Printing MEMS: Application of Inkjet Techniques to the Manufacturing of Inertial Accelerometers.

In the last few years, the manufacturing of microelectromechanical systems (MEMS) by means of innovative tridimensional and bidimensional printing technologies has significantly catalyzed the attention of researchers. Inkjet material deposition, in particular, can become a key enabling technology for the production of polymer-based inertial sensors characterized by low cost, high manufacturing scalability and superior sensitivity. In this paper, a fully inkjet-printed polymeric accelerometer is proposed, and its manufacturing steps are described. The manufacturing challenges connected with the inkjet deposition of SU-8 as a structural material are identified and addressed, resulting in the production of a functional spring-mass sensor. A step-crosslinking process allows optimization of the final shape of the device and limits defects typical of inkjet printing. The resulting device is characterized from a morphological point of view, and its functionality is assessed in performing optical readout. The acceleration range of the optimized device is 0-0.7 g, its resolution is 2 × 10-3 g and its sensitivity is 6745 nm/g. In general, the work demonstrates the feasibility of polymeric accelerometer production via inkjet printing, and these characteristic parameters demonstrate their potential applicability in a broad range of uses requiring highly accurate acceleration measurements over small displacements.

Electrochemically-gated graphene broadband microwave waveguides for ultrasensitive biosensing.

Identification of non-amplified DNA sequences and single-base mutations is essential for molecular biology and genetic diagnostics. This paper reports a novel sensor consisting of electrochemically-gated graphene coplanar waveguides coupled with a microfluidic channel. Upon exposure to analytes, propagation of electromagnetic waves in the waveguides is modified as a result of interactions with the fringing field and modulation of graphene dynamic conductivity resulting from electrostatic gating. Probe DNA sequences are immobilised on the graphene surface, and the sensor is exposed to DNA sequences which either perfectly match the probe, contain a single-base mismatch or are unrelated. By monitoring the scattering parameters at frequencies between 50 MHz and 50 GHz, unambiguous and reproducible discrimination of the different strands is achieved at concentrations as low as one attomole per litre (1 aM). By controlling and synchronising frequency sweeps, electrochemical gating, and liquid flow in the microfluidic channel, the sensor generates multidimensional datasets. Advanced data analysis techniques are utilised to take full advantage of the richness of the dataset. A classification accuracy >97% between all three sequences is achieved using different Machine Learning models, even in the presence of simulated noise and low signal-to-noise ratios. The sensor exceeds state-of-the-art sensitivity of field-effect transistors and microwave sensors for the identification of single-base mismatches.

Efficient BiVO4-Based Photoanode with Chemically Precipitated Hierarchical Cobalt Borate (Co-Bi) Oxygen Evolution Reaction Catalysts.

The integration of cobalt borate OER catalysts with electrodeposited BiVO4-based photoanodes through a simple drop casting technique was shown to provide an improvement of the photoelectrochemical performance of electrodes under simulated solar light. Catalysts were obtained by chemical precipitation mediated by NaBH4 at room temperature. Scanning electron microscopy (SEM) investigation of precipitates showed a hierarchical structure with globular features covered in nanometric thin sheets providing a large active area, whereas X-ray diffraction (XRD) and Raman spectroscopy highlighted their amorphous structure. The photoelectrochemical behavior of samples was investigated by linear scan voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) techniques. The amount of particles loaded onto BiVO4 absorbers was optimized by variation of the drop cast volume. The enhancement of photocurrent generation by Co-Bi-decorated electrodes with respect to bare BiVO4 was observed with an increase from 1.83 to 3.65 mA/cm2 at 1.23 V vs RHE under AM 1.5 simulated solar light, corresponding to a charge transfer efficiency of 84.6%. The calculated maximum applied bias photon-to-current efficiency (ABPE) value for optimized samples was 1.5% at 0.5 V applied bias. Under constant illumination at 1.23 V vs RHE, a depletion of photoanode performances was observed within an hour, likely due to the detachment of the catalyst from the electrode surface.

A Combined Raman Spectroscopy and Atomic Force Microscopy System for In Situ and Real-Time Measures in Electrochemical Cells.

An innovative and versatile set-up for in situ and real time measures in an electrochemical cell is described. An original coupling between micro-Raman spectroscopy and atomic force microscopy enables one to collect data on opaque electrodes. This system allows for the correlation of topographic images with chemical maps during the charge exchange occurring in oxidation/reduction processes. The proposed set-up plays a crucial role when reactions, both reversible and non-reversible, are studied step by step during electrochemical reactions and/or when local chemical analysis is required.

Inkjet-Assisted Electroformation of Magnetically Guidable Water Striders for Interfacial Microfluidic Manipulation.

Gerridae, colloquially called water striders, are a peculiar class of insects characterized by the extraordinary ability to walk on the surface of water bodies. Owing to this capacity, they constitute an ideal source of inspiration for designing untethered microdevices capable of navigating the interface between two fluids. Such steerable micrometric objects can be of great interest for various applications, ranging from the handling of floating objects to the remote control of microreactions and the manipulation of self-assembled monolayers. This paper describes the realization of artificial water striders via an inkjet-assisted electroforming approach. Inkjet deposition patterns the negative mask, which is subsequently filled with different layers of metals through electroforming. One of such layers is the magnetic alloy NiFe, which allows wireless propulsion of the striders by means of externally applied magnetic fields. The magnetic actuation tests prove good maneuverability at the water-air and silicone oil-air interfaces, with superior control over the speed and position of the devices. The surface of the devices is modified to tune its superficial energy in order to maximize buoyancy on these different combinations of fluids. A magnetic field-controlled strider manipulates a droplet and demonstrates collecting oil microdroplets and synthesizing platinum nanoparticles by chemical microreactions. Finally, the remotely operated microrobot could be employed in laboratories as a real avatar of chemists.

Flexible Perfluoropolyethers-Functionalized CNTs-Based UHMWPE Composites: A Study on Hydrogen Evolution, Conductivity and Thermal Stability.

Flexible conductive composites based on ultra-high molecular weight polyethylene (UHMWPE) filled with multi-walled carbon nanotubes (CNTs) modified by perfluoropolyethers (PFPEs) were produced. The bonding of PFPE chains, added in 1:1 and 2:1 weight ratios, on CNTs influences the dispersion of nanotubes in the UHMWPE matrix due to the non-polar nature of the polymer, facilitating the formation of nanofillers-rich conductive pathways and improving composites' electrical conductivity (two to five orders of magnitude more) in comparison to UHMWPE-based nanocomposites obtained with pristine CNTs. Electrochemical atomic force microscopy (EC-AFM) was used to evaluate the morphological changes during cyclic voltammetry (CV). The decrease of the overpotential for hydrogen oxidation peaks in samples containing PFPE-functionalized CNTs and hydrogen production (approximately -1.0 V vs. SHE) suggests that these samples could find application in fuel cell technology as well as in hydrogen storage devices. Carbon black-containing composites were prepared for comparative study with CNTs containing nanocomposites.

Accuracy of a new electronic nose for prostate cancer diagnosis in urine samples.

OBJECTIVE: To evaluate the accuracy of a new electronic nose to recognize prostate cancer in urine samples. METHODS: A blind, prospective study on consecutive patients was designed. Overall, 174 subjects were included in the study: 88 (50.6%) in prostate cancer group, and 86 (49.4%) in control group. Electronic nose performance for prostate cancer was assessed using sensitivity and specificity. The diagnostic accuracy of electronic nose was reported as area under the receiver operating characteristic curve. RESULTS: The electronic nose in the study population reached a sensitivity 85.2% (95% confidence interval 76.1-91.9; 13 false negatives out of 88), a specificity 79.1% (95% confidence interval 69.0-87.1; 18 false positives out of 86). The accuracy of the electronic nose represented as area under the receiver operating characteristic curve 0.821 (95% confidence interval 0.764-0.879). CONCLUSIONS: The diagnostic accuracy of electronic nose for recognizing prostate cancer in urine samples is high, promising and susceptible to supplemental improvement. Additionally, further studies will be necessary to design a clinical trial to validate electronic nose application in diagnostic prostate cancer nomograms.

Graphene Growth on Electroformed Copper Substrates by Atmospheric Pressure CVD.

Chemical vapor deposition (CVD) is regarded as the most promising technique for the mass production of graphene. CVD synthesis under vacuum is the most employed process, because the slower kinetics give better control on the graphene quality, but the requirement for high-vacuum equipment heavily affects the overall energy cost. In this work, we explore the possibility of using electroformed Cu substrate as a catalyst for atmospheric-pressure graphene growth. Electrochemical processes can produce high purity, freestanding metallic films, avoiding the surface defects that characterize the rolled foils. It was found that the growth mode of graphene on the electroformed catalyst was related to the surface morphology, which, in turn, was affected by the preliminary treatment of the substrate material. Suitable conditions for growing single layer graphene were identified.

Compared EC-AFM Analysis of Laser-Induced Graphene and Graphite Electrodes in Sulfuric Acid Electrolyte.

Flexible and economic sensor devices are the focus of increasing interest for their potential and wide applications in medicine, food analysis, pollution, water quality, etc. In these areas, the possibility of using stable, reproducible, and pocket devices can simplify the acquisition of data. Among recent prototypes, sensors based on laser-induced graphene (LIGE) on Kapton represent a feasible choice. In particular, LIGE devices are also exploited as electrodes for sensing in liquids. Despite a characterization with electrochemical (EC) methods in the literature, a closer comparison with traditional graphite electrodes is still missing. In this study, we combine atomic force microscopy with an EC cell (EC-AFM) to study, in situ, electrode oxidation reactions when LIGE or other graphite samples are used as anodes inside an acid electrolyte. This investigation shows the quality and performance of the LIGE electrode with respect to other samples. Finally, an ex situ Raman spectroscopy analysis allows a detailed chemical analysis of the employed electrodes.

Flexible Screen-Printed Electrochemical Sensors Functionalized with Electrodeposited Copper for Nitrate Detection in Water.

Nitrate (NO3 -) contamination is becoming a major concern due to the negative effects of an excessive NO3 - presence in water which can have detrimental effects on human health. Sensitive, real-time, low-cost, and portable measurement systems able to detect extremely low concentrations of NO3 - in water are thus becoming extremely important. In this work, we present a novel method to realize a low-cost and easy to fabricate amperometric sensor capable of detecting small concentrations of NO3 - in real water samples. The novel fabrication technique combines printing of a silver (Ag) working electrode with subsequent modification of the electrode with electrodeposited copper (Cu) nanoclusters. The process was tuned in order to reach optimized sensor response, with a high catalytic activity toward electroreduction of NO3 - (sensitivity: 19.578 µA/mM), as well as a low limit of detection (LOD: 0.207 nM or 0.012 µg/L) and a good dynamic linear concentration range (0.05 to 5 mM or 31 to 310 mg/L). The sensors were tested against possible interference analytes (NO2 -, Cl-, SO4 2-, HCO3 -, CH3COO-, Fe2+, Fe3+, Mn2+, Na+, and Cu2+) yielding only negligible effects [maximum standard deviation (SD) was 3.9 µA]. The proposed sensors were also used to detect NO3 - in real samples, including tap and river water, through the standard addition method, and the results were compared with the outcomes of high-performance liquid chromatography (HPLC). Temperature stability (maximum SD 3.09 µA), stability over time (maximum SD 3.69 µA), reproducibility (maximum SD 3.20 µA), and repeatability (maximum two-time useable) of this sensor were also investigated.

Graphene Flake Self-Assembly Enhancement via Stretchable Platforms and External Mechanical Stimuli.

While the green production and application of 2D functional nanomaterials, such as graphene flakes, in films for stretchable and wearable technologies is a promising platform for advanced technologies, there are still challenges involved in the processing of the deposited material to improve properties such as electrical conductivity. In applications such as wearable biomedical and flexible energy devices, the widely used flexible and stretchable substrate materials are incompatible with high-temperature processing traditionally employed to improve the electrical properties, which necessitates alternative manufacturing approaches and new steps for enhancing the film functionality. We hypothesize that a mechanical stimulus, in the form of substrate straining, may provide such a low-energy approach for modifying deposited film properties through increased flake packing and reorientation. To this end, graphene flakes were exfoliated using an unexplored combination of ethanol and cellulose acetate butyrate for morphological and percolative electrical characterization prior to application on polydimethylsiloxane (PDMS) substrates as a flexible and stretchable electrically conductive platform. The deposited percolative free-standing films on PDMS were characterized via in situ resistance strain monitoring and surface morphology measurements over numerous strain cycles, with parameters extracted describing the dynamic modulation of the film's electrical properties. A reduction in the film resistance and strain gauge factor was found to correlate with the surface roughness and densification of a sample's (sub)surface and the applied strain. High surface roughness samples exhibited enhanced reduction in resistance as well as increased sensitivity to strain compared to samples with low surface roughness, corresponding to surface smoothing, which is related to the dynamic settling of graphene flakes on the substrate surface. This procedure of incorporating strain as a mechanical stimulus may find application as a manufacturing tool/step for the routine fabrication of stretchable and wearable devices, as a low energy and compatible approach, for enhancing the properties of such devices for either high sensitivity or low sensitivity of electrical resistance to substrate strain.

Layer-by-Layer Fabrication of Hydrogel Microsystems for Controlled Drug Delivery From Untethered Microrobots.

Targeted drug delivery from untethered microrobots is a topic of major interest in current biomedical research. The possibility to load smart materials able to administer active principles on remotely in vivo guidable microdevices constitutes one of the most attractive opportunities to overcome the drawbacks of classical untargeted delivery methodologies. Hydrogels, in particular, are ideal candidates as drug-carrying materials due to their biocompatibility, low cost, and ease of manufacturing. On the other hand, these polymers suffer from poor control over release rate and overall released amount. Starting from these premises, the present article demonstrates the possibility to tune the release of hydrogels applied on magnetically steerable microrobots by fabricating microsystems via layer-by-layer self-assembly. By doing this, the diffusion of chemicals from the hydrogel layers to the external environment can be optimized and the phenomenon of burst release can be strongly limited. The microrobotic platforms employed to transport the hydrogel active material are fabricated by employing 3D printing in combination with wet metallization and present a gold layer on their surface to enhance biocompatibility. The maneuverability of microdevices coated with both thin and thick multilayers is investigated, individuating optimized parameters for efficient actuation.

Electrochemical Characterization of Magnetite (Fe3O4) Nanoaggregates in Acidic and Alkaline Solutions.

The electrochemical behavior of magnetite (Fe3O4) aggregates with submicrometric size is investigated. Specifically, cyclic voltammetry tests were performed in both acidic (pH ∼ 4.5) and alkaline (pH ∼ 12.8) solutions, exploiting a conventional three-electrode cell. In the first case, the working electrode was made of a glassy carbon substrate loaded with magnetite nanoaggregates, forming a continuous film. In a second configuration, magnetite nanoaggregates were dispersed in solution, kept under stirring, as a fluidized electrode. The latter approach showed an increase in the electrochemical response of the particles, otherwise limited by the reduced active area as in the former case. Electrochemical-atomic force microscopy (EC-AFM) investigation was carried out in an acidic environment, showing the topography evolution of nanoaggregates during the electrochemical characterization. X-ray diffraction (XRD) analysis was carried out to evaluate the microstructural variation in the Fe3O4 electrodes after cathodic polarization tests in an alkaline environment.

Electrochemical scanning probe analysis used as a benchmark for carbon forms quality test.

Carbon forms (graphite, pyrolytic graphite, highly oriented pyrolytic graphite (HOPG), glassy carbon, carbon foam, graphene, buckypaper, etc) are a wide class of materials largely used in technology and energy storage. The huge request of carbon compounds with reliable and tunable physical and chemical properties is tackled by contriving new production protocols and/or compound functionalizations. To achieve these goals, new samples must be tested in a trial-and-error strategy with techniques that provide information in terms of both specimen quality and properties. In this work, we prove that electrochemical scanning probe techniques allow testing the performances of carbon compounds when are used as an electrode inside an electrochemical cell. Comparing the results with a reference sample (namely, HOPG) gives an insight on defects in the specimen structure, performances, and possible applications of the new samples. In this study, we concentrate on traditional carbon forms already employed in many fields versus new recently-developed specimens, in view of possible applications to the field of energy storage.

On the production of 52gMn by deuteron irradiation on natural chromium and its radionuclidic purity.

The positron emitter 52gMn is used for the Positron Emission Tomography - PET imaging.In this work we investigate the nuclear reactions for production of 52gMn and 54Mn induced by deuteron beams on natural chromium targets at energies up to Ed = 28 MeV using the stacked-foils activation technique. We calculate the thick target yields for 52gMn and for the radionuclidic impurity 54Mn, and we compare the radionuclidic purity of 52gMn with that achievable in proton activation of Cr. The cross-sections of the reactions natCr(d,pxn)51Cr and natCr(d,x)48V are also presented.

Red phosphorus decorated electrospun carbon anodes for high efficiency lithium ion batteries.

Electrospinning is a powerful and versatile technique to produce efficient, specifically tailored and high-added value anodes for lithium ion batteries. Indeed, electrospun carbon nanofibers (CNFs) provide faster intercalation kinetics, shorter diffusion paths for ions/electrons transport and a larger number of lithium insertion sites with respect to commonly employed powder materials. With a view to further enhance battery performances, red phosphorous (RP) is considered one of the most promising materials that can be used in association with CNFs. RP/CNFs smart combinations can be exploited to overcome RP low conductivity and large volume expansion during cycling. In this context, we suggest a simple and cost effective double-step procedure to obtain high-capacity CNFs anodes and to enhance their electrochemical performances with the insertion of red phosphorous in the matrix. We propose a simple dropcasting method to confine micro- and nanosized RP particles within electrospun CNFs, thus obtaining a highly efficient, self-standing, binder-free anode. Phosphorous decorated carbon mats are characterized morphologically and tested in lithium ion batteries. Results obtained demonstrate that the reversible specific capacity and the rate capability of the obtained composite anodes is significantly improved with respect to the electrospun carbon mat alone.

Microstructural Development and Rheological Study of a Nanocomposite Gel Polymer Electrolyte Based on Functionalized Graphene for Dye-Sensitized Solar Cells.

For a liquid electrolyte-based dye-sensitized solar cell (DSSC), long-term device instability is known to negatively affect the ionic conductivity and cell performance. These issues can be resolved by using the so called quasi-solid-state electrolytes. Despite the enhanced ionic conductivity of graphene nanoplatelets (GNPs), their inherent tendency toward aggregation has limited their application in quasi-solid-state electrolytes. In the present study, the GNPs were chemically modified by polyethylene glycol (PEG) through amidation reaction to obtain a dispersible nanostructure in a poly(vinylidene fluoride-co-hexafluoro propylene) copolymer and polyethylene oxide (PVDF-HFP/PEO) polymer-blended gel electrolyte. Maximum ionic conductivity (4.11 × 10-3 S cm-1) was obtained with the optimal nanocomposite gel polymer electrolyte (GPE) containing 0.75 wt% functionalized graphene nanoplatelets (FGNPs), corresponding to a power conversion efficiency of 5.45%, which was 1.42% and 0.67% higher than those of the nanoparticle-free and optimized-GPE (containing 1 wt% GNP) DSSCs, respectively. Incorporating an optimum dosage of FGNP, a homogenous particle network was fabricated that could effectively mobilize the redox-active species in the amorphous region of the matrix. Surface morphology assessments were further performed through scanning electron microscopy (SEM). The results of rheological measurements revealed the plasticizing effect of the ionic liquid (IL), offering a proper insight into the polymer-particle interactions within the polymeric nanocomposite. Based on differential scanning calorimetry (DSC) investigations, the decrease in the glass transition temperature (and the resultant increase in flexibility) highlighted the influence of IL and polymer-nanoparticle interactions. The obtained results shed light on the effectiveness of the FGNPs for the DSSCs.

Modulation of electrostatic interactions to improve controlled drug delivery from nanogels.

The synthesis of nanogels as devices capable to maintain the drug level within a desired range for a long and sustained period of time is a leading strategy in controlled drug delivery. However, with respect to the good results obtained with antibodies and peptides there are a lot of problems related to the quick and uncontrolled diffusion of small hydrophilic molecules through polymeric network pores. For these reasons research community is pointing toward the use of click strategies to reduce release rates of the linked drugs to the polymer chains. Here we propose an alternative method that considers the electrostatic interactions between polymeric chains and drugs to tune the release kinetics from nanogel network. The main advantage of these systems lies in the fact that the carried drugs are not modified and no chemical reactions take place during their loading and release. In this work we synthesized PEG-PEI based nanogels with different protonation degrees and the release kinetics with charged and uncharged drug mimetics (sodium fluorescein, SF, and rhodamine B, RhB) were studied. Moreover, also the effect of counterion used to induce protonation was taken into account in order to build a tunable drug delivery system able to provide multiple release rates with the same device.

3D Printing of Cantilever-Type Microstructures by Stereolithography of Ferromagnetic Photopolymers.

In the present work, prototypes of polymeric cantilever-based magnetic microstructures were fabricated by means of stereolithography (SL). To this end, a UV-curable system suitable for high-resolution SL-processing was formulated by blending a bifunctional acrylic monomer with photoinitiator and visible dye whose content was tuned to tailor resin SL sensitivity. Subsequently, to confer ferromagnetic properties to the photopolymer, two different strategies were implemented. A two-step approach involved selective deposition of a metal layer on photopolymer SL-cured surfaces through an electroless plating process. On the other hand, SL-processable ferromagnetically responsive nanocomposites (FRCs) were obtained by directly loading magnetite nanoparticles within the photopolymer matrix. In order to achieve high-printing resolution, resin SL sensitivities were studied as a function of the various additives contents. Photocalorimetric analyses were also performed to investigate the photopolymer conversion efficiency upon light exposure. High-performing formulations were characterized by reduced penetration depth (<50 µm) and small critical energies thus enabling for fast printing of micrometric structures. Finally, the self-standing characteristics of the resin combined with the layered-fashion deposition typical of the 3D printing technologies were exploited for the fabrication of cantilever (CL)-based beams presented as possible magnetic sensors. As a demonstration of the feasibility of the two approaches, the magnetic beams were successfully actuated and their sensing performances in terms of static deflection vs applied magnetic field applied were qualitatively studied. Being not restricted to CL-based geometries, the combination of SL-printing with the formulation of novel smart photopolymers open the way toward the fabrication of high-customized complex 3D models integrating functional microstructures.