Rapid ultrasensitive and specific BNP biosensor with LED readout.

Biosensing for diagnostics has risen rapidly in popularity over the past decades. With the discovery of new nanomaterials and morphologies, sensitivity is being constantly improved enough for reliable detection of trace biomarkers in human samples, like serum or sweat. This precision has enabled detailed research on the efficacy of biosensors. However, current biosensors suffer from reduced speed of operation. To make better use of this sensitivity, the development of a conductometric biosensor with in-situ use of an Laser Emitting Device (LED) display can provide rapid determination of sample results, steadily pushing biosensors toward more clinical, point-of-care (POC) applications. In this research, a simple LED was used for facile optical determination and visual output of an ultrasensitive bio-signal amplification circuit was made to interface with a B-type Natriuretic Peptide (BNP) biosensor. Tuning circuit gain enables an elegant method for adjustable separation of concentrations into 3 discrete categories: sub-threshold, analog, and saturation regions. These regions corresponded to 0 < [C] < 500 pg/mL (25, 100, 250 pg/mL, LED off), 500 < [C] < 1000 pg/mL (LED varying intensity), and 1000 pg/mL < [C] (LED full intensity). System efficacy was tested using human blood serum samples from University of Pittsburgh Medical Center patients, which were able to be accurately detected and sorted for rapid low cost and power. determination without need for complex digital elements. Additional specificity testing suggests insignificant impact of non-target biomarkers.

Optical Duality of Molybdenum Disulfide: Metal and Semiconductor.

The two different light-matter interactions between visible and infrared light are not switchable because control mechanisms have not been elucidated so far, which restricts the effective spectral range in light-sensing devices. In this study, modulation of the effective spectral range is demonstrated using the metal-insulator transition of MoS2. Nondegenerate MoS2 exhibits a photoconductive effect in detecting visible light. In contrast, degenerate MoS2 responds only to mid-infrared (not visible) light by displaying a photoinduced heating effect via free carrier absorption. Depending on the doping level, the optical behavior of MoS2 simulates the photoconductivity of either the semiconductor or the metal, further indicating that the optical metal-insulator transition is coherent with its electrical counterpart. The electrical switchability of MoS2 enables the development of an unprecedented and novel design optical sensor that can detect both visible and mid-IR (wavelength of 9.6 µm) ranges with a singular optoelectronic device.

Asymmetric Bipolar Resistive Switching of Halide Perovskite Film in Contact with TiO2 Layer.

Halide perovskite materials such as methylammonium lead iodide (CH3NH3PbI3) have attracted considerable interest for the resistive random-access memory applications, which exploit a dramatic change in the resistance by an external electric bias. In many semiconductor films, the drift, accumulation, and chain formation of defects explain the change in the resistance by an external bias. This study demonstrates that the interface of CH3NH3PbI3 with TiO2 has a significant impact on the formation and rupture of defect chains and causes the asymmetric bipolar resistive switching in the Au/CH3NH3PbI3/TiO2/FTO device (FTO = fluorine-doped tin oxide). When a negative bias is applied to the Au electrode, iodine interstitials with the lowest migration activation energy move toward TiO2 in the CH3NH3PbI3 layer and pile up at the CH3NH3PbI3-TiO2 interface. Under the same condition, oxygen vacancies in the TiO2 layer also travel to the CH3NH3PbI3-TiO2 interface and strongly attract iodine interstitials. As a result, a Schottky barrier appears at the CH3NH3PbI3-TiO2 interface, and the resistance of Au/CH3NH3PbI3/TiO2/FTO becomes much larger than that of Au/CH3NH3PbI3/FTO in the high resistance state. The frequency dependence of the capacitance confirms the asymmetric appearance of a large space charge polarization at the CH3NH3PbI3-TiO2 interface, which causes the unique bipolar resistive switching behavior with the on/off ratio (103) and retention time (>104 seconds) at -0.85 V in Au/CH3NH3PbI3/TiO2/FTO film.

Induced bioresistance via BNP detection for machine learning-based risk assessment.

Machine Learning (ML) is a powerful tool for big data analysis that shows substantial potential in the field of healthcare. Individual patient data can be inundative, but its value can be extracted by ML's predictive power and ability to find trends. A great area of interest is early diagnosis and disease management strategies for cardiovascular disease (CVD), the leading cause of death in the world. Treatment is often inhibited by analysis delays, but rapid testing and determination can help improve frequency for real time monitoring. In this research, an ML algorithm was developed in conjunction with a flexible BNP sensor to create a quick diagnostic tool. The sensor was fabricated as an ion-selective field effect transistor (ISFET) in order to be able to quickly gather large amounts of electrical data from a sample. Artifical samples were tested to characterize the sensors using linear sweep voltammetry, and the resulting data was utilized as the initial training set for the ML algorithm, an implementation of quadratic discriminant analysis (QDA) written in MATLAB. Human blood serum samples from 30 University of Pittsburgh Medical Center (UPMC) patients were tested to evaluate the effective sorting power of the algorithm, yielding 95% power in addition to ultra fast data collection and determination.

Effects of Surface Modifications to Single and Multilayer Graphene Temperature Coefficient of Resistance.

Interfacial effects on single-layer graphene (SLG) or multilayer graphene (MLG) properties greatly affect device performance. Thus, the effect of the interface on the temperature coefficient of resistance (TCR) on SLG and MLG due to surface-deposited core-shell metallic nanoparticles (MNPs) and various substrates was experimentally investigated. Observed substrates included glass, SiO2, and Si3N4. We show that these modifications can be used to strongly influence SLG interface effects, thus increasing the TCR up to a 0.456% per K resistance change when in contact with the SiO2 substrate at the bottom surface and MNPs on the top surface. However, these surface interactions are muted in MLG due to the screening effect of nonsuperficial layers, only achieving a -0.0998% per K resistance change in contact with the bottom Si3N4 substrate and the top MNPs. We also demonstrate contrary thermal sensitivity responses between SLG and MLG after the addition of MNP to the surface.

Low-Power, Electrochemically Tunable Graphene Synapses for Neuromorphic Computing.

Brain-inspired neuromorphic computing has the potential to revolutionize the current computing paradigm with its massive parallelism and potentially low power consumption. However, the existing approaches of using digital complementary metal-oxide-semiconductor devices (with "0" and "1" states) to emulate gradual/analog behaviors in the neural network are energy intensive and unsustainable; furthermore, emerging memristor devices still face challenges such as nonlinearities and large write noise. Here, an electrochemical graphene synapse, where the electrical conductance of graphene is reversibly modulated by the concentration of Li ions between the layers of graphene is presented. This fundamentally different mechanism allows to achieve a good energy efficiency (<500 fJ per switching event), analog tunability (>250 nonvolatile states), good endurance, and retention performances, and a linear and symmetric resistance response. Essential neuronal functions such as excitatory and inhibitory synapses, long-term potentiation and depression, and spike timing dependent plasticity with good repeatability are demonstrated. The scaling study suggests that this simple, two-dimensional synapse is scalable in terms of switching energy and speed.

Two-dimensional polyaniline nanostructure to the development of microfluidic integrated flexible biosensors for biomarker detection.

In this work, we report a flexible field-effect-transistor (FET) biosensor design based on two-dimensional (2-D) polyaniline (PANI) nanostructure. The flexible biosensor devices were fabricated through a facile and inexpensive method that combines top-down and bottom-up processes. The chemically synthesized PANI nanostructure showed excellent p-type semiconductor properties as well as good compatibility with flexible design. With the 2-D PANI nanostructure being as thin as 80 nm and its extremely large surface-area-to-volume (SA/V) ratio due to the intrinsic properties of PANI chemical synthesis, the developed flexible biosensor exhibited outstanding sensing performance in detecting B-type natriuretic peptide (BNP) biomarkers, and was able to achieve high specificity (averagely 112 folds) with the limit of detection as low as 100 pg/mL. PANI nanostructure under bending condition was also investigated and showed controllable conductance changes being less than 20% with good restorability which may open up the possibility for wearable applications.

Detection and identification of breast cancer volatile organic compounds biomarkers using highly-sensitive single nanowire array on a chip.

A single nanowire array on a chip with different materials of Palladium, Polypyrrole and Zinc Oxide has been fabricated using electrochemical deposition method. The fabricated single nanowire array has been demonstrated for highly sensitive and specific diagnosis of breast cancer by detecting four volatile organic compound biomarkers: Heptanal, Acetophenone, Isopropyl Myristate and 2-Propanol. The demonstrated sensing limits for Heptanal, Acetophenone, Isopropyl Myristate and 2-propanol using individual Palladium, Polypyrrole and Zinc Oxide nanowires were 8.982 ppm, 798 ppb, 134 ppm, and 129.5 ppm, respectively, and the corresponding sensitivities of resistance change were in the range of 0.3%-5% which indicated excellent sensing performance of the single nanowires. The response time for Palladium, Polypyrrole and Zinc Oxide nanowires to achieve maximum conductance change was less than 200 seconds while also illustrating excellent signal repeatability. With the principal component analysis of the resistance change versus time in each detection period of the nanowire array, the smell prints for the four volatile organic compounds biomarkers of Breast Cancer are discriminated in the 3-D plots.

Transferred wrinkled Al2O3 for highly stretchable and transparent graphene-carbon nanotube transistors.

Despite recent progress in producing transparent and bendable thin-film transistors using graphene and carbon nanotubes, the development of stretchable devices remains limited either by fragile inorganic oxides or polymer dielectrics with high leakage current. Here we report the fabrication of highly stretchable and transparent field-effect transistors combining graphene/single-walled carbon nanotube (SWCNT) electrodes and a SWCNT-network channel with a geometrically wrinkled inorganic dielectric layer. The wrinkled Al2O3 layer contained effective built-in air gaps with a small gate leakage current of 10(-13) A. The resulting devices exhibited an excellent on/off ratio of ~10(5), a high mobility of ~40 cm(2) V(-1) s(-1) and a low operating voltage of less than 1 V. Importantly, because of the wrinkled dielectric layer, the transistors retained performance under strains as high as 20% without appreciable leakage current increases or physical degradation. No significant performance loss was observed after stretching and releasing the devices for over 1,000 times. The sustainability and performance advances demonstrated here are promising for the adoption of stretchable electronics in a wide variety of future applications.

Shadow masking for nanomaterial-based biosensors incorporated with a microfluidic device.

Integrating PDMS channels and chips containing pre-functionalized biosensors into microfluidic devices with irreversible sealing has been challenging because the integration process requires use of an O2 plasma treatment that usually destroys the biosensors. In this study, we examined the usefulness of introducing a shadow mask into the process as a method of protecting the pre-functionalized biosensors. Single nanowire sensors were pre-functionalized with fluorescently labeled biomolecules and then subjected to O2 plasma with and without the shadow mask. Results from the two groups were then compared. Those sensors without a shadow mask were destroyed, giving the sensor an infinite resistance and reduced fluorescence intensity. In contrast, the sensors with the shadow mask were protected and exhibited little changes in the resistance and fluorescence intensity. Then two different nanowires, aptamers incorporated polypyrrole nanowire (entrapment) and antibodies immobilized polyaniline nanowire (surface covalent binding), were used to investigate their detection performance before and after the plasma treatment in the presence of shadow mask. The protected samples showed a good sensitivity to the targets with a slight reduction in response compared with the as-prepared samples. After the O2 plasma treatment, the microfluidic channels were integrated with single nanowire biosensors. This microfluidic biosensor showed a high sensitivity with about ~0.5 % change in conductance at the lowest IgE protein concentration of 10 pM.

Integrating metal-oxide-decorated CNT networks with a CMOS readout in a gas sensor.

We have implemented a tin-oxide-decorated carbon nanotube (CNT) network gas sensor system on a single die. We have also demonstrated the deposition of metallic tin on the CNT network, its subsequent oxidation in air, and the improvement of the lifetime of the sensors. The fabricated array of CNT sensors contains 128 sensor cells for added redundancy and increased accuracy. The read-out integrated circuit (ROIC) was combined with coarse and fine time-to-digital converters to extend its resolution in a power-efficient way. The ROIC is fabricated using a 0.35 µm CMOS process, and the whole sensor system consumes 30 mA at 5 V. The sensor system was successfully tested in the detection of ammonia gas at elevated temperatures.

Detection of cardiac biomarkers using single polyaniline nanowire-based conductometric biosensors.

The detection of myoglobin (Myo), cardiac troponin I (cTnI), creatine kinase-MB (CK-MB), and b-type natriuretic peptide (BNP) plays a vital role in diagnosing cardiovascular diseases. Here we present single site-specific polyaniline (PANI) nanowire biosensors that can detect cardiac biomarkers such as Myo, cTnI, CK-MB, and BNP with ultra-high sensitivity and good specificity. Using single PANI nanowire-based biosensors integrated with microfluidic channels, very low concentrations of Myo (100 pg/mL), cTnI (250 fg/mL), CK-MB (150 fg/mL), and BNP (50 fg/mL) were detected. The single PANI nanowire-based biosensors displayed linear sensing profiles for concentrations ranging from hundreds (fg/mL) to tens (ng/mL). In addition, devices showed a fast (few minutes) response satisfying respective reference conditions for Myo, cTnI, CK-MB, and BNP diagnosis of heart failure and for determining the stage of the disease. This single PANI nanowire-based biosensor demonstrated superior biosensing reliability with the feasibility of label free detection and improved processing cost efficiency due to good biocompatibility of PANI to monoclonal antibodies (mAbs). Therefore, this development of single PANI nanowire-based biosensors can be applied to other biosensors for cancer or other diseases.

Rapid real-time electrical detection of proteins using single conducting polymer nanowire-based microfluidic aptasensor.

Single polypyrrole (PPy) nanowire-based microfluidic aptasensors were fabricated using a one-step electrochemical deposition method. The successful incorporation of the aptamers into the PPy nanowire was confirmed by fluorescence microscopy image. The microfluidic aptasensor showed responses to IgE protein solutions in the range from 0.01 nM to 100 nM, and demonstrated excellent specificity and sensitivity with faster response and rapid stabilization times (~20 s). At the lowest examined IgE concentration of 0.01 nM, the microfluidic aptasensor still exhibited ~0.32% change in the conductance. The functionality of this aptasensor was able to be regenerated using an acid treatment with no major change in sensitivity. In addition, the detection of cancer biomarker MUC1 was performed using another microfluidic aptasensor, which showed a very low detection limit of 2.66 nM MUC1 compared to commercially available MUC1 diagnosis assay (800 nM).

Materialization of single multicomposite nanowire: entrapment of ZnO nanoparticles in polyaniline nanowire.

We present materialization of single multicomposite nanowire (SMNW)-entrapped ZnO nanoparticles (NPs) via an electrochemical growth method, which is a newly developed fabrication method to grow a single nanowire between a pair of pre-patterned electrodes. Entrapment of ZnO NPs was controlled via different conditions of SMNW fabrication such as an applied potential and mixture ratio of NPs and aniline solution. The controlled concentration of ZnO NP results in changes in the physical properties of the SMNWs, as shown in transmission electron microscopy images. Furthermore, the electrical conductivity and elasticity of SMNWs show improvement over those of pure polyaniline nanowire. The new nano-multicomposite material showed synergistic effects on mechanical and electrical properties, with logarithmical change and saturation increasing ZnO NP concentration.

Ultrasensitive protein detection using an aptamer-functionalized single polyaniline nanowire.

A highly sensitive, conductometric and label-free biosensor for the detection of immunoglobulin E (IgE) is developed based on the immobilzation of the IgE aptamer onto a single polyaniline nanowire electrochemically synthesized in a facile and controllable way.

Small hysteresis nanocarbon-based integrated circuits on flexible and transparent plastic substrate.

We report small hysteresis integrated circuits by introducing monolayer graphene for the electrodes and a single-walled carbon nanotube network for the channel. Small hysteresis of the device originates from a defect-free graphene surface, where hysteresis was modulated by oxidation. This uniquely combined nanocarbon material device with transparent and flexible properties shows remarkable device performance; subthreshold voltage of 220 mV decade(-1), operation voltage of less than 5 V, on/off ratio of approximately 10(4), mobility of 81 cm(2) V(-1) s(-1), transparency of 83.8% including substrate, no significant transconductance changes in 1000 times of bending test, and only 36% resistance decrease at a tensile strain of 50%. Furthermore, because of the nearly Ohmic contact nature between the graphene and carbon nanotubes, this device demonstrated a contact resistance 100 times lower and a mobility 20 times higher, when compared to an Au electrode.

Thermionic field emission transport in carbon nanotube transistors.

With experimental and analytical analysis, we demonstrate a relationship between the metal contact work function and the electrical transport properties saturation current (Isat) and differential conductance (σsd=∂Isd/∂Vsd) in ambient exposed carbon nanotubes (CNT). A single chemical vapor deposition (CVD) grown 6 mm long semiconducting single-walled CNT is electrically contacted with a statistically significant number of Hf, Cr, Ti, Pd, and Au electrodes, respectively. The observed exponentially increasing relationship of Isat and σsd with metal contact work function is explained by a theoretical model derived from thermionic field emission. Statistical analysis and spread of the data suggest that the conduction variability in same CNT devices results from differences in local surface potential of the metal contact. Based on the theoretical model and methodology, an improved CNT-based gas sensing device layout is suggested. A method to experimentally determine gas-induced work function changes in metals is also examined.

Highly sensitive single polyaniline nanowire biosensor for the detection of immunoglobulin G and myoglobin.

A single polyaniline (PANI) nanowire-based biosensor was established to detect immunoglobulin G (IgG) and myoglobin (Myo), which is one of the cardiac biomarkers. The single PANI nanowires were fabricated via an electrochemical growth method, in which single nanowires were formed between a pair of patterned electrodes. The single PANI nanowires were functionalized with monoclonal antibodies (mAbs) of IgG or Myo via a surface immobilization method, using 1-ethyl-3-(3-dimethyaminopropyl) carbodiimide (EDC), and N-hydroxysuccinimde (NHS). The functionalization was then verified by Raman spectroscopy and fluorescence microscopy. The target proteins of IgG and Myo were detected by measuring the conductance change of functionalized single PANI nanowires owing to the capturing of target proteins by mAbs. The detection limit was found to be 3 ng/mL for IgG and 1.4 ng/mL for Myo. No response was observed when single nanowires were exposed to a non-specific protein, demonstrating excellent specificity to expected target detection. Together with the fast response time (a few seconds), high sensitivity, and good specificity, this single PANI nanowire-based biosensor shows great promise in the detection of cardiac markers and other proteins.

Synthesis of edge-closed graphene ribbons with enhanced conductivity.

Edge-closed and edge-opened graphene ribbons were synthesized on Pd nanowire templates using plasma-enhanced chemical vapor deposition (PECVD). After metal nanowire etching, the tubular shaped thin graphene layers were collapsed to edge-closed graphene ribbon. In order to make edge-opened graphene ribbons, the graphene layers on the top part of the metal nanowire were selectively etched by O(2) plasma. The protected graphene layers at the bottom of nanowire are transformed to edge-opened graphene ribbon after nanowire etching. Because of defect-free edges, edge-closed graphene ribbon showed reduced D-band intensity compared to edge-opened graphene ribbons, and moreover, the conductivity of edge-closed graphene ribbon was much higher than that of edge-opened graphene ribbon.

Anomalous Schottky barriers and contact band-to-band tunneling in carbon nanotube transistors.

Devices incorporating nanoscale materials, particularly carbon nanotubes (CNTs), offer exceptional electrical performance. Absent, however, is an experimentally backed model explaining contact-metal work function, device layout, and environment effects. To fill the void, this report introduces a surface-inversion channel model based on low temperature and electrical measurements of a distinct single-walled semiconducting CNT contacted by Hf, Cr, Ti, and Pd electrodes. Anomalous barrier heights and metal-contact dependent band-to-band tunneling phenomena are utilized to show that, dependent upon contact work function and gate field, transport occurs either directly between the metal and CNT channel or indirectly via injection of carriers from the metal-covered CNT region to the CNT channel. The model is consistent with previously contradictory experimental results, and the methodology is simple enough to apply in other contact-dominant systems.