Electrochemical engineering of hollow nanoarchitectures: pulse/step anodization (Si, Al, Ti) and their applications.

Hollow nanoarchitectured materials with straight channels play a crucial role in the fields of renewable energy, environment and biotechnology due to their one-dimensional morphology and extraordinary properties. The current challenge is the difficulty on tailoring hollow nanoarchitectures with well-controlled morphology at a relatively low cost. As a conventional technique, electrochemistry exhibits its unique advantage on machining nanostructures. In this review, we present the progress of electrochemistry as a valuable tool in construction of novel hollow nanoarchitectures through pulse/step anodization, such as surface pre-texturing, modulated, branched and multilayered pore architectures, and free-standing membranes. Basic principles for electrochemical engineering of mono- or multi-ordered nanostructures as well as free-standing membranes are extracted from specific examples (i.e. porous silicon, aluminum and titanium oxide). The potential of such nanoarchitectures are further demonstrated for the applications of photovoltaics, water splitting, organic degradation, nanostructure templates, biosensors and drug release. The electrochemical techniques provide a powerful approach to produce nanostructures with morphological complexity, which could have far-reaching implications in the design of future nanoscale systems.

Improved Crystallinity of Annealed 0002 AlN Films on Sapphire Substrate.

AlN is a piezoelectric material used in telecommunication applications due to its high surface acoustic wave (SAW) velocity, stability, and mechanical strength. Its performance is linked to film quality, and one method to achieve high-quality films goes through the process of annealing. Consequently, c-orientated AlN film with a thickness of 1.1 µm deposited on sapphire was annealed at temperatures of 1100 °C and 1150 °C in a N2 controlled atmosphere. This was compared to annealing at 1100 °C, 1450 °C, and 1700 °C with N2 flow in an open atmosphere environment. Sample rotation studies revealed a significant impact on the ⍵-2θ X-ray rocking curve. A slight variation in the film crystallinity across the wafer was observed. After the annealing, it was found that the lattice parameter c was increased by up to 2%, whereas the screw dislocation density dropped from 3.31 × 1010 to 0.478 × 1010 cm-2, and the full width at half maximum (FWHM) of reflection (0002) was reduced from 1.16° to 0.41° at 1450 °C. It was shown that annealing in a N2-controlled atmosphere plays a major role in reducing the oxidation of the AlN film, which is important for acoustic wave devices where the electrodes are placed directly on the piezoelectric substrate. The face-to-face arrangement of the samples could further reduce this oxidation effect.

Evaluation of sampling methods for monitoring effluent phosphorus for on-site wastewater treatment systems.

More than 1,600 prefabricated on-site wastewater treatment plants are in operation in the Morsa watershed in Norway. As of 2010 a monitoring program on the performance of these plants is in effect. Sampling methods for wastewater treatment plants is discussed, and different methods are compared. The study includes six different plant models, of which all are prefabricated package plants. The parameters investigated were total phosphorus (Tot-P), orthophosphate (PO(4)-P) and suspended solids (SS). Diurnal curves showed no apparent repetitive variation over 24 h intervals, indicating good equalization and robust design to compensate for highly variable loadings. A comparison of grab samples and time proportional composite samples showed almost identical average values, and a paired two-tailed Student's t-test indicates no statistically significant difference between the sampling methods. The results indicate that equivalent results should be expected irrespective of sampling method, and, as composite sampling is attributed to much higher costs, it is recommended that grab sampling should be used when a large number of plants are evaluated.

Long term in-line sludge storage in wastewater treatment plants: the potential for phosphorus release.

Phosphorus removal in on-site wastewater treatment plants is normally obtained by chemical precipitation. Aluminium-based chemicals are the favoured coagulants as they are not affected by redox potential. On-site wastewater treatment package plants do not have separate sludge treatment facilities, and sludge is normally collected on an annual basis. This can potentially increase the risk of phosphorus release into the water phase, subsequently reducing treatment efficiency. This study aimed to detect release of phosphorus as a result of chemical and biological processes. Variables in the study were time, aluminium dosage and pH. Wastewater sludge was monitored for 46 weeks to investigate the different mechanisms of phosphorus release and the longevity of the aluminium treatment involving varying aluminium dosages. Phosphorus compounds were analysed based on a modified Psenner sequential fractionation method. Both pH and aluminium dosage affect the longevity of the phosphorus retention of chemically precipitated wastewater sludge, where sufficient longevity is obtained with pH control and increased aluminium dosages. Chemical dosages similar to what is considered normal levels are sufficient to retain the phosphorus in the sludge for annual sludge collection intervals. Release of soluble phosphorus was attributed to microbial activity and crystallization of Al-hydroxide complexes.

Sodium Persulfate Pre-treatment of Copper Foils Enabling Homogenous Growth of Cu(OH)2 Nanoneedle Films for Electrochemical CO2 Reduction.

Oxide-derived copper (OD-Cu) catalysts have received widespread attention for their ability to produce energy-dense multicarbon products. Within this class of materials, nanostructured copper hydroxide (Cu(OH)2 ) has shown excellent catalytic properties, but its synthesis requires complex pre-treatment steps of the Cu surface. In this study, we have developed a simple two-step synthesis method for homogenous Cu(OH)2 nanoneedle films using a sodium persulfate pre-treatment step prior to anodization. The Cu(OH)2 nanoneedle films show drastically enhanced uniformity after the pre-treatment due to improved current distribution and can be grown over large surface areas (63 cm2 ). As a catalyst for CO2 reduction, the Cu(OH)2 favours ethylene formation, with a near total suppression of methane production. A peak faradaic efficiency (FE) of 36.5 % is found at -1.0 V vs. the reversible hydrogen electrode (RHE), and the catalyst remains stable while providing an ethylene to methane ratio of 27.8 after 6 h of reaction.

Hybrid electrochemical sensor platform for capsaicin determination using coarsely stepped cyclic squarewave voltammetry.

A small, standalone electrochemical hybrid sensor platform, combining flexible electronics and screen-printed electrodes, is demonstrated in the determination of capsaicin through adsorptive stripping voltammetry. The sensing scheme was simplified to be compatible with a low-cost device. The simplification involved eliminating the need for additional modification of the electrode and employing a coarsely stepped squarewave voltammetry, a technique which is applicable with less sophisticated instrumentation. This architecture was found to be suitable for concentrations up to at least 5000 µM with a detection limit of 1.98 µM. The screen-printed carbon graphite electrodes were made reusable through an ethanol rinsing protocol. The effect of ethanol/buffer volumetric ratio in the test sample was shown to greatly influence the analytical data, and a fixed 10% (v/v) was chosen as a compromise between signal-to-noise ratio and not exceeding the solubility limit of the desired upper range.

Implementation of radiotelemetry in a lab-in-a-pill format.

A miniaturised lab-in-a-pill device has been produced incorporating a temperature and pH sensor with wireless communication using the 433.92 MHz ISM band. The device has been designed in order to enable real time in situ measurements in the gastrointestinal (GI) tract, and accordingly, issues concerning the resolution and accuracy of the data, and the lifetime of the device have been considered. The sensors, which will measure two key parameters reflecting the physiological environment in the GI (as indicators for disease) were both controlled by an application specific integrated circuit (ASIC). The data were sampled at 10-bit resolution prior to communication off chip as a single interleaved data stream. This incorporated a power saving serial bitstream data compression algorithm that was found to extend the service lifetime of the pill by 70%. An integrated on-off keying (OOK) radio transmitter was used to send the signal to a local receiver (base station), prior to acquisition on a computer. A permanent magnet was also incorporated in the device to enable non-visual tracking of the system. We report on the implementation of this device, together with an initial study sampling from within the porcine GI tract, showing that measurements from the lab-on-a-pill, in situ, was within 90% of literature values.

Biocompatibility of a lab-on-a-pill sensor in artificial gastrointestinal environments.

In this paper, we present a radiotelemetry sensor, designed as a lab-in-a-pill, which incorporates a two-channel microfabricated sensor platform for real-time measurements of temperature and pH. These two parameters have potential application for use in remote biological sensing (for example they may be used as markers that reflect the physiological environment or as indicators for disease, within the gastrointestinal tract). We have investigated the effects of biofouling on these sensors, by exploring their response time and sensitivity in a model in vitro gastrointestinal system. The artificial gastric and intestinal solutions used represent a model both for fasting, as well as for the ingestion of food and subsequent digestion to gastrointestinal chyme. The results showed a decrease in pH sensitivity after exposure of the sensors for 3 h. The response time also increased from an initial measurement time of 10 s in pure GI juice, to ca. 25 s following the ingestion of food and 80 s in simulated chyme. These in vitro results indicate that changes in viscosity in our model gastrointestinal system had a pronounced effect on the unmodified sensor.

A programmable microsystem using system-on-chip for real-time biotelemetry.

A telemetry microsystem, including multiple sensors, integrated instrumentation and a wireless interface has been implemented. We have employed a methodology akin to that for System-on-Chip microelectronics to design an integrated circuit instrument containing several "intellectual property" blocks that will enable convenient reuse of modules in future projects. The present system was optimized for low-power and included mixed-signal sensor circuits, a programmable digital system, a feedback clock control loop and RF circuits integrated on a 5 mm x 5 mm silicon chip using a 0.6 microm, 3.3 V CMOS process. Undesirable signal coupling between circuit components has been investigated and current injection into sensitive instrumentation nodes was minimized by careful floor-planning. The chip, the sensors, a magnetic induction-based transmitter and two silver oxide cells were packaged into a 36 mm x 12 mm capsule format. A base station was built in order to retrieve the data from the microsystem in real-time. The base station was designed to be adaptive and timing tolerant since the microsystem design was simplified to reduce power consumption and size. The telemetry system was found to have a packet error rate of 10(-3) using an asynchronous simplex link. Trials in animal carcasses were carried out to show that the transmitter was as effective as a conventional RF device whilst consuming less power.

A suspended membrane nanocalorimeter for ultralow volume bioanalysis.

A nanocalorimetric suspended membrane sensor for pL volumes of aqueous media was fabricated by bulk silicon micromachining using anisotropic wet etching and photo and electron beam lithographic techniques. A high-temperature sensitivity of 125 microK and a rapid unfiltered time constant of 12 ms have been achieved by integrating a miniaturized reaction vessel of 0.7-nL volume on a 800-nm-thick and 300 x 300- microm2-large silicon nitride membrane, thermally insulated from the surrounding bulk silicon. The combination of a ten-junction gold and nickel thermoelectric sensor with an integrated ultralow noise preamplifier has enabled the resolution of 15-nW power in a single measurement, a result confirmed by electrical calibration. The combination of a high sensitivity and rapid response time is a consequence of miniaturization. The choice of gold and nickel as sensor material provided the maximum thermal sensitivity in the context of ease of fabrication and cost. The nanocalorimetric sensor has the potential for integration in an ultralow-volume high-density array format for the characterization of processes in which there is an exchange of heat.

Implementation of multichannel sensors for remote biomedical measurements in a microsystems format.

A novel microelectronic "pill" has been developed for in situ studies of the gastro-intestinal tract, combining microsensors and integrated circuits with system-level integration technology. The measurement parameters include real-time remote recording of temperature, pH, conductivity, and dissolved oxygen. The unit comprises an outer biocompatible capsule encasing four microsensors, a control chip, a discrete component radio transmitter, and two silver oxide cells (the latter providing an operating time of 40 h at the rated power consumption of 12.1 mW). The sensors were fabricated on two separate silicon chips located at the front end of the capsule. The robust nature of the pill makes it adaptable for use in a variety of environments related to biomedical and industrial applications.

Design and Characterization of an Osmotic Sensor for the Detection of Events Associated with Dehydration and Overhydration.

The level of hydration in the human body is carefully adjusted to control the electrolyte balance that governs the biochemical processes that sustain life. An electrolyte deficiency caused by de- or overhydration will not only limit human performance, but can also lead to serious health problems and death if left untreated. Because humans can withstand a change in hydration of only [Formula: see text], frequent monitoring should be performed in risk groups. This paper presents an osmotic hydration sensor that can record the level of hydration as a function of osmotic pressure in phosphate buffered saline or sodium-chloride solutions that simulate the interstitial fluid in the body. The osmotic pressure is recorded with the aid of an ion-exchange membrane that facilitates the migration of water and cations, in favor of reverse osmosis or gas separation membranes. The hydration sensor is designed to be coupled to an inductively powered readout circuit designed for integration in a micro-implant that has previously been shown to consume only 76 [Formula: see text] of power. The dynamic range spans a state of serious overhydration (220 [Formula: see text]) to a serious state of dehydration (340 [Formula: see text]) with a response time of [Formula: see text] (for a variation of hydration of 20%).

The assessment of potentially interfering metabolites and dietary components in blood using an osmotic glucose sensor based on the concanavalin A-dextran affinity assay.

Continuous surveillance of blood glucose is a prerogative of maintaining a tight glycaemic control in people suffering from diabetes mellitus. Implantable sensor technology offers the potential of conducting direct long term continuous glucose measurements, but current size restrictions and operational challenges have limited their applications. The osmotic sensor utilises diffusion to create a hydrostatic pressure that is independent of sensor operation and power consumption. This permits ultra-low power architectures to be realized with a minimal start-up time in a package suitable for miniaturization. In contrast, osmotic sensors suffer from the inability of their membranes to discriminate between different constituents in blood or the interstitial fluid that are of comparable size to glucose. By implementing an affinity assay based on the competitive bonding between concanavalin A and dextran, the selectivity of the membrane can be transferred to the glucose specific recognition of the affinity assay. The osmotic effect from the physiological levels of several key metabolites and nutritional components has been addressed identifying in particular ethanol, lactate and amino acids as potential interfering constituents. Both ascorbic acid and mannose would have a normal physiological concentration that is too low to be detected. The studies shows that an osmotic glucose sensor equipped with the con A-dextran affinity assay, is able to filter out potential interfering constituents present in blood, plasma and the interstitial fluid yet retaining a pressure that is proportional to glucose only.

Complement activation by candidate biomaterials of an implantable microfabricated medical device.

Implantable devices realized by microfabrication have introduced a new class of potential biomaterials whose properties would need to be assessed. Such devices include sensors for measuring biological substances like glucose. Thus, 14 different candidate materials intended for design of such a device were investigated with respect to their complement activation potential in human serum. The fluid-phase activation was measured by the products C4d, Bb, C3bc, and the terminal complement complex (TCC), whereas solid-phase activation was measured by deposition of TCC on the material surfaces. No fluid-phase activation was found for materials related to the capsule, carrier, or sealing. Fluid-phase activation was, however, triggered to a various extent in three of the four nanoporous membranes (cellulose, polyamide, and aluminium oxide), whereas polycarbonate was rendered inactive. Solid-phase activation discriminated more sensitively between all the materials, revealing that the capsule candidate polydimethylsiloxane and sealing candidate silicone 3140 were highly compatible, showing significantly lower TCC deposition than the negative control (p < 0.01). Three of the candidate materials were indifferent, whereas the remaining nine showed significantly higher deposition of TCC than the negative control (p < 0.01). In conclusion, complement activation, in particular when examined on the solid phase, discriminated well between the different candidate materials tested and could be used as a guide for the selection of the best-suited materials for further investigation and development of the device.

Activation of polymorphonuclear leukocytes by candidate biomaterials for an implantable glucose sensor.

BACKGROUND: Continuous monitoring of glucose by implantable microfabricated devices offers key advantages over current transcutaneous glucose sensors that limit usability due to their obtrusive nature and risk of infection. A successful sensory implant should be biocompatible and retain long-lasting function. Polymorphonuclear leukocytes (PMN) play a key role in the inflammatory system by releasing enzymes, cytokines, and reactive oxygen species, typically as a response to complement activation. The aim of this study was to perform an in vitro analysis of PMN activation as a marker for biocompatibility of materials and to evaluate the role of complement in the activation of PMN. METHODS: Fifteen candidate materials of an implantable glucose sensor were incubated in lepirudin-anticoagulated whole blood. The cluster of differentiation molecule 11b (CD11b) expression on PMN was analyzed with flow cytometry and the myeloperoxidase (MPO) concentration in plasma was analyzed with enzyme-linked immunosorbent assay. Complement activation was prevented by the C3 inhibitor compstatin or the C5 inhibitor eculizumab. RESULTS: Three of the biomaterials (cellulose ester, polyamide reverse osmosis membrane, and polyamide thin film membrane), all belonging to the membrane group, induced a substantial and significant increase in CD11b expression and MPO release. The changes were virtually identical for these two markers. Inhibition of complement with compstatin or eculizumab reduced the CD11b expression and MPO release dose dependently and in most cases back to baseline. The other 12 materials did not induce significant PMN activation. CONCLUSION: Three of the 15 candidate materials triggered PMN activation in a complement-dependent manner and should therefore be avoided for implementation in implantable microsensors.

Toward an injectable continuous osmotic glucose sensor.

BACKGROUND: The growing pandemic of diabetes mellitus places a stringent social and economic burden on the society. A tight glycemic control circumvents the detrimental effects, but the prerogative is the development of new more effective tools capable of longterm tracking of blood glucose (BG) in vivo. Such discontinuous sensor technologies will benefit from an unprecedented marked potential as well as reducing the current life expectancy gap of eight years as part of a therapeutic regime. METHOD: A sensor technology based on osmotic pressure incorporates a reversible competitive affinity assay performing glucose-specific recognition. An absolute change in particles generates a pressure that is proportional to the glucose concentration. An integrated pressure transducer and components developed from the silicon micro- and nanofabrication industry translate this pressure into BG data. RESULTS: An in vitro model based on a 3.6 x 8.7 mm large pill-shaped implant is equipped with a nanoporous membrane holding 4-6 nm large pores. The affinity assay offers a dynamic range of 36-720 mg/dl with a resolution of +/-16 mg/dl. An integrated 1 x 1 mm(2) large control chip samples the sensor signals for data processing and transmission back to the reader at a total power consumption of 76 microW. CONCLUSIONS: Current studies have demonstrated the design, layout, and performance of a prototype osmotic sensor in vitro using an affinity assay solution for up to four weeks. The small physical size conforms to an injectable device, forming the basis of a conceptual monitor that offers a tight glycemic control of BG.

Micromachined nanocalorimetric sensor for ultra-low-volume cell-based assays.

Current strategies for cell-based screening generally focus on the development of highly specific assays, which require an understanding of the nature of the signaling molecules and cellular pathways involved. In contrast, changes in temperature of cells provides a measure of altered cellular metabolism that is not stimulus specific and hence could have widespread applications in cell-based screening of receptor agonists and antagonists, as well as in the assessment of toxicity of new lead compounds. Consequently, we have developed a micromachined nanocalorimetric biological sensor using a small number of isolated living cells integrated within a subnanoliter format, which is capable of detecting 13 nW of generated power from the cells, upon exposure to a chemical or pharmaceutical stimulus. The sensor comprises a 10-junction gold and nickel thermopile, integrated on a silicon chip which was back-etched to span a 800-nm-thick membrane of silicon nitride. The thin-film membrane, which supported the sensing junctions of the thermoelectric transducer, gave the system a temperature resolution of 0.125 mK, a low heat capacity of 1.2 nJ mK(-1), and a rapid (unfiltered) response time of 12 ms. The application of the system in ultra-low-volume cell-based assays could provide a rapid endogenous screen. It offers important additional advantages over existing methods in that it is generic in nature, it does not require the use of recombinant cell lines or of detailed assay development, and finally, it can enable the use of primary cell lines or tissue biopsies.