Multiplex electrochemical sensing platforms for the detection of breast cancer biomarkers.

Herein, advancements in electroanalytical devices for the simultaneous detection of diverse breast cancer (BC) markers are demonstrated. This article identifies several important areas of exploration for electrochemical diagnostics and highlights important factors that are pivotal for the successful deployment of novel bioanalytical devices. We have highlighted that the limits of detection (LOD) reported for the multiplex electrochemical biosensor can surpass the sensitivity displayed by current clinical standards such as ELISA, FISH, and PCR. HER-2; a breast cancer marker characterised by increased metastatic potential, more aggressive development, and poor clinical outcomes; can be sensed with a LOD of 0.5 ng/ml using electrochemical multiplex platforms, which falls within the range of that measured by ELISA (from picogram/ml to nanogram/ml). Electrochemical multiplex biosensors are reported with detection limits of 0.53 ng/ml and 0.21 U/ml for MUC-1 and CA 15-3, respectively, or 5.8 × 10-3 U/ml for CA 15-3 alone. The sensitivity of electrochemical assays is improved when compared to conventional analysis of MUC-1 protein which is detected at 11-12 ng/ml, and ≤30 U/ml for CA 15-3 in the current clinical blood tests. The LOD for micro-ribonucleic acid (miRNA) biomarkers analyzed by electrochemical multiplex assays were all notedly superior at 9.79 × 10-16 M, 3.58 × 10-15 M, and 2.54 × 10-16 M for miRNA-155, miRNA-21, and miRNA-16, respectively. The dogma in miRNA testing is the qRT-PCR method, which reports ranges in the ng/ml level for the same miRNAs. Breast cancer exosomes, which are being explored as a new frontier of biosensing, have been detected electrochemically with an LOD of 103-108 particles/mL and can exceed detection limits seen by the tracking and analysis of nanoparticles (∼ 107 particles/ml), flow cytometry, Western blotting and ELISA, etc. A range of concentration at 78-5,000 pg/ml for RANKL and 16-1,000 pg/ml for TNF is reported for ELISA assay while LOD values of 2.6 and 3.0 pg/ml for RANKL and TNF, respectively, are demonstrated by the electrochemical dual immunoassay platform. Finally, EGFR and VEGF markers can be quantified at much lower concentrations (0.01 and 0.005 pg/ml for EGFR and VEGF, respectively) as compared to their ELISA assays (EGRF at 0.31-20 ng/ml and VEGF at 31.3-2,000 pg/ml). In this study we hope to answer several questions: (1) Are the limits of detection (LODs) reported for multiplex electrochemical biosensors of clinical relevance and how do they compare to well-established methods like ELISA, FISH, or PCR? (2) Can a single sensor electrode be used for the detection of multiple markers from one blood drop? (3) What mechanism of electrochemical biosensing is the most promising, and what technological advancements are needed to utilize these devices for multiplex POC detection? (4) Can nanotechnology advance the sensitive and selective diagnostics of multiple BC biomarkers? (5) Are there preferred receptors (antibody, nucleic acid or their combinations) and preferred biosensor designs (complementary methods, sandwich-type protocols, antibody/aptamer concept, label-free protocol)? (6) Why are we still without FDA-approved electrochemical multiplex devices for BC screening?

Electrochemical Detection of Borrelia burgdorferi Using a Biomimetic Flow Cell System.

Lyme disease, caused by infection with pathogenic Borrelia bacteria, has emerged as a pervasive illness throughout North America and many other regions of the world in recent years, owing in part to climate-mediated habitat expansion of the tick vectors. Standard diagnostic testing has remained largely unchanged over the past several decades and is indirect, relying on detection of antibodies against the Borrelia pathogen, rather than detection of the pathogen itself. The development of new rapid, point-of-care tests for Lyme disease that directly detects the pathogen could drastically improve patient health by enabling faster and more frequent testing that could better inform patient treatment. Here, we describe a proof-of-concept electrochemical sensing approach to the detection of the Lyme disease-causing bacteria, which utilizes a biomimetic electrode to interact with the Borrelia bacteria that induce impedance alterations. In addition, the catch-bond mechanism between bacterial BBK32 protein and human fibronectin protein, which exhibits improved bond strength with increased tensile force, is tested within an electrochemical injection flow-cell to achieve Borrelia detection under shear stress.

Innovations and Challenges in Electroanalytical Tools for Rapid Biosurveillance of SARS-CoV-2.

Since the onset of the coronavirus disease 2019 (COVID-19) pandemic, preventive social paradigms and vaccine development have undergone serious renovations, which drastically reduced the viral spread and increased collective immunity. Although the technological advancements in diagnostic systems for severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2) detection are groundbreaking, the lack of sensitive, robust, and consumer-end point-of-care (POC) devices with smartphone connectivity are conspicuously felt. Despite its revolutionary impact on biotechnology and molecular diagnostics, the reverse transcription polymerase chain reaction technique as the gold standard in COVID-19 diagnosis is not suitable for rapid testing. Today's POC tests are dominated by the lateral flow assay technique, with inadequate sensitivity and lack of internet connectivity. Herein, the biosensing advancements in Internet of Things (IoT)-integrated electroanalytical tools as superior POC devices for SARS-CoV-2 detection will be demonstrated. Meanwhile, the impeding factors pivotal for the successful deployment of such novel bioanalytical devices, including the incongruous standards, redundant guidelines, and the limitations of IoT modules will be discussed.

Heterometallic cobalt(ii) calix[6 and 8]arenes: synthesis, structure and electrochemical activity.

Heterometallic cobalt p-tert-butylcalix[6 and 8]arenes have been generated from the in situ reaction of lithium reagents (n-BuLi or t-BuOLi) or NaH with the parent calix[n]arene and subsequent reaction with CoBr2. The reverse route, involving the addition of in situ generated Li[Co(Ot-Bu)3] to p-tert-butylcalix[6 and 8]arene, has also been investigated. X-ray crystallography reveals the formation of complicated products incorporating differing numbers of cobalt and lithium or sodium centers, often with positional disorder, as well as, in some cases, the retention of halide. The electrochemical analysis revealed several oxidation events related to the subsequent oxidation of Co(ii) centers and the reduction of the metal cation at negative potentials. Moreover, the electrochemical activity of the phenol moieties of the parent calix[n]arenes resulted in dimerized products or quinone derivatives, leading to insoluble oligomeric products that deposit and passivate the electrode. Preliminary screening for electrochemical proton reduction revealed good activity for a number of these systems. Results suggest that [Co6Na(NCMe)6(µ-O)(p-tert-butylcalix[6]areneH)2Br]·7MeCN (6·7MeCN) is a promising molecular catalyst for electrochemical proton reduction, with a mass transport coefficient, catalytic charge transfer resistance and current magnitude at the catalytic turnover region that are comparable to those of the reference electrocatalyst (Co(ii)Cl2).

Breast Cancer Aptamers: Current Sensing Targets, Available Aptamers, and Their Evaluation for Clinical Use in Diagnostics.

Breast cancer is the most commonly occurring cancer in women worldwide, and the rate of diagnosis continues to increase. Early detection and targeted treatment towards histological type is crucial to improving outcomes, but current screening methods leave some patients at risk of late diagnosis. The risk of late diagnosis and progressed disease is of particular concern for young women as current screening methods are not recommended early in life. Aptamers are oligonucleotides that can bind with high specificity to target molecules such as proteins, peptides, and other small molecules. They are relatively cheap to produce and are invariable from batch to batch, making them ideal for use in large-scale clinical or screening programs. The use of aptamers for breast cancer screening, diagnosis, and therapeutics is promising, but comparison of these aptamers and their corresponding biomarkers for use in breast cancer is significantly lacking. Here, we compare the currently available aptamers for breast cancer biomarkers and their respective biomarkers, as well as highlight the electrochemical sensors that are in development.

Van der Waals Heterostructures-Recent Progress in Electrode Materials for Clean Energy Applications.

The unique layered morphology of van der Waals (vdW) heterostructures give rise to a blended set of electrochemical properties from the 2D sheet components. Herein an overview of their potential in energy storage systems in place of precious metals is conducted. The most recent progress on vdW electrocatalysis covering the last three years of research is evaluated, with an emphasis on their catalytic activity towards the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). This analysis is conducted in pair with the most active Pt-based commercial catalyst currently utilized in energy systems that rely on the above-listed electrochemistry (metal-air battery, fuel cells, and water electrolyzers). Based on current progress in HER catalysis that employs vdW materials, several recommendations can be stated. First, stacking of the two types vdW materials, with one being graphene or its doped derivatives, results in significantly improved HER activity. The second important recommendation is to take advantage of an electronic coupling when stacking 2D materials with the metallic surface. This significantly reduces the face-to-face contact resistance and thus improves the electron transfer from the metallic surface to the vdW catalytic plane. A dual advantage can be achieved from combining the vdW heterostructure with metals containing an excess of d electrons (e.g., gold). Despite these recent and promising discoveries, more studies are needed to solve the complexity of the mechanism of HER reaction, in particular with respect to the electron coupling effects (metal/vdW combinations). In addition, more affordable synthetic pathways allowing for a well-controlled confined HER catalysis are emerging areas.

The electrochemical detection of bioterrorism agents: a review of the detection, diagnostics, and implementation of sensors in biosafety programs for Class A bioweapons.

During the past year, disease has shown us the iron grip it can hold over a population of people. Health systems can be overwhelmed, economies can be brought into recession, and many people can be harmed or killed. When weaponized, diseases can be manipulated to create a detriment to health while becoming an economic burden on any society. It is consequently prudent that easy detection of bioweapons is available to governments for protecting their people. Electrochemical sensing displays many distinct advantages, such as its low limit of detection, low cost to run, rapid generation of results, and in many instances portability. We therefore present a wide array of electrochemical sensing platforms currently being fabricated, a brief summary of Class A bioweapons, and the potential future of bioweapon detection and biosafety.

Lyme Disease Biosensors: A Potential Solution to a Diagnostic Dilemma.

Over the past four decades, Lyme disease has remained a virulent and pervasive illness, persisting throughout North America and many other regions of the world. Recent increases in illness in many countries has sparked a renewed interest in improved Lyme diagnostics. While current standards of diagnosis are acceptable for the late stages of the disease, it remains difficult to accurately diagnose early forms of the illness. In addition, current diagnostic methods tend to be relatively expensive and require a large degree of laboratory-based analysis. Biosensors represent the fusion of biological materials with chemical techniques to provide simple, inexpensive alternatives to traditional diagnostic methods. Lyme disease biosensors have the potential to better diagnose early stages of the illness and provide possible patients with an inexpensive, commercially available test. This review examines the current state of Lyme disease biosensing, with a focus on previous biosensor development and essential future considerations.

Flexible Electrode Based on MWCNT Embedded in a Cross-Linked Acrylamide/Alginate Blend: Conductivity vs. Stretching.

A polyacrylamide-alginate hydrogel electrolyte, blended with Multi-Walled Carbon Nanotubes (MWCNT) as an electronically conductive fraction, allows for the creation of a flexible, durable, and resilient electrode. The MWCNT content is correlated with mechanical characteristics such as stretch modulus, tensile resistance, and electrical conductivity. The mechanical analysis demonstrates tensile strength that is comparable to similar hydrogels reported in the literature, with increasing strength for MWCNT-embedded hydrogels. The impedance spectroscopy reveals that the total resistance of electrodes decreases with increasing MWCNT content upon elongation and that bending and twisting do not obstruct their conductivity. The MWCNT-inserted hydrogels show mixed ionic and electronic conductivities, both within a range of 1-4 × 10-2 S cm-1 in a steady state. In addition, the thermal stability of these materials increases with incrementing MWCNT content. This observation agrees with long-term charge-discharge cycling that shows enhanced electrochemical durability of the MWCNT-hydrogel hybrid when compared to pure hydrogel electrolyte. The hydrogel-carbon films demonstrate an increased interfacial double-layer current at a high MWCNT content (giving an area-specific capacitance of ~30 mF cm-2 at 2.79 wt.% of MWCNT), which makes them promising candidates as printable and flexible electrodes for lightweight energy storage applications. The maximum content of MWCNT within the polymer electrolyte was estimated at 2.79 wt.%, giving a very elastic polymer electrode with good electrical characteristics.

Polypyrrole decorated metal-organic frameworks for supercapacitor devices.

Due to their large specific surface areas and porosity, metal-organic frameworks (MOFs) have found many applications in catalysis, gas separation, and gas storage. However, their use as electronic components such as supercapacitors is stunted due to their poor electrical conductivity. We report a remedy for this by combining the MOF structure with polypyrrole (PPy), a well-known conductive polymer. Three MOFs are studied for modification to this end: CPO-27-Ni and CPO-27-Co (M2DOBDC, M = Ni2+, Co2+, DOBDC = 2,5-dihydroxy-1,4-benzenedicarboxylate) and HKUST-1 (Cu3(BTC)2, BTC = 1,3,5 benzenetricarboxylate). The gravimetric capacitance of pure MOFs is boosted several orders of magnitude after reinforcement of PPy (e.g., from 0.679 to 185 F g-1 for HKUST-1 and PPy-HKUST-1, respectively), and is much higher than reported for pure PPy. In total, these PPy-d-MOFs exhibit specific capacitances up to 354 F g-1, retaining 70% of this value even after 2500 cycles. Among them, the highest capacitance is found for PPy-CPO-27-Ni (354 F g-1), followed by PPy-CPO-27-Co (263 F g-1) and PPy-HKUST-1 (185 F g-1). The maximum operating potential for these electrodes is 0.5 V, which is restricted by the contact of MOF with aqueous electrolyte and with extremely low PPy content. As a solution, higher PPy loading and rational adjustment of particle size and porosity of both MOF and PPy are recommended so that the MOF/electrolyte interface is limited, leading to more robust electrode. The work completed here describes a highly promising approach to tackling the electrically insulating nature of MOFs, paving the way for their use in electrochemical energy storage devices.

Nanostructured Cu2O Synthesized via Bipolar Electrochemistry.

Cuprous oxide (Cu2O) was synthesized for the first time via an open bipolar electrochemistry (BPE) approach and characterized in parallel with the commercially available material. As compared to the reference, Cu2O formed through a BPE reaction demonstrated a decrease in particle size; an increase in photocurrent; more efficient light scavenging; and structure-correlated changes in the flat band potential and charge carrier concentration. More importantly, as-synthesized oxides were all phase-pure, defect-free, and had an average crystallite size of 20 nm. Ultimately, this study demonstrates the impact of reaction conditions (e.g., applied potential, reaction time) on structure, morphology, surface chemistry, and photo-electrochemical activity of semiconducting oxides, and at the same time, the ability to maintain a green synthetic protocol and potentially create a scalable product. In the proposed BPE synthesis, we introduced a common food supplement (potassium gluconate) as a reducing and complexing agent, and as an electrolyte, allowing us to replace the more harmful reactants that are conventionally used in Cu2O production. In addition, in the BPE process very corrosive reactants, such as hydroxides and metal precursors (required for synthesis of oxides), are generated in situ in stoichiometric quantity, providing an alternative methodology to generate various nanostructured materials in high yields under mild conditions.

ZnO Synthesized Using Bipolar Electrochemistry: Structure and Activity.

The photoactive materials broadly applied in catalysis and energy conversion are generally composed of metal oxides. Among these oxides, ZnO showed a promising photocatalytic activity; however, traditional synthetic routes generated by-products and large amounts of secondary waste. Herein, we report the use of bipolar electrochemistry to generate ZnO nanoparticles using deionized water and a zinc metal to conform to green chemistry practices. TEM imaging demonstrated that the sizes of the bipolar-made ZnO particles were smaller than the commercial sample. The presence of structural defects in ZnO was correlated with the chemical shifts analyzed by X-ray photoelectron spectroscopy (XPS) and by different concentrations of O2- ions in stoichiometric and defected lattice. Further, the diffuse reflectance UV⁻Vis studies demonstrated a blue-shift in the reflectance spectrum for the bipolar-made oxide. This was also an indication of defects in the ZnO lattice, which related to the formation of shallow levels in the bandgap of the material. The structural and morphological differences influenced the photocatalytic characteristics, revealing a higher photocurrent for the bipolar-made ZnO when compared to the reference sample. This was further manifested in lower total resistivity for all anodes made from the non-stoichiometric ZnO, and also in their shorter diffusion length for charge exchange and electron lifetimes.

Structure of Ni(OH)2 intermediates determines the efficiency of NiO-based photocathodes - a case study using novel mesoporous NiO nanostars.

We report the wet chemical synthesis of mesoporous NiO nanostars (NS) as photocathode material for dye-sensitized solar cells (DSSCs). The growth mechanism of NiO NS as a new morphology of NiO is assessed by TEM and spectroscopic investigations. The NiO NS are obtained upon annealing of preformed ß-Ni(OH)2 into pristine NiO with low defect concentrations and favorable electronic configuration for dye sensitization. The NiO NS consist of fibers self-assembled from nanoparticles yielding a specific surface area of 44.9 m2 g-1. They possess a band gap of 3.83 eV and can be sensitized by molecular photosensitizers bearing a range of anchoring groups, e.g. carboxylic acid, phosphonic acid, and pyridine. The performance of NiO NS-based photocathodes in photoelectrochemical application is compared to that of other NiO morphologies, i.e. nanoparticles and nanoflakes, under identical conditions. Sensitization of NiO NS with the benchmark organic dye P1 leads to p-DSSCs with a high photocurrent up to 3.91 mA cm-2 whilst the photoelectrochemical activity of the NiO NS photocathode in aqueous medium in the presence of an irreversible electron acceptor is reflected by generation of a photocurrent up to 23 µA cm-2.

Vanadyl sulfates: molecular structure, magnetism and electrochemical activity.

Reaction of differing amounts of vanadyl sulfate with p-tert-butylthiacalix[4]areneH4 and base allows access to the vanadyl-sulfate species [NEt4]4[(VO)4(µ3-OH)4(SO4)4]·½H2O (1), [HNEt3]5[(VO)5(µ3-O)4(SO4)4]·4MeCN (2·4MeCN) and [NEt4]2[(VO)6(O)2(SO4)4(OMe)(OH2)]·MeCN (3·MeCN). Similar use of p-tert-butylsulfonylcalix[4]areneH4, p-tert-butylcalix[8]areneH8 or p-tert-butylhexahomotrioxacalix[3]areneH3 led to the isolation of [HNEt3]2[H2NEt2]2{[VO(OMe)]2p-tert-butylcalix[8-SO2]areneH2} (4), [HNEt3]2[V(O)2p-tert-butylcalix[8]areneH5] (5) and [HNEt3]2[VIV2VV4O11(OMe)8] (6), respectively. Dc magnetic susceptibility measurements were performed on powdered microcrystalline samples of 1-3 in the T = 300-2 K temperature range. Preliminary screening for electrochemical water oxidation revealed some activity for 2 with turnover frequency (TOF) and number (TON) of 2.2 × 10-4 s-1 and 6.44 × 10-6 (mmol O2/mmol cat.), respectively. The compound 3 showed an improved electrochemical activity in the presence of water. This is related to the increased number and the rate of electrons exchanged during oxidation of V4+ species, facilitated by protons generated in the water discharge process.

Biomass-derived nanostructured carbons and their composites as anode materials for lithium ion batteries.

Since ever-increasing energy demands stimulated intensive research activities on lithium-ion batteries (LIBs), biomass as an earth-abundant renewable energy source has played an intriguing and promising role in developing sustainable biomass-derived carbons and their composite materials for high-performance LIB anodes. Different from other materials (e.g., silicon, tin, metal oxides, etc.), biomass-derived carbons and their composite materials have been applied more and more to LIBs due to their advantages such as low cost, green and eco-friendly synthesis, easy accessibility, sustainable strategy, and improved battery performance, including capacity, cycling property, and stability/durability. This tutorial review focusing on biomass-derived carbons and their composites in the application of LIB anodes will act as a strategic guide to build a close connection between renewable materials and electrochemical energy storage devices. Also, this review provides a critical analysis and comparison of biomass-derived carbons and their composites for LIB anodes, coupled with an important insight into the remaining challenges and future directions in the field.

Synthesis of Electrical Conductive Silica Nanofiber/Gold Nanoparticle Composite by Laser Pulses and Sputtering Technique.

Biocompatible-sensing materials hold an important role in biomedical applications where there is a need to translate biological responses into electrical signals. Increasing the biocompatibility of these sensing devices generally causes a reduction in the overall conductivity due to the processing techniques. Silicon is becoming a more feasible and available option for use in these applications due to its semiconductor properties and availability. When processed to be porous, it has shown promising biocompatibility; however, a reduction in its conductivity is caused by its oxidization. To overcome this, gold embedding through sputtering techniques are proposed in this research as a means of controlling and further imparting electrical properties to laser induced silicon oxide nanofibers. Single crystalline silicon wafers were laser processed using an Nd:YAG pulsed nanosecond laser system at different laser parameters before undergoing gold sputtering. Controlling the scanning parameters (e.g., smaller line spacings) was found to induce the formation of nanofibrous structures, whose diameters grew with increasing overlaps (number of laser beam scanning through the same path). At larger line spacings, nano and microparticle formation was observed. Overlap (OL) increases led to higher light absorbance's by the wafers. The gold sputtered samples resulted in greater conductivities at higher gold concentrations, especially in samples with smaller fiber sizes. Overall, these findings show promising results for the future of silicon as a semiconductor and a biocompatible material for its use and development in the improvement of sensing applications.

Specific Surface versus Electrochemically Active Area of the Carbon/Polypyrrole Capacitor: Correlation of Ion Dynamics Studied by an Electrochemical Quartz Crystal Microbalance with BET Surface.

Carbon/polypyrrole (PPy) composites are promising electrode materials for energy storage applications such as lightweight capacitors. Although these materials are composed of relatively inexpensive components, there is a gap of knowledge regarding the correlation between surface, porosity, ion exchange dynamics, and the interplay of the double layer capacitance and pseudocapacitance. In this work we evaluate the specific surface area analyzed by the BET method and the area accessible for ions using electrochemical quartz-crystal microbalance (EQCM) for SWCNT/PPy and carbon black Vulcan XC72-R/PPy composites. The study revealed that the polymer has significant influence on the pore size of the composites. Although the BET surface is low for the polypyrrole, the electrode mass change and thus the electrochemical area are large for the polymer-containing electrodes. This indicates that multiple redox active centers in the charged polymer chain are good ion scavengers. Also, for the composite electrodes, the effective charge storage occurs at the polypyrrole-carbon junctions, which are easy to design/multiply by a proper carbon-to-polymer weight ratio. The specific BET surface and electrochemically accessible surface area are both important parameters in calculation of the electrode capacitance. SWCNTs/PPy showed the highest capacitances normalized to the BET and electrochemical surface as compared to the polymer-carbon black. TEM imaging revealed very homogeneous distribution of the nanosized polymer particles onto the CNTs, which facilitates the synergistic effect of the double layer capacitance (CNTs) and pseudocapacitance (polymer). The trend in the electrode mass change in correlation with the capacitance suggest additional effects such as a solvent co-insertion into the polymer and the contribution of the charge associated with the redox activity of oxygen-containing functional groups on the carbon surface.

ZnO Nanostructures for Dye-Sensitized Solar Cells Using the TEMPO+ /TEMPO Redox Mediator and Ruthenium(II) Photosensitizers with 1,2,3-Triazole-Derived Ligands.

A series of thiocyanate-free bis(tridentate) ruthenium(II) complexes incorporating 1,2,3-triazole-derived NNN-, NCN-, and CNC-coordinating ligands has been employed for sensitizing ZnO photoanodes for dye-sensitized solar cells (DSSCs). Additionally, the first use of the TEMPO+ /TEMPO (2,2,6,6-tetramethyl-piperidine-1-oxyl) redox mediator as a surrogate for the I3 - /I- redox couple in ZnO nanostructured DSSCs is presented. Compared with I3 - /I- -based electrolytes, shorter charge lifetimes and diffusion lengths were determined for the TEMPO+ /TEMPO-based electrolyte. Nonetheless, similar power conversion efficiencies (PCEs) were achieved with both electrolytes for the RuNCN and RuCNC complexes, whereas higher PCEs are enabled by the iodine-free electrolyte in case of RuNNN. The combination of the molecular sensitizers and the TEMPO-based electrolyte exhibits relatively high external quantum efficiency (EQE) and promising PCEs, ranging from 4.48 to 1.47 %, which are-in part-comparable to that of ZnO-DSSCs with the benchmark N749 black dye. The TEMPO-based electrolyte also exhibits less absorption compared with its I3 - /I- counterpart, a favorable feature for enhancing the light harvesting ability of the photoanode. Furthermore, the results show the effect of the dye-sensitization procedure on the PCE values: The use of ethanol as the solvent compared with methanol increases the DSSC's efficiency, which is attributed to improved chemisorption of the sensitizer onto the ZnO surface.

Micropatterns of [Fe-Fe]-Hydrogenase Active-Site Model Complexes Fabricated by Electro-Oxidative Lithography.

[Fe-Fe]-hydrogenase active site model complexes ([Fe(CO)3]2[(µ-SCH2)2C(CH2OH)2]) were immobilized on micropatterned n-octadecyltrichlorosilane (OTS) monolayers deposited on a Si substrate to form a microscale catalytic system. The micropatterns were generated by electro-oxidative lithography performed with a conductive TEM grid. The [Fe-Fe]-hydrogenase active-site complex molecules were selectively anchored in lithographic line areas with good coverage. Additionally, the biomimetic metal centers of the hydrogenase active-site complex molecules still maintained their catalytic activity and their redox-active properties after the immobilization process, which was proven by cyclic voltammetry.

The correlation of the binding mechanism of the polypyrrole-carbon capacitive interphase with electrochemical stability of the composite electrode.

Carbon-polymer composites have great application potential in the field of organic batteries, capacitors, capacitive water desalination reactors and as the conductive platforms for electrochemical sensors. Although numerous studies have been carried out with respect to the synthesis, the optimization of composition, the carbon type and the morphology control, there is still a lack of understanding about which kind of intermolecular connection between carbon and polymer phases is preferential, and how the system should be designed to achieve the application demand of long-term electrochemical stability. Herein, we propose two model systems that employ the most well-known commercial carbons (SWCNTs and carbon black Vulcan XC72-R) to generate polypyrrole-C composites and validate the type of chemical bonding that is preferential to maintain electrochemical stability. In this work we used a simple oxidative polymerization of pyrrole and generated various formulations (with variable polymer content). Based on the surface XPS combined with bulk TGA-MS analysis we were able to evaluate the concentration and type of oxygen-containing functionalities, revealing a high oxygen content for the carbon black. It was further correlated with XPS analysis of the respective composites showed evidence of the electronic interaction called π-π* stacking between SWCNTs and PPy, and the binding energy shifts associated with the formation of hydrogen bridge bonds in the case of Vulcan XC-72R-PPy. Furthermore, the electrochemical stability of these model samples was investigated by AC impedance spectroscopy. The charge transfer resistance (Rct) was analyzed upon the oxidative potential, revealing SWCNT-PPy as an ultra-stable composite, even for the high polymer content (1 : 4 weight ratio of C-PPy). In contrast, the carbon black-PPy underwent rapid degradation in the whole composition range. The durability is associated with the type and strength of the polymer-carbon bonding as revealed by EIS impedance correlated with spectroscopic studies. The electronic interactions between SWCNTs and PPy result in superior stability while the carbon black-PPy, where the hydrogen bridge bonds are generated, is not stable under the same experimental conditions.