Liquid crystal membranes for serum-compatible diabetes management-assisting subcutaneously implanted amperometric glucose sensors

Membranes formed of thermodynamically stable cubic phase lyotropic liquid crystals (LLCs) could replace the presently used polymeric membranes, applied to reduce the flux of glucose in semicontinuous, subcutaneously implanted, user-replaced, miniature, amperometric glucose sensors, assisting in the management of diabetes. LLC-forming amphiphilic compounds set and toughen spontaneously after mixing with water, without undergoing chemical change. When applied by doctor-blading, they form membranes having three-dimensionally interconnected water channels of uniform diameter, with reproducible glucose transport-characteristics. We find that the best studied cubic phase LLCs, which are formed of monoolein and water, are not useful in their intended application because they are hydrolyzed by serum lipases. Those formed of phytantriol, a liquid at ambient temperature, and water, are not hydrolyzed but change their shape and size in a dehydration and rehydration cycle. Because glucose sensors are sterilized and stored in a sealed package in a dry atmosphere, drying and rehydration must not change the transport characteristics. A third, novel, LLC-forming, amphiphile 1-O-beta-(3,7,11,15-tetramethylhexadecyl)-d-ribopyranoside, I, was synthesized, and its phase diagram was tailored by adding Vitamin E acetate, to form a cubic phase. The phase was stable through the 20 degrees C-90 degrees C temperature range in excess of water and had the desired glucose-transport characteristics. A preferred LLC, II, was formed of water and I containing 7 wt % of Vitamin E acetate. When II was applied to a wired glucose oxidase bioelectrocatalyst, sensors of reproducible glucose-sensitivity were formed. At a 0.1 mm thickness of II, the membrane reduced the glucose flux 5-fold and increased the 90% response-time by less than 2 min. The membrane was mechanically rugged, withstanding the approximately 1 N m(-2) maximal shear stress at 5 mm diameter electrodes rotating at 4000 rpm. The activation energy for glucose permeation through II was reduced to 15.6 kJ/mol, making the sensors's current less temperature-dependent than that of the polymeric-membrane overcoated implantable glucose sensors.     

A percutaneous device as model to study the in vivo performance of implantable amperometric glucose sensors

Glucose kinetics were investigated in subcutaneous tissue of rabbits, in which a percutaneous device was implanted. The device was used for collection of tissue fluid and as carrier of an amperometric glucose sensor. Changes in glycaemia were reflected in subcutaneous tissue fluid. However, a limited number of responses of the implanted sensors were observed. Histologic evaluation showed thin fibrous capsules surrounding the implants. Accumulations of inflammatory cells were observed inside the subcutaneous chamber. The experiments again showed that changes in blood glucose concentration can be measured in subcutaneous tissue fluid collected with a percutaneous device. Nevertheless, implanted glucose sensors could not reliably monitor these changes. Supported by our histological observations and sufficient in vitro performance, we suppose that the cellular reaction to the sensor plays an important role in this poor in vivo performance. In combination with adsorption of tissue fluid proteins, this results in a reversible deactivation of implanted sensors. The exact mechanisms involved in this process are currently unknown and need further investigation.     

In-situ growth of copper sulfide nanocrystals on multiwalled carbon nanotubes and their application as novel solar cell and amperometric glucose sensor materials

Single-crystalline copper sulfide (beta-Cu2S) nanocrystals (NCs) were grown in situ on multiwalled carbon nanotubes (MWCNTs) by the solvothermal method. The morphology of the Cu2S NCs was varied from spherical particles (av size=4 nm) to triangular plates (av size=12 nm) by increasing the concentration of the precursors. The lattice matching between Cu2S and the MWCNTs would be an important factor in the growth of Cu2S NCs on the MWCNTs. The solar cells and the amperometric glucose sensors fabricated using these Cu2S-MWCNT hybrid nanostructures respond more sensitively than those using the Cu2S NCs (or MWCNTs) alone. The utilization of the active Cu2S NCs through direct binding with the conductive MWCNTs would lead to excellent performance of these nanodevices.     

In situ trace analysis of oil in water with mid-infrared fiberoptic chemical sensors

The determination of trace amounts of oil in water facilitates the forensic analysis on the presence and origin of oil in the aqueous environment. To this end, the present study focuses on direct sensing schemes for quantifying trace amounts of oil in water using mid-infrared (MIR) evanescent field absorption spectroscopy via fiberoptic chemical sensors. MIR transparent silver halide fibers were utilized as optical transducer for interrogating oil-in-water emulsions via the evanescent field emanating from the waveguide surface, and penetrating the surrounding aqueous environment by a couple of micrometers. Unmodified fibers and fibers surface-modified with grafted epoxidized polybutadiene layers enabled the direct detection of crude oil in a deionized water matrix at the ppm level to ppb concentration level, respectively. Thus, direct chemical sensing of crude oil IR signatures without any sample preparation as low as 46 ppb was achieved with a response time of a few seconds.     

Acetylcholine and choline amperometric enzyme sensors characterized in vitro and in vivo

Acetylcholine (ACh) and choline (Ch) are important neuroactive molecules, yet detection of these substances in vivo presents significant analytical challenges. New multienzyme amperometric biosensors are presented here with measurement of physiologically relevant levels of ACh and Ch in vivo. Poly(m-(1,3)-phenylenediamine) (pmPD) electropolymerized on a platinum iridium wire (Pt) served as a template for immobilization of enzymes. A multienzyme layer containing choline oxidase (ChOx) and ascorbic acid oxidase (AAO) for a Ch sensor or ChOx, acetylcholinesterase (AChE), and AAO for a ACh/Ch sensor was immobilized with bovine serum albumin by cross-linking with glutaraldeyhyde. The pmPD enzyme sensors displayed enhanced sensitivity, stability, and selectivity compared to the same multienzyme systems immobilized to solvent cast Nafion and cellulose acetate-modified Pt. Sensor response was linear up to 100 microM ACh or Ch. Detection limits were 0.66 +/- 0.46 microM ACh and 0.33 +/- 0.09 microM Ch, and response times were <1 s. Selectivity for Ch and ACh relative to potential interferences and pharmacological agents commonly used to examine cholinergic physiology was demonstrated. Temperature and pH dependence and the effect of storage conditions on sensor sensitivity and selectivity were determined. Exogenous and endogenous Ch and ACh were measured in the rat brain in vivo.     

Nanocrystalline cobalt-oxide powders by solution-combustion synthesis and their application in chemical sensors

The present study demonstrates the relationship between the combustion reaction mechanism induced by the exothermicity of the cobalt nitrate-glycine solution-combustion reactions and morphological details of the nanocrystalline Co₃O₄. The thermal decomposition pathway and the amount of the heat liberated in combustion are defined by the exothermic reaction between gaseous NH₃ and N₂O species. A direct evidence that the exothermicity of the combustion reaction plays an important role in formation of the powders with different morphology was obtained from the scanning and transmission electron microscopies. In contrast to stoichiometric reaction, where the short-string Co₃O₄ particles form hard agglomerates, the energetically softer 50% fuel lean reaction is responsible for weak bonds between Co₃O₄ particles and formation of the loose cauliflower-like agglomerates. The latter powder with the specific surface area of 64.4 m²/g and the average crystallite size of ～11 nm was used for the processing of drop-coated sensors, which showed a superior sensor response toward 20 ppm of acetone in 25% r.h. humidity and at low operating temperature of 150 °C.     

In vivo biocompatibility and analytical performance of intravascular amperometric oxygen sensors prepared with improved nitric oxide-releasing silicone rubber coating

The in vivo biocompatibility and analytical performance of amperometric oxygen-sensing catheters prepared with a new type of nitric oxide (NO)-releasing silicone rubber polymer (DACA/N2O2 SR) is reported. The NO-release silicone rubber coating contains diazeniumdiolated secondary amine sites covalently anchored to a dimethylsiloxane matrix. Narrow diameter (0.9 mm, o.d.) silicone rubber tubing coated with this polymer can be employed to construct functional oxygen-sensing catheters that release NO continuously at levels > 1 x 10(-10) mol/cm2-min for more than 20 h. In vivo evaluation of such sensors within the carotid and femoral arteries of swine over a 16-h time period demonstrates that sensors prepared with the new NO-release coating exhibit no significant platelet adhesion or thrombus formation, but control sensors (non-NO release) implanted within the same animals do show a high propensity for cell adhesion and bulk clot formation. Furthermore, the in vivo analytical data provided by sensors fabricated with NO-release coatings (N = 9) are shown to be statistically equivalent to PO2 levels measured in vitro on discrete samples of blood. Control sensors (N = 9) placed within the same animals yield average PO2 values that are statistically different (p < or = 0.05) (lower) from both the levels measured on discrete samples and those provided by the NO-release sensors over a 16-h in vivo monitoring period.     

Preparation of quaternary nitrogen-containing plasma films and their application to moisture sensors

To seek the possible formation of positively charged plasma films the chemical composition of plasma films formed from organosilicones containing nitrogen (hexamethyldisilazane (HMDSZ), trimethylsilyldimethylamine (TMSDMA) and a mixture of tetramethylsilane and NH₃) was analysed by elemental analysis and IR spectroscopy, and quaternization of these films with methyl bromide was carried out. IR spectroscopic and electron spectroscopy for chemical analysis studies revealed that the plasma films from TMSDMA and the TMS-NH₃ mixture were successfully quaternized but those from HMDSZ were not. This indicates that the structural characteristics of the starting compounds exert a powerful influence on the polymer-forming process. The quaternized plasma films prepared from TMSDMA were used to prepare moisture sensor devices.     

TiO2 nanotube-based field effect transistors and their application as humidity sensors

TiO₂ nanotubes are the building units of various devices of energy- and environment-related applications and the property studies of individual TiO₂ nanotubes are important to understand and improve the performance of TiO₂ nanotubes-based devices. Here we report the electrical property study of individual TiO₂ nanotubes enabled by the construction of field effect transistors based on individual TiO₂ nanotubes. It is found that individual TiO₂ nanotubes exhibit typical n-type electrical conduction characteristics, with electron mobility of 6.9 × 10^?3 cm²/V s at V_ds = 1 V, and electron concentration of 2.8 × 10¹⁷ cm^?3. Moreover, the on–off ratio of the TiO₂ nanotube-based field effect transistors is as high as 10³. Humidity sensing test shows the sensitive response of the individual TiO₂ nanotubes to water vapor.     

In situ monitoring of friction surfaces and their sequence pattern analysis

Friction occurs between solid surfaces, and even sometimes on lubricated surfaces. To understand tribological subjects, it is important to know the changes that occur in friction surfaces. In this study, a laser strobe technique is applied to a friction surface observation. The recorded surface images were analysed using pattern-matching methods and their correlations are discussed. A test using pin-on-plate methods with carbon steels was performed using a reciprocating motion speed of 10 Hz for 4.9 N. A pulsed laser light (Nd:YAG SHG=532 nm, 5 ns per pulse) was irradiated onto the friction surface. It was induced using an optical microscope that was located just to the side of the pin. The laser pulse was synchronized with the plate motion, which was a trigger of the laser pulse. The surface image was stored for every cycle. These sequences were calculated and their correlations were analysed as a function of the surface pattern and the friction track size and shape. Analysis revealed that some groups were distinguishable as parameters of the damage size and shape.     

ZnO nanonails: synthesis and their application as glucose biosensor

Well-crystallized zinc oxide nanonails were grown in a high density by thermal evaporation process and were used as supporting matrixes for glucose oxidase (GOx) immobilization to construct efficient glucose biosensor. The GOx attached to the surfaces of ZnO nanonails had more spatial freedom in its orientation, which facilitated the direct electron transfer between the active sites of immobilized GOx and electrode surface. The fabricated biosensor showed a high sensitivity of 24.613 microA cm(-2) mM(-1) with a response time less than 10 s. Moreover, it shows a linear range from 0.1 to 7.1 mM with a correlation coefficient of R = 0.9937 and detection limit of 5 microM.     

Superparamagnetic iron oxide nanoparticles assembled magnetic nanobubbles and their application for neural stem cells labeling

Micro/nanobubbles for use as ultrasound contrast agents have been fabricated with different shell materials.When various biomedical nanoparticles have been embedded in the shells of bubbles,the composite structures have shown promising applications in multi-modal imaging,drug/gene delivery,and biomedical sensing.In this study,we developed a new gas-liquid interface self-assembly method to prepare magnetic nanobubbles embedded with superparamagnetic iron oxide nanoparticles(SPIONs).The diameter of the generated assembled nanobubbles was 227.40±87.21 nm with a good polydispersity index(PDI)of 0.29.Under the condition of 150 compression cycles,the nanobubble concentration could reach about 6.12×10⁹/mL.Transmission electron microscopy(TEM)and scanning electronic microscopy(SEM)demonstrated that the assembled nanobubbles had a hollow gas core with SPIONs adsorbed on the surface.Ultrasound(US)imaging and magnetic resonance imaging(MRI)experiments indicated that the assembled magnetic nanobubbles exhibited good US and MR contrast capabilities.Moreover,the assembled magnetic nanobubbles were used to label neural stem cells under ultrasound exposure.After 40 s US exposure,the magnetic nanobubbles could be delivered into cells with 2.80 pg Fe per cell,which could be observed in the intracellular endosome by TEM.Compared with common incubation methods,the ultrasound exposure method did not introduce the potential cytotoxicity of transfection reagents and the efficiency was about twice as high as the efficiency of incubation.Therefore,the assembled magnetic nanobubbles prepared through the pressure-driven gas-liquid interface assembly approach could be a potential US/MRI dual model imaging nanocarrier for regenerative applications.     

Air-stable n-type transistors based on assembled aligned carbon nanotube arrays and their application in complementary metal-oxide-semiconductor electronics

Carbon nanotubes(CNTs)are ideal candidates for beyond-silicon nano-electronics because of their high mobility and low-cost processing.Recently,assembled massively aligned CNTs have emerged as an important platform for semiconductor electronics.However,realizing sophisticated complementary nano-electronics has been challenging due to the p-type nature of carbon nanotubes in air.Fabrication of n-type behavior field effect transistors(FETs)based on assembled aligned CNT arrays is needed for advanced CNT electronics.Here in this paper,we report a scalable process to make n-type behavior FETs based on assembled aligned CNT arrays.Air-stable and high-performance n-type behavior CNT FETs are achieved with high yield by combining the atomic layer deposition dielectric and metal contact engineering.We also systematically studied the contribution of metal contacts and atomic layer deposition passivation in determining the transistor polarity.Based on these experimental results,we report the successful demonstration of complementary metal-oxide-semiconductor inverters with good performance,which paves the way for realizing the promising future of carbon nanotube nano-electronics.     

In situ synthesis of graphene/cobalt nanocomposites and their magnetic properties

Graphene, which possesses unique nanostructure and excellent properties, is considered as a low cost alternative to carbon nanotubes in nanocomposites. In this study, we present a simple in situ approach for the deposition of cobalt (Co) nanoparticles onto surfaces of graphene sheets by hydrazine hydrate reduction. The as-synthesized composites were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, Raman spectroscopy, transmission electron microscopy (TEM) and thermogravimetry and differential scanning calorimetry. It was shown that the as-formed Co nanoparticles were densely and homogeneously deposited on the surfaces of the graphene sheets and as a result, the restacking of the as-reduced graphene sheets was effectively inhibited. Magnetic studies reveal that the graphene/Co nanocomposite displays ferromagnetic behavior with saturation magnetizations of 53.4 emu g⁻¹, remanent magnetization of 6.0 emu g⁻¹ and coercivity of 226 Oe at room temperature, which make it promising for practical applications in future nanotechnology.     

In situ synthesis of metal nanoparticles in polymer matrix and their optical limiting applications

We present an overview of the simple and environmentally benign protocol we have developed recently, for the in situ generation of metal nanoparticles inside polymer films by mild thermal annealing, leading to free-standing as well as supported thin films of nanoparticle-embedded polymer. The fabrication chemistry is discussed and spectroscopic/microscopic characterizations of silver and gold nanoparticles in poly(vinyl alcohol) film are presented. Optical limiting characteristics of the silver-polymer system are investigated in detail and preliminary results for the gold-polymer system are reported.     

Synthesis of Ba-doped CeO(2) nanowires and their application as humidity sensors

Ba-doped CeO(2) nanowires were obtained from CeO(2) particles through a facile composite-hydroxide-mediated (CHM) route. The products were characterized by x-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscope (HRTEM). The formation process of the product was discussed. Humidity sensors based on the source material CeO(2) particles, Ba-doped CeO(2) nanowires grown for 12 and 72?h, were fabricated. The responses to humidity for static and dynamic testing proved that both doping Ba into CeO(2) and converting morphology into a nanowire can improve the humidity sensitivity. The resistance changes from 465 to 3.9?MΩ as the relative humidity (RH) increases from 25% to 88%, indicating promising applications of Ba-doped CeO(2) nanowires in environmental monitoring.     

In situ measurement of Cl- concentrations and pH at the reinforcing steel/concrete interface by combination sensors

This paper presents an in situ, nondestructive method of monitoring Cl- concentrations and pH values at the steel/concrete interface. The Ag/AgCl electrodes prepared by the electrochemical anodization and the Ir/IrO2 electrodes prepared by thermal oxidation in carbonate served as Cl- concentration and pH sensors, respectively. The potentiometric response of the Ag/AgCl electrode to the logarithm of Cl- concentrations ranging from 1 x 10(-4) to 2 M in saturated Ca(OH)2 solution simulating the inner electrolytic medium of concrete shows good linearity. The Ir/IrO2 electrode also exhibits an ideal Nernstian response in the range of pH 1-14. The Ag/AgCl and Ir/IrO2 electrodes were combined into a multiplex Cl-/pH sensor, and the sensor was embedded in concrete close to the steel/concrete interface to realize an in situ and long-term measurement of Cl- concentrations and pH values. The results indicate that the combined sensor is robust and sensitive enough to in situ measure Cl- concentrations and pH quantitatively at the steel/concrete interface, which is of indispensable importance to the study of corrosion and protection of the steel in concrete.