Ferrocyanide Solution Research Articles

Modification Of a Screen-Printed Carbon Electrode with Nanoporous Gold by Electrodeposition and Dealloying of a Gold-Copper Alloy

In this study, a three-dimensional structure of nanoporous gold (NPG) was made by selectively corroding copper (Cu) from gold-copper (Au-Cu) alloys using a two-step electrochemical method. Given its large surface area and interconnected porous network, nanoporous gold is a suitable material for the advancement of electrochemical sensors. The screen-printed carbon electrode (SPCE) modified with nanoporous gold (NPG/SPCE) was fabricated by electrodepositing a gold-copper alloy from gold ion (Au3+) and copper ion (Cu2+) solution via cyclic voltammetry (CV) by scanning from -0.3 V to -0.8 V for 80 cycles. The copper is then removed via a dealloying process in 3M HNO3 using the cyclic voltammogram (CV) method by scanning potential from 0 V to +1.0 V for 100 cycles at 100 mV/s. The morphology, elemental composition, and electrochemical active surface area (ECSA) of NPG/SPCE electrodes were characterized using FESEM, EDX, and CV analysis, respectively. The electrochemical performance of the NPG/SPCE was compared with bare SPCE in a 10 mM potassium ferrocyanide (K4FeCN6) solution using cyclic voltammetry. The morphological study using FESEM revealed that the NPG/SPCE had an average pore diameter of 53 nm. The quantification of elements using EDX shows that 84 % of the copper in the electrodeposited gold-copper alloy electrode was successfully removed by the dealloying process. The higher number of cycles during the dealloying process led to producing NPG with higher ECSA electrodes. The ECSA of NPG/SPCE is 12 times greater than that of bare or unmodified SPCE in an equivalent geometrical area. NPG/SPCE has a much better electron transfer surface than bare SPCE due to its high surface area and gold surface properties, making it a potential sensing material for biosensing applications.

P-EcStat: A Versatile Design of Photoelectrochemical and Electrochemical Sensing System with Smartphone Interface via Bluetooth Low Energy

Electrochemical and photoelectrochemical sensors are a rapidly developing field in analytical chemistry. However, commercial systems often lack versatility and affordability, hindering wider adoption. Additionally, the absence of integrated excitation light sources limits their application in photoelectrochemical sensing. Here, we present a highly precise, versatile, affordable measurement system for both electrochemical and photoelectrochemical sensing applications. The system incorporates a three-electrode potentiostat with a synchronized excitation light source. This design enables the system to perform conventional electrochemical measurements like cyclic voltammetry, chronoamperometry, and photoelectrochemical amperometric measurements with controlled light excitation. The developed measurement system operates within a voltage range suitable for a measurable current range of 1 nA to 18 mA, with a high precision of 99%. The excitation source is a monochromatic LED system offering seven distinct wavelengths with digitally controlled intensity via a digital-to-analog converter. Furthermore, an Android-based user interface allows wireless system control via Bluetooth Low Energy. The report also details the construction of a photoelectrochemical experiment using copper (II) oxide nanorods synthesized by the hydrothermal process as the photoactive material employed to test the experiment on a potassium ferricyanide/potassium ferrocyanide solution. This user-friendly system allows broader exploration of electrochemical and photoelectrochemical sensing applications.

The Fast Quantification of Vitamin B12 in Milk Powder by High-Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry.

This study presents a new technique for determining vitamin B12 in milk powder using high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS). We used ultrasonics with potassium ferrocyanide and zinc acetate solutions to extract the samples. 59Co was employed as the analytical target for cyanocobalamin. It was separated using a Phenomenex Luna 5 μm C18 (250 × 4.6 mm) chromatographic column with a mobile phase consisting of 1.6 mmol/L EDTA and 0.4 mmol/L KH2PO4 in a 60% v/v methanol solution (pH = 4.0). The sample has an excellent separating degree for free cobalt and cyanocobalamin, and isocratic elution can be finished within 4.0 min. To eliminate the matrix interference due to the presence of milk powder, we applied collision mode (KED). The linear range of cyanocobalamine ranged from 1.0 μg/L to 20 μg/L, with correlation coefficients (r2) of 0.9994. The limit of detection (LOD) was 0.63 μg/kg, and the limit of quantitation (LOQ) was 2.11 μg/kg. The mean recoveries were in the range of 87.4-103.6%. The accuracy and precision of the developed method are well suited for the fast quantification of the trace vitamin B12 in milk powder.

Construction of a self–reporting molecularly–imprinted electrochemical sensor based on CuHCF modified by rGNR–rGO for the detection of zearalenone

A self–reporting molecularly–imprinted electrochemical sensor is prepared for the detection of Zearalenone (ZEA). Firstly, the reduced graphene nanoribbons and reduced graphene oxide (rGNR–rGO) were simultaneously modified onto a glassy carbon electrode (GCE) to improve the sensor's sensitivity. After electrodepositing copper nanoparticles onto the rGNR–rGO/GCE, cyclic voltammetry scanning was performed in potassium ferrocyanide solution, and copper hexacyanoferrate (CuHCF) was deposited onto rGNR–rGO/GCE to further improve the sensor's sensitivity while giving it self–reporting capability. Then, molecularly–imprinted polymer films were prepared on the CuHCF/rGNR–rGO/GCE to ensure the selectivity of the sensor. It is found that the linear range of ZEA detection by the constructed sensor is 0.25–500 ng·mL −1, with a detection limit of 0.09 ng·mL −1. This sensor shows the merits of good selectivity, high sensitivity and accurate detection, providing a great possibility for the precise detection of low concentration ZEA in food.

New Sorbents Based on Polyacrylonitrile Fiber and Transition Metal Ferrocyanides for 137Cs Recovery from Various Composition Solutions

For the first time, new sorbents based on polyacrylonitrile (PAN) fiber and transition metal ferrocyanides were obtained. The main difference between the obtained sorbents and the existing ones is the stage of preliminary preparation of the initial support by converting it into the forms PAN-Fe(OH)3 or PAN-MnO2, due to which additional ion exchange groups (carboxyl, carbonyl, etc.) are formed, which increases the amount of ferrocyanide fixed to the support. The best components and conditions for the synthesis of new sorbents were determined (concentration (0.1–0.2 mol/L), as well as pH (1 for sorbents based on PAN-Fe(OH)3, and 1–5—PAN-MnO2) of potassium ferrocyanide solution, concentration of transition metal salts (0.02 mol/L), temperature conditions). The influence of the studied solution composition (pH, concentration of Na+, K+, NH4+ ions) on the cesium distribution coefficients during its recovery by the obtained sorbents was assessed. The possibility of cesium recovery from solutions with pH 1–9 containing macro quantities of cations was demonstrated. The sorbents derived were characterized by modern structural methods such as infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy with EDS analysis. A study of the trace amount sorption of 137Cs was carried out in comparison with commercially available highly efficient sorbents (FNS-10 and Termoksid-35), and it was shown that the resulting sorbents are not inferior to industrial ferrocyanide sorbents and can be used for 137Cs selective sorption from technological solutions and natural waters.

Deaeration of incubation buffer to minimize electrochemical impedance spectroscopy signal drift on screen-printed gold electrodes and its use for label-free detection of vancomycin

Disposable screen-printed gold electrodes (SPAuEs) are used for the development of numerous immunosensors owing to their ease of modification with biorecognition molecules. A major limitation in the development of SPAuEs based biosensors is the single-use of the electrodes leading to higher costs for sensor development, whereas multiple measurements can affect the sensor stability and reproducibility. Especially, label-free electrochemical impedance spectroscopy (EIS) based SPAuEs sensors are prone to signal drift resulting in false-positive or false-negative data questioning the reliability of the assay. We found that repeated EIS measurements on SPAuEs in ferri- and ferrocyanide solution yielded a significant increase in resistance to charge transfer (Rct) value (positive signal drift) even in a control solution (without the target analyte). The positive signal drift follows the typical pattern of a concentration-dependent calibration curve, rendering repeated measurement error-prone for sensing purposes. In this study, it is shown that the incubation of the SPAuEs in nitrogen purged deaerated phosphate buffered saline (N-PBS) minimized this signal drift in repeated/multiple EIS measurements. This method was then used to develop a peptide-based EIS biosensor for the detection of Vancomycin, a last-line antibiotic used for the treatment of severe multidrug-resistant bacterial infection. This protocol can be followed for the biosensing of other clinically important biomarkers.

Long-Term Stability of Ferri-/Ferrocyanide as an Electroactive Component for Redox Flow Battery Applications: On the Origin of Apparent Capacity Fade

We assess the suitability of potassium ferri-/ferrocyanide as an electroactive species for long-term utilization in aqueous organic redox flow batteries. A series of electrochemical and chemical characterization experiments was performed to distinguish between structural decomposition and apparent capacity fade of ferri-/ferrocyanide solutions used in the capacity-limiting side of a flow battery. Our results indicate that, in contrast with previous reports, no structural decomposition of ferri-/ferrocyanide occurs at tested pH values as high as 14 in the dark or in diffuse indoor light. Instead, an apparent capacity fade takes place due to a chemical reduction of ferricyanide to ferrocyanide, via chemical oxygen evolution reaction. We find that this parasitic process can be further exacerbated by carbon electrodes, with apparent capacity fade rates at pH 14 increasing with an increased ratio of carbon electrode surface area to ferricyanide in solution. Based on these results, we report a set of operating conditions that enables the long-duration cycling of alkaline ferri-/ferrocyanide electrolytes and demonstrate how apparent capacity fade rates can be engineered by the initial system setup. If protected from direct exposure to light, the structural stability of ferri-/ferrocyanide anions allows for their practical deployment as electroactive species in long duration energy storage applications.

Modification of graphene oxide with imidazolium-based ionic liquid for significant sorption of La(III) and Pr(III) from aqueous solutions

A straightforward ferrocyanide immobilization on the surface of graphene oxide (GO) was conducted for rapid and efficient adsorption capacity for lanthanum and praseodymium from an aqueous solution. The GO was mixed with 1-methyl imidazole in the presence of epichlorohydrin to form GO-imidazole-Cl and thereafter suspended in a potassium ferrocyanide solution to fabricate GO-imidazole-FeCN. The prepared materials were characterized with different advanced techniques confirming the preparation method. The adsorption ability of GO-imidazole-FeCN towards La(III) and Pr(III) ions was evaluated. Moreover, the adsorption isotherm showed that the sorption process was fitted with the Langmuir isotherm model with a considerable maximum adsorption capacity of 781.25 mg g−1 for La(III) and 862.07 mg g−1 for Pr(III). The thermodynamic studies showed that the adsorption of both metal ions was spontaneous and endothermic. In addition, the adsorbent showed excellent adsorption–desorption behavior over 5 times, suggesting that GO-imidazole-FeCN may be considered a potential candidate for La(III) and Pr(III) removal from different metal ions which present in fission products.

Detection of prostate specific antigen using a magnetic sulfonated reduced graphene oxide/gold nanoparticle aptasensor

Prostate-specific antigen (PSA), is a protein produced by cancerous cells in the prostate gland, and its presence may indicate the likelihood of prostate cancer. For the purpose of detecting PSA, an innovative aptasensor utilizing magnetic sulfonated reduced graphene oxide/gold nanoparticles was developed. This unique nanocomposite has been used for the first time for biosensing of prostate cancer which resulted in significant enhancement of the biosensor’s performance. Unlike previous works, our biosensor incorporates two detection modes: a label-free detection mode in ferrocyanide solution and a labeled mode using methylene blue. Different tests such as FTIR, XRD and TEM were applied to recognize the characterization of the nanoparticles and to make sure of the linkage of particles. To examine the aptasensor at various stages, a range of electroanalytical techniques, such as cyclic voltammetry (CV), square-wave voltammetry (SWV), and electrochemical impedance spectroscopy (EIS), were employed. The aptasensor exhibited significant selectivity for PSA, as demonstrated by its ability to distinguish PSA from other components like glucose, carcinoembryonic antigen (CEA), etc. Ultimately, the detection limit (LOD) reached 1.371 ng/mL in the ferrocyanide environment with an R2 value of 0.9777. Furthermore, the labeled electrode in phosphate buffer achieved the remarkable detection limit of 1.566 pg/mL with an R2 value of 0.9676 and linear range of 2.5–12.5 pg/mL, demonstrating the impressive sensitivity and accuracy of the method.

Synthesis, chracterization, and analytical application of silver dopamine magnetic nanomaterial

Silver nanocubes decorated dopamine-magnetic (AgNCs-Dop@ Fe3O4) based nanomaterial has been synthesized for analytical application. The formation of AgNCs-Dop@ Fe3O4 materials was confirmed by X-ray powder diffraction, scanning electron microscopy, energy dispersive x-ray analysis, fourier transform infrared spectroscopy, and atomic force microscopy. Electrochemical characteristics of AgNCs-Dop@Fe3O4 NPs were investigated for histamine using chronoamperometry, linear sweep voltammetry, cyclic voltammetry, and electrochemical impedance spectroscopy. The AgNCs-Dop@Fe3O4 NPs (2 μL) drop casted electrode showed higher catalytic activity for histamine in potassium ferrocyanide and PBS solution. The AgNCs-Dop@Fe3O4 NPs modified electrode showed 1.2 μA/ μM sensitivity, linear range from 0.1 to 0.7 μM (R2 = 0.990), and LOD of 0.0025 μM for histamine. The proposed material showed good stability, selectivity, and sensitivity for histamine in interferences with good recoveries (>96%). The silver nanocubes decorated dopamine-magnetic nanomaterials can be used successfully as a screening tool for sensing histamine in various analytical samples.

Development of a novel microfluidic biosensing platform integrating micropillar array electrode and acoustic microstreaming techniques

Quantifying biomarkers at the early stage of the disease is challenging due to the low abundance of biomarkers in the sample and the lack of sensitive techniques. This article reports the development of a novel microfluidic electrochemical biosensing platform to address this challenge. The electrochemical sensing is achieved by utilizing a micropillar array electrode (μAE) coated with 3D bimetallic Pt–Pd nanotrees to enhance the sensitivity. A bubble-based acoustic microstreaming technique is integrated with the device to increase the contact of analyte molecules with the surface of electrodes to further enhance the electrochemical performance. The current density of Pt–Pd NTs/μAE with acoustic microstreaming is nearly 22 times that of the bare planar electrode in potassium ferrocyanide solution. The developed biosensor has demonstrated excellent sensing performance. For hydrogen peroxide detection, both the Pt–Pd NTs/μAE and acoustic microstreaming contribute to the sensitivity enhancement. The current density of the Pt–Pd NTs/μAE is approximatively 28 times that of the bare μAE. With acoustic microstreaming, this enhancement is further increased by nearly 1.6 times. The platform has a linear detection range of 5–1000 μM with a LOD of 1.8 μM toward hydrogen peroxide detection, while for sarcosine detection, the linear range is between 5 and 100 μM and LOD is 2.2 μM, respectively. Furthermore, the sarcosine biosensing shows a high sensitivity of 667 μA mM−1∙cm−2. Such a sensing platform has the potential as a portable device for high sensitivity detection of biomarkers.

The Redox‐Mediated Nickel–Metal Hydride Flow Battery

AbstractEach battery technology possesses intrinsic advantages and disadvantages, e.g., nickel–metal hydride (MH) batteries offer relatively high specific energy and power as well as safety, making them the power of choice for hybrid electric vehicles, whereas aqueous organic flow batteries (AORFBs) offer sustainability, simple replacement of their active materials and independent scalability of energy and power, making them very attractive for stationary energy storage. Herein, a new battery technology that merges the above mentioned battery technologies through the use of redox‐mediated reactions is proposed that intrinsically possesses the main features of each separate technology, e.g., high energy density of the solid active materials, easy recyclability, and independent scalability of energy and power. To achieve this, Ni(OH)2 and MHs are confined in the positive and negative reservoirs of an AORFB that employs alkaline solutions of potassium ferrocyanide and a mixture of 2,6‐dihydroxyanthraquinone and 7,8‐dihydroxyphenazine‐2‐sulfonic acid as catholyte and anolyte, respectively. An energy density of 128 Wh L–1 is achieved based on the capacity of the reservoirs leaving ample room for improvement up to the theoretical limit of 378 Wh L–1. This new battery technology opens up new market opportunities never before envisaged, for redox flow batteries, e.g., domestic energy storage and heavy‐duty vehicle transportation.

Novel sinuous band microelectrode array for electrochemical amperometric sensing

Pursuing a higher response signal is the core challenge in improving the detection performance of a microelectrode-based amperometric electrochemical sensor. Band microelectrode arrays (bMEAs) are attractive due to their high response current and economical fabrication process. However, further amplifying the response current by arranging the array more compactly or increasing its size is generally hindered by the shielding effect or the restricted construction region. A novel array of sinuous band microelectrodes (sbMEA) is proposed, produced by deforming a bMEA by tilting and bending. Its response and diffusion characteristics are simulated and analyzed. The effects of structural parameters on its performance are revealed, and their optimal value is deduced. The simulation demonstrates that a sbMEA can generate a larger current than a MEA of traditional shape. Production of such a sbMEA does not involve any additional fabrication costs compared with a bMEA. Cyclic voltammetry (CV) tests with potassium ferrocyanide solution verify the theoretical performance of the sbMEA, and a 10% higher current was obtained compared to the corresponding bMEA.

Recovery of Gold from Ore with Potassium Ferrocyanide Solution under UV Light

In this study, potassium ferrocyanide, a nontoxic cyanide precursor in dark and diffuse reflection environment, was applied as reagent for the leaching of gold. The free cyanide ions could gradually release from potassium ferrocyanide solution under the ultraviolet light. Orthogonal leaching experiments were performed in gold ore to analyze the effect of solution pH, potassium ferrocyanide dosage, and temperature in a potassium ferrocyanide solution system under UV light. Response surface methodology (RSM) was applied to explore the role of potassium ferrocyanide in gold leaching; optimized results showed that the gold recovery reached 67.74% in a high-alkaline environment at a 12.6 pH, 3.8 kg/t potassium ferrocyanide dosage, 62 °C, and irradiance of 10 mW·cm−2. The gold leaching kinetics were monitored by quartz crystal microbalance with dissipation (QCM-D) of potassium ferrocyanide solution. The results indicate that the gold extraction process could be divided into two stages: adsorption and leaching, and a rigid adsorption layer formed on the reaction surface. Furthermore, X-ray photoelectron spectroscopy (XPS) analysis of the gold sensor surface after leaching reaction showed that –C≡N appears on the gold sensor surface, and the gold is oxidized to form AuCN complexes.

Low energy consumption and mechanism study of redox flow desalination

Low-energy desalination technologies capable of continuous throughput at reasonable operating and maintenance cost are now critically needed. Herein, we present a continuous desalination process with average energy consumption as low as 2.14 kJ mole−1 salt removed achievable when using a 10 mM/10 mM ferri-/ferrocyanide solution that flows continuously between anode and cathode chambers. The salt feed at ~3000 ppm can be continuously desalted to a potable level of less than 150 ppm during the desalination process. At the anode, ferrocyanide is oxidized with electrons released to the external circuit and cations captured to achieve charge balance. Ferricyanide is reduced at the cathode, resulting in the constant transfer of anions from the dilute stream to the concentrate stream. The recycling of the redox mediators maintains an extremely low operating potential (~100 mV) and continuous salt extraction with unlimited removal capacity. Comparison of the use of ferri-/ferrocyanide, pure ferricyanide and ferrocyanide solutions indicate that the ultra-low energy consumption can be ascribed to the excellent electrochemical properties of the ferri-/ferrocyanide couple and the extremely low overpotential of the redox reactions owing to the synergistic effect of sufficient simultaneous ferrocyanide oxidation and ferricyanide reduction in the flow electrolyte streams. Our research provides a route for ultra-low energy desalination based on voltage suppression via use of facile redox couple mediators.

In Situ Real-Time Monitoring of ITO Film under a Chemical Etching Process Using Fourier Transform Electrochemical Impedance Spectroscopy.

As a novel approach to the in situ real-time investigation of an ITO electrode during the wet etching process, step-excitation Fourier-transform electrochemical impedance spectroscopy (FT-EIS) was implemented. The equivalent circuit parameters (e.g., Rct, Cdl) continuously obtained by the FT-EIS measurements during the entire etching process showed an electrode activation at the initial period as well as the completion of etching. The FT-EIS results were further validated by cyclic voltammograms and impedance measurements of partially etched ITO films using ferri- and ferrocyanide solution in combination with FESEM imaging, EDS, XRD analyses, and COMSOL simulation. We also demonstrated that this technique can be further utilized to obtain intact interdigitated array (IDA) electrodes in a reproducible manner, which is generally considered to be quite tricky due to delicacy of the pattern. Given that the FT-EIS allows for instantaneous snapshots of the electrode at every moment, this work may hold promise for in situ real-time examination of structural, electrokinetic, or mass transfer-related information on electrochemical systems undergoing constantly changing, transient processes including etching, which would be impossible with conventional electroanalytical techniques.

Optimization of Fc-Thiolate SAMs for Electrochemically Mediated Bacterial Biosensors

Alkanethiol Self-Assembled Monolayers (SAMs), typically deposited on Au substrates, have been commonly utilized to immobilize receptor biomolecules in the construction of a variety of biosensors, such as the detection of glucose oxidase by the immobilization of calixarenes thiols 1. The appeal of using SAMs derives from their ease of fabrication and component flexibility, allowing for more than one alkanethiol to be deposited in a single monolayer. This results in the formation of SAMs in which each thiol component adds a different property or role, thus introducing versatility to the construction and operation of resulting sensors 2.In our recent work, alkanethiol SAMs, composed of three different thiol molecules, were constructed for use as an electrochemical Toll-Like Receptor 4 (TLR4)-based sensor that can detect Gram-negative bacteria. TLRs are a family of immunoproteins in the innate immune system, which are able to detect a broad category of pathogens, rather than specific targets, as is the case with the adaptive system (e.g., antibodies). In our published work 3, SAMs consisted of a carboxylic acid terminated thiol that allowed for the conversion to a nitrilotriacetic (NTA) group. This moiety could then chelate a Ni2+ cation, followed by attachment of the TLR4 immunoprotein via its His-tag. The second thiol in the SAM contained a terminal ferrocene (Fc) group, where the Fc group was bound to the C11 chain via an amide group. Here, the Fc group serves as a mediator for charge transfer between ferrocyanide in solution and the Au substrate, resulting in relatively high current signals, thus making the sensor potentially field deployable. The third thiol in these SAMs was a hydroxy-terminated thiol, added as a diluent between the immobilized TLR4 receptors. SAMs were prepared by co-deposition on sputter Au on glass.Electrochemical testing involved cyclic voltammetry (CV) studies in pH 7 buffer solution in order to determine the amount of Fc-thiol present, as well as CV and electrochemical impedance spectroscopy (EIS) studies in ferrocyanide solutions to examine its redox-mediation response and to obtain a measure of the charge transfer rate. In the presence of lysed bacteria, the immobilized TLR4 dimerizes, which blocks electrochemical mediation between ferrocyanide and the surface bound Fc. This results in an increase in RCT which is our biosensor signal. However, a key problem with these sensors is that their RCT increased with electrochemical testing in the absence of lysed bacteria, producing signal drift. Thus, in the present work, the reasons for sensor signal drift and methods to overcome it were explored.It was found in recent work that the drift of the full TLR4 sensor was correlated with the loss in the Fc redox signal, although it was not clear if underlying SAM was at the root of the problem. If so, then it was necessary to determine if the loss in the Fc redox activity was caused by the physical loss of the Fc thiol from the Au surface or deactivation of the Fc surface complex and/or its electrochemistry. To determine which of these options was responsible for signal drift, the relative % v/v fraction of the three thiols was varied, and in later work, based on chemical considerations, the Fc molecule containing an amide group was replaced with a C11 chain bonded directly to the Fc. It was found that this latter strategy led to a very stable SAM, showing negligible drift in the Fc CV charges and in the RCT values in ferrocyanide solutions, with or without the TLR4 receptor attached on the outer surface of the SAM.This presentation will focus on presenting the electrochemistry of the various binary and ternary thiol SAMs investigated in this work and examining the Fc CV peak charges, potential, and kinetics, as well as the double layer capacitance, to better understand how and why the Fc redox response was stabilized. This is important because this correlates directly with the stability of the TLR4/Gram-negative bacteria sensor, as will be demonstrated for a TLR2 biosensor tested against Gram-positive bacteria cell wall ligands.

Sensitive and fast measurement of surface temperature with a thermogalvanic cell

Thermogalvanic cells may be viewed as electrochemical thermocouples. Here, we demonstrate their potential for sensitive and fast sensing of the surface temperature of a thin Au sheet, in contact with a 0.08 M equimolar ferri-/ferrocyanide solution in 26% KOH. We obtained a sensitivity of about 10 μK, because of the large Peltier coefficient of the electrochemical reaction at the electrode-electrolyte junction. The resolution is limited by the thermal noise of the electrochemical system and could be quantitatively explained by the thermal noise of a Randles equivalent circuit of the cell. Since no thermal contact resistances to bulky temperature sensors are involved, we achieved a response time smaller than 300 μs, which may be potentially lowered to a few microseconds. By using the thermogalvanic cell as a sensor for electrochemical microcalorimetry, we calibrated the system, in full agreement with a simulation of its thermal behavior.

Structural Changes of Mercaptohexanol Self-Assembled Monolayers on Gold and Their Influence on Impedimetric Aptamer Sensors.

Despite a large number of publications describing biosensors based on electrochemical impedance spectroscopy (EIS), little attention has been paid to the stability and reproducibility issues of the sensor interfaces. In this work, the stability and reproducibility of faradaic EIS analyses on the aptamer/mercaptohexanol (MCH) self-assembled monolayer (SAM)-functionalized gold surfaces in ferri- and ferrocyanide solution were systematically evaluated prior to and after the aptamer-probe DNA hybridization. It is shown that the EIS data exhibited significant drift, and this significantly affected the reproducibility of the EIS signal of the hybridization. As a result, no significant difference between the charge transfer resistance (RCT) changes induced by the aptamer-target DNA hybridization and that caused by the drift could be identified. A conditioning of the electrode in the measurement solution for more than 12 h was required to reach a stable RCT baseline prior to the aptamer-probe DNA hybridization. The monitored drift in RCT and double layer capacitance during the conditioning suggests that the MCH SAM on the gold surface reorganized to a thinner but more closely packed layer. We also observed that the hot binding buffer used in the following aptamer-probe DNA hybridization process could induce additional MCH and aptamer reorganization, and thus further drift in RCT. As a result, the RCT change caused by the aptamer-probe DNA hybridization was less than that caused by the hot binding buffer (blank control experiment). Therefore, it is suggested that the use of high temperature in the EIS measurement should be carefully evaluated or avoided. This work provides practical guidelines for the EIS measurements. Moreover, because SAM-functionalized gold electrodes are widely used in biosensors, for example, DNA sensors, an improved understanding of the origin of the observed drift is very important for the development of well-functioning and reproducible biosensors.

Introducing a mammalian nerve-muscle preparation ideal for physiology and microscopy, the transverse auricular muscle in the ear of the mouse

A new mammalian neuromuscular preparation is introduced for physiology and microscopy of all sorts: the intrinsic muscle of the mouse ear. The great utility of this preparation is demonstrated by illustrating how it has permitted us to develop a wholly new technique for staining muscle T-tubules, the critical conductive-elements in muscle. This involves sequential immersion in dilute solutions of osmium and ferrocyanide, then tannic acid, and then uranyl acetate, all of which totally blackens the T-tubules but leaves the muscle pale, thereby revealing that the T-tubules in mouse ear-muscles become severely distorted in several pathological conditions. These include certain mouse-models of muscular dystrophy (specifically, dysferlin-mutations), certain mutations of muscle cytoskeletal proteins (specifically, beta-tubulin mutations), and also in denervation-fibrillation, as observed in mouse ears maintained with in vitro tissue-culture conditions. These observations permit us to generate the hypothesis that T-tubules are the “Achilles' heel” in several adult-onset muscular dystrophies, due to their unique susceptibility to damage via muscle lattice-dislocations. These new observations strongly encourage further in-depth studies of ear-muscle architecture, in the many available mouse-models of various devastating human muscle-diseases. Finally, we demonstrate that the delicate and defined physical characteristics of this 'new' mammalian muscle are ideal for ultrastructural study, and thereby facilitate the imaging of synaptic vesicle membrane recycling in mammalian neuromuscular junctions, a topic that is critical to myasthenia gravis and related diseases, but which has, until now, completely eluded electron microscopic analysis. This article is part of a Special Issue entitled: Honoring Ricardo Miledi - outstanding neuroscientist of XX-XXI centuries.