Electrochemical and Plasmonic Detection of Myocardial Infarction Using Microfluidic Biochip Incorporated with Mesoporous Nanoscaffolds.

This paper reports a microfluidic device for the electrochemical and plasmonic detection of cardiac myoglobin (cMb) and cardiac troponin I (cTnI) with noticeable limits of detection (LoD) as low as a few picograms per milliliter (pg/mL) ranges, achieved in a short detection time. The device features two working electrodes, each with a mesoporous Ni3V2O8 nanoscaffold grafted with reduced graphene oxide (rGO) that improves the interaction of diffusing analyte molecules with the sensing surface by providing a high surface area and reaction kinetics. Electrochemical studies reveal sensitivities as high as 9.68 µA ng/mL and a LoD of 2.0 pg/mL for cTnI, and 8.98 µA ng/mL and 4.7 pg/mL for cMb. Additionally, the surface plasmon resonance (SPR) studies demonstrate a low-level LoD of 8.8 pg/mL for cMb and 7.3 pg/mL for cTnI. The dual-modality sensor enables dynamic tracking of kinetic antigen-antibody interactions during sensing, self-verification through providing signals of two modes, and reduced false readout. This study demonstrates the complementary nature of the electrochemical and SPR modes in biosensing, with the electrochemical mode being highly sensitive and the SPR mode providing superior tracking of molecular recognition behaviors. The presented sensor represents a significant innovation in cardiovascular disease management and can be applied to monitor other clinically important biomolecules.

Metal-organic frameworks for advanced transducer based gas sensors: review and perspectives.

The development of gas sensing devices to detect environmentally toxic, hazardous, and volatile organic compounds (VOCs) has witnessed a surge of immense interest over the past few decades, motivated mainly by the significant progress in technological advancements in the gas sensing field. A great deal of research has been dedicated to developing robust, cost-effective, and miniaturized gas sensing platforms with high efficiency. Compared to conventional metal-oxide based gas sensing materials, metal-organic frameworks (MOFs) have garnered tremendous attention in a variety of fields, including the gas sensing field, due to their fascinating features such as high adsorption sites for gas molecules, high porosity, tunable morphologies, structural diversities, and ability of room temperature (RT) sensing. This review summarizes the current advancement in various pristine MOF materials and their composites for different electrical transducer-based gas sensing applications. The review begins with a discussion on the overview of gas sensors, the significance of MOFs, and their scope in the gas sensing field. Next, gas sensing applications are divided into four categories based on different advanced transducers: chemiresistive, capacitive, quartz crystal microbalance (QCM), and organic field-effect transistor (OFET) based gas sensors. Their fundamental concepts, gas sensing ability towards various gases, sensing mechanisms, and their advantages and disadvantages are discussed. Finally, this review is concluded with a summary, existing challenges, and future perspectives.

Dual-modality microfluidic biosensor based on nanoengineered mesoporous graphene hydrogels.

A dual-modality microfluidic biosensor is fabricated using a mesoporous nanostructured cysteine-graphene hydrogel for the quantification of human cardiac myoglobin (cMb). In this device, the nanoengineered mesoporous l-cysteine-graphene (Cys-RGO) hydrogel performs the role of a dual-modality sensing electrode for the measurements conducted using differential pulse voltammetry and surface plasmon resonance (SPR) techniques. High surface reactivity, mesoporous structure and fast electron transfer combined with good reaction kinetics of the graphene hydrogel in this device indicate excellent performance for the detection of human cardiac myoglobin in serum samples. In electrochemical modality, this microfluidic chip exhibits a high sensitivity of 196.66 µA ng-1 mL cm-2 for a linear range of concentrations (0.004-1000 ng mL-1) with a low limit of detection (LOD) of 4 pg mL-1 while the SPR technique shows a LOD of 10 pg mL-1 for cMb monitoring in the range 0.01-1000 ng mL-1. The intra-assay coefficient of variation was less than 8% for standard samples and 9% for real serum samples, respectively. This Cys-RGO hydrogel-based microfluidic SPR chip allows real-time dynamic tracking of cMb molecules with a high association constant of 4.93 ± 0.2 × 105 M-1 s-1 and a dissociation constant of 1.37 ± 0.08 × 10-4 s-1, self-verification, reduced false readout, and improved detection reliability.

Microporous Nanocomposite Enabled Microfluidic Biochip for Cardiac Biomarker Detection.

This paper demonstrates an ultrasensitive microfluidic biochip nanoengineered with microporous manganese-reduced graphene oxide nanocomposite for detection of cardiac biomarker, namely human cardiac troponin I. In this device, the troponin sensitive microfluidic electrode consisted of a thin layer of manganese-reduced graphene oxide (Mn3O4-RGO) nanocomposite material. This nanocomposite thin layer was formed on surface of a patterned indium tin oxide substrate after modification with 3-aminopropyletriethoxysilane and was assembled with a polydimethylsiloxane-based microfluidic system. The nanoengineered microelectrode was functionalized with antibodies specific to cardiac troponin I. The uniformly distributed flower-shaped nanostructured manganese oxide (nMn3O4) onto RGO nanosheets offered large surface area for enhanced loading of antibody molecules and improved electrochemical reaction at the sensor surface. This microfluidic device showed an excellent sensitivity of log [87.58] kΩ/(ng mL-1)/cm2 for quantification of human cardiac troponin I (cTnI) molecules in a wide detection range of 0.008-20 ng/mL. This device was found to have high stability, high reproducibility, and minimal interference with other biomarkers cardiac troponin C and T, myoglobin, and B-type natriuretic peptide. These advantageous features of the Mn3O4-RGO nanocomposite, in conjunction with microfluidic integration, enabled a promising microfluidic biochip platform for point-of-care detection of cardiac troponin.

Facile Approach to Synthesize Au@ZnO Core-Shell Nanoparticles and Their Application for Highly Sensitive and Selective Gas Sensors.

We successfully prepared Au@ZnO core-shell nanoparticles (CSNPs) by a facile low-temperature solution route and studied its gas-sensing properties. The obtained Au@ZnO CSNPs were carefully characterized by X-ray diffraction, transmission electron microscopy (TEM), high-resolution TEM, and UV-visible spectroscopy. Mostly spherical-shaped Au@ZnO CSNPs were formed by 10-15 nm Au NPs in the center and by 40-45 nm smooth ZnO shell outside. After the heat-treatment process at 500 °C, the crystallinity of ZnO shell was increased without any significant change in morphology of Au@ZnO CSNPs. The gas-sensing test of Au@ZnO CSNPs was examined at 300 °C for various gases including H2 and compared with pure ZnO NPs. The sensor Au@ZnO CSNPs showed the high sensitivity and selectivity to H2 at 300 °C. The response values of Au@ZnO CSNPs and pure ZnO NPs sensors to 100 ppm of H2 at 300 °C were 103.9 and 12.7, respectively. The improved response of Au@ZnO CSNPs was related to the electronic sensitization of Au NPs due to Schottky barrier formation. The high selectivity of Au@ZnO CSNPs sensor toward H2 gas might be due to the chemical as well as catalytic effect of Au NPs.

Design of highly sensitive and selective Au@NiO yolk-shell nanoreactors for gas sensor applications.

Au@NiO yolk-shell nanoparticles (NPs) were synthesized by simple solution route and applied for efficient gas sensor towards H2S gas. Carbon encapsulated Au (Au@C core-shell) NPs were synthesized by glucose-assisted hydrothermal method, whereas Au@NiO yolk-shell NPs were synthesized by precipitation method using Au@C core-shell NPs as a template. Sub-micrometer Au@NiO yolk-shell NPs were formed having 50-70 nm Au NPs at the periphery of NiO shell (10-20 nm), which was composed of 6-12 nm primary NiO particles. Au@NiO yolk-shell NPs showed higher response for H2S compared to other interfering gases (ethanol, p-xylene, NH3, CO and H2). The maximum response was 108.92 for 5 ppm of H2S gas at 300 °C, which was approximately 19 times higher than that for the interfering gases. The response of Au@NiO yolk-shell NPs to H2S was approximately 4 times higher than that of bare NiO hollow nanospheres. Improved performance of Au@NiO yolk-shell NPs was attributed to hollow spaces that allowed the accessibility of Au NPs to gas molecules. It was suggested that adsorption of H2S on Au NPs resulted in the formation of sulfide layer, which possibly lowered its work function, and therefore tuned the electron transfer from Au to NiO rather NiO to Au, which leaded to increase in resistance and therefore response.

Effect of Au nanorods on potential barrier modulation in morphologically controlled Au@Cu2O core-shell nanoreactors for gas sensor applications.

In this work, Au@Cu2O core-shell nanoparticles (NPs) were synthesized by simple solution route and applied for CO sensing applications. Au@Cu2O core-shell NPs were formed by the deposition of 30-60 nm Cu2O shell layer on Au nanorods (NRs) having 10-15 nm width and 40-60 nm length. The morphology of Au@Cu2O core-shell NPs was tuned from brick to spherical shape by tuning the pH of the solution. In the absence of Au NRs, cubelike Cu2O NPs having ∼200 nm diameters were formed. The sensor having Au@Cu2O core-shell layer exhibited higher CO sensitivity compared to bare Cu2O NPs layer. Tuning of morphology of Au@Cu2O core-shell NPs from brick to spherical shape significantly lowered the air resistance. Transition from p- to n-type response was observed for all devices below 150 °C. It was demonstrated that performance of sensor depends not only on the electronic sensitization of Au NRs but also on the morphology of the Au@Cu2O core-shell NPs.

Au@Cu2O core-shell nanoparticles as chemiresistors for gas sensor applications: effect of potential barrier modulation on the sensing performance.

Au@Cu2O core-shell nanoparticles (NPs) were synthesized by a solution method at room temperature and applied for gas sensor applications. Transmission electron microscopy (TEM) images showed the formation of Au@Cu2O core-shell NPs, where 12-15 nm Au NPs were covered with 60-30 nm Cu2O shell layers. The surface plasmon resonance (SPR) peak of Au NPs was red-shifted (520-598 nm) after Cu2O shell formation. The response of Au@Cu2O core-shell NPs was higher than that of bare Cu2O NPs to CO at different temperatures and concentrations. Similarly, the response of Au@Cu2O core-shell NPs was higher than that of bare Cu2O NPs for NO2 gas at low temperature. The improved performance of Au@Cu2O core-shell NPs was attributed to the pronounced electronic sensitization, high thermal stability and low screening effect of Au NPs.

Solvothermal synthesis of ZnO nanostructures and their morphology-dependent gas-sensing properties.

Single-crystalline ZnO nanostructures were synthesized by solvothermal method using methanol as solvent. The effect of counterions of zinc salts (nitrate, acetate, and chloride) on the morphology of ZnO nanostructures was investigated. ZnO nanorods (NRs) were formed for all kinds of zinc salts except zinc chloride, where nanoparticles (NPs) were formed. The length and width of ZnO NRs were 100-150 nm and 20-25 nm, respectively, whereas NPs were 20-25 nm in diameter. Replacing methanol to ethanol generated only NRs for all kinds of zinc salts and they were about 10 times larger than those in methanol. The effect of morphology on sensing property was investigated by comparing their response. ZnO NRs showed very high response as compared to ZnO NPs for NO2 and vice versa for CO, although the surface area of ZnO NPs (42.83 m(2)/g) was much higher than those of ZnO NRs (17.6 m(2)/g). The response of ZnO NRs was 30 times higher than those of NPs for NO2 gas, whereas 4 times lower for CO gas. The maximum response of as prepared ZnO NRs was 44.2 to 50 ppm of NO2 gas at 300 °C. A relationship between morphology and interelectrode gap was established. It was demonstrated that the number of grains present between interelectrode gaps has significantly affected the response.

Effect of ammonia water on the morphology of monoethanolamine-assisted sonochemicaly synthesized ZnO nanostructures.

In the present work, ZnO nanostructures were synthesized by monoethanolamine (MEA)-assisted ultrasonic method at low temperature. Structural analysis was carried out by X-ray diffraction (XRD) confirmed the formation of hexagonal wurtzite structure of ZnO. The effect of ammonia water on the molecular structure of MEA, and its effect on the morphology of ZnO nanostructures were monitored by electron microscopy. Scanning electron microscopy (SEM) results suggest that ZnO nanoparticles with 100 nm in diameter were produced in case of MEA-assisted ultrasonic method. However, as ammonia water was added into the reaction system the morphology of ZnO nanoparticles changed into nanorods, flower-like nanostructures and finally microrods. Transmission electron microscopy (TEM) and selected area electron diffraction (SAED) studies showed that as prepared ZnO nanostructures were single crystalline in nature and grew in different directions resulted in the formation of various structures. The growth mechanism of as prepared ZnO nanostructures was discussed in detail. It was proposed that the addition of ammonia water into the reaction system resulted into the formation of ethylene diamine (EDA) which directed the growth of ZnO. The optical property was studied by photoluminescence (PL) spectroscopy showed only UV emission and no defects mediated visible emission.

Synthesis of well dispersed, regular shape ZnO nanorods: effect of pH, time and temperature.

In this paper we presented a systematic study on the morphological variation of ZnO nanostructure by varying the pH of precursor solution, reaction time and reaction temperature via cetyl trimethylammonium bromide-assisted hydrothermal method. The phase and structural analysis was carried out by X-ray diffraction, showed the formation of single phase ZnO with hexagonal wurtzite structure in all the specimens. Morphological and structural analysis was carried out by scanning electron microscopy and transmission electron microscopy showed that the shape of ZnO nanorods were greatly influenced by pH of precursor precipitate while size was affected by reaction time as well as temperature. The selected area diffraction pattern showed that the as synthesized ZnO nanorods were single crystalline in nature and preferentially grow along [0001] direction. A plausible growth mechanism of as prepared ZnO nanostructures was discussed in detail. Furthermore, the optical property of as prepared ZnO nanostructures was studied by photoluminescence spectroscopy.