vapor-liquid-solid (VLS) method. The critical load for the ZnO nanorods grown on the Si, SiC and Al(2)O(3) substrates was found to be 188, 205 and 130 µN, respectively. These observed critical loads were for nanorods with 280 nm diameters and 900 nm length using Si as a substrate, while the corresponding values were 330 nm, 3300 nm, and 780 nm, 3000 nm in the case of SiC and Al(2)O(3) substrates, respectively. The corresponding buckling energies calculated from the force displacement curves were 8.46 × 10(-12), 1.158 × 10(-11) and 1.092 × 10(-11) J, respectively. Based on the Euler model for long nanorods and the J B Johnson model (which is an extension of the Euler model) for intermediate nanorods, the modulus of elasticity of a single rod was calculated for each sample. Finally, the critical buckling stress and strain were also calculated for all samples. We found that the buckling characteristic is strongly dependent on the quality, lattice mismatch and adhesion of the nanorods with the substrate.

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Nanomechanical tests of bending flexibility, kinking, and buckling failure characterization of vertically aligned single crystal ZnO nanorods/nanowires were performed quantitatively by nanoindentation technique. These nanostructures were grown by the vapor liquid solid ͑VLS͒ method, a relatively high temperature approach, and the aqueous chemical growth ͑ACG͒ method, a relatively low temperature approach on different substrates, including SiC and Si. The first critical load at the inflection point found for the ZnO nanorods/nanowires grown by ACG method was 105 N on the SiC substrates and 114 N on the Si substrates. The corresponding buckling energies calculated from the force-displacement curves were 3.15ϫ 10 −12 and 2.337ϫ 10 −12 J, respectively. Similarly, for the samples grown by the VLS method, the first critical load at the inflection point and the corresponding buckling energies were calculated from the force-displacement curves as 198 N and 7.03ϫ 10 −12 J on the SiC substrates, and 19 N and 1.805ϫ 10 −13 J on the Si substrates. Moreover, the critical buckling stress, strain, and strain energy were also calculated for all samples. The strain energy for all samples was much less than the corresponding buckling energy. This shows that our as-grown samples are elastic and flexible. The elasticity measurement was performed for all the samples before reaching the first critical and kinking inflection point, and we subsequently observed the bending flexibility, kinking, and buckling phenomena on the same nanorods/nanowires. We observed that the loading and unloading behaviors during the bending test of the as-grown samples were highly symmetrical, and also that the highest point on the bending curves and the first inflection and critical point were very close. ZnO nanorods/nanowires grown on SiC by the ACG method, and those grown by the VLS method on Si substrates, show a linear relation and high modulus of elasticity for the force and displacement up to the first inflection and critical point. The results also show that the elasticity of the ZnO single crystal is approximately linear up to the first inflection point, is independent of the growth method and is strongly dependent on the verticality on the surface of the substrates. In addition, the results show that after the first buckling point, the nanorods/nanowires have plasticity, and become more flexible to produce multiple kinks.