Electrochemical detection of bacterial endotoxin lipopolysaccharide (LPS) on gold electrode modified with DAL-PEG-DK5-PEG-OH - Antimicrobial peptide conjugate.

This work describes fabrication of gold electrodes modified with peptide conjugate DAL-PEG-DK5-PEG-OH that enables ultra-sensitive detection of lipopolysaccharide (LPS) isolated from the reference strain of Escherichia coli O26:B6. The initial step of the established procedure implies immobilization of the fully protected DAL-PEG-DK5-PEG-OH peptide on the surface of the gold electrode previously modified by cysteamine. Then side chain- and Fmoc-deprotection was performed in situ on the electrode surface, followed by its incubation in 1 % of BSA solution to block non-specific bindings sites before LPS detection. The efficiency of the modification was confirmed by X-ray Photoelectron Spectroscopy (XPS) measurements. Additionally, the cyclic voltammetry (CV) and electrochemical impendance spectroscopy (EIS) were employed to monitor the effectiveness of each step of the modification. The obtained results confirmed that the presence of the surface-attached covalently bound peptide DAL-PEG-DK5-PEG-OH enables LPS detection by means of CV technique within the range from 5 × 10-13 to 5 × 10-4 g/mL in PBS solution. The established limit of detection (LOD) for EIS measurements was 4.93 × 10-21 g/mL with wide linear detection range from 5 × 10-21 to 5 × 10-14 g/mL in PBS solution. Furthermore, we confirmed the ability of the electrode to detect LPS in a complex biological samples, like mouse urine and human serum. The effectiveness of the electrodes in identifying LPS in both urine and serum matrices was confirmed for samples containing LPS at both 2.5 × 10-15 g/mL and 2.5 × 10-9 g/mL.

Imidazole-Based Lithium Salt LiHDI as a Solid Electrolyte Interphase-Stabilising Additive for Lithium-Conducting Electrolytes.

Lithium salt LiHDI (lithium 4,5-dicyano-2-(n-heptafluoropropyl)imidazolide) is proposed as a solid electrolyte interphase-stabilising additive for lithium-ion batteries, which can be added in a smaller amount than fluoroethylene carbonate (FEC) and vinylene carbonate (VC) additives. Electrolytes containing either lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide (LiTDI) or battery-standard LiPF6 were tested with various amounts of LiHDI additive. Chemical stability in the presence of water and the thermal stability of LiHDI are on par with LiTDI. LiHDI additive does not negatively affect the properties of electrolytes. Conductivity measurements of solutions, galvanostatic cycling of graphite-LiFePO4 cells at room temperature, cells' cycling at 60 °C, internal cell resistance monitoring during cycling, and XPS analysis of electrodes' surfaces after cycling have been performed. LiHDI, unlike the FEC-VC mixture, does not negatively affect the properties of the electrolyte. Cycling showed improved capacity retention with LiHDI additive with both graphite and LiFePO4 as capacity-limiting electrodes over samples without additives. At elevated temperatures, samples with LiHDI exhibited better capacity retention during cycling than those with FEC-VC. Internal cell resistance can be correlated with capacity retention. XPS results show changes in the composition of SEI depending on the composition of the electrolyte and the duration of cycling.

Phospholipid-functionalized gold electrode for cellular membrane interface studies - interactions between DMPC bilayer and human cystatin C.

This work describes the electrochemical studies on the interactions between V57G mutant of human cystatin C (hCC V57G) and membrane bilayer immobilized on the surface of a gold electrode. The electrode was modified with 6-mercaptohexan-1-ol (MCH) and 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC). DMPC was used as a membrane mimetic for monitoring electrochemical changes resulting from the interactions between the functionalized electrode surface and human cystatin C. The interactions between the modified electrode and hCC V57G were investigated by cyclic voltammetry and electrochemical impedance spectroscopy in a phosphate buffered saline (PBS) containing Fe(CN)63-/4- as a redox probe. The electrochemical measurements confirm that fabricated electrode is sensitive to hCC V57G at the concentration of 1 × 10-14 M. The incubation studies carried out at higher concentrations resulted in insignificant changes observed in cyclic voltammetry and electrochemical impedance spectroscopy measurements. The calculated values of surface coverage θR confirm that the electrode is equally covered at higher concentrations of hCC V57G. Measurements of wettability and surface free energy made it possible to determine the influence of individual structural elements of the modified gold electrode on its properties, and thus allowed to understand the nature of the interactions. Contact angle values confirmed the results obtained during electrochemical measurements, indicating the sensitivity of the electrode towards hCC V57G at the concentration of 1 × 10-14 M. In addition, the XPS spectra confirmed the successful anchoring of hCC V57G to the DMPC-functionalized surface.

Laser-Induced Graphitization of Polydopamine on Titania Nanotubes.

Since the discovery of laser-induced graphite/graphene, there has been a notable surge of scientific interest in advancing diverse methodologies for their synthesis and applications. This study focuses on the utilization of a pulsed Nd:YAG laser to achieve graphitization of polydopamine (PDA) deposited on the surface of titania nanotubes. The partial graphitization is corroborated through Raman and XPS spectroscopies and supported by water contact angle, nanomechanical, and electrochemical measurements. Reactive molecular dynamics simulations confirm the possibility of graphitization in the nanosecond time scale with the evolution of NH3, H2O, and CO2 gases. A thorough exploration of the lasing parameter space (wavelength, pulse energy, and number of pulses) was conducted with the aim of improving either electrochemical activity or photocurrent generation. Whereas the 532 nm laser pulses interacted mostly with the PDA coating, the 365 nm pulses were absorbed by both PDA and the substrate nanotubes, leading to a higher graphitization degree. The majority of the photocurrent and quantum efficiency enhancement is observed in the visible light between 400 and 550 nm. The proposed composite is applied as a photoelectrochemical (PEC) sensor of serotonin in nanomolar concentrations. Because of the suppressed recombination and facilitated charge transfer caused by the laser graphitization, the proposed composite exhibits significantly enhanced PEC performance. In the sensing application, it showed superior sensitivity and a limit of detection competitive with nonprecious metal materials.

Boron-doped diamond nanosheet volume-enriched screen-printed carbon electrodes: a platform for electroanalytical and impedimetric biosensor applications.

This paper focuses on the development of a novel electrode based on boron-doped diamond nanosheet full-volume-enriched screen-printed carbon electrodes (BDDPE) for use as an impedimetric biosensor. Impedimetric biosensors offer high sensitivity and selectivity for virus detection, but their use as point-of-care devices is limited by the complexity of nanomaterials' architecture and the receptor immobilisation procedures. The study presents a two-step modification process involving the electroreduction of diazonium salt at the BDDPE and the immobilisation of antibodies using zero-length cross-linkers for a selective impedimetric biosensor of Haemophilus influenzae (Hi). The incorporation of diamond nanosheets into BDDPE leads to enhanced charge transfer and electrochemical behaviour, demonstrating greatly improved electrochemically active surface area compared with unmodified screen-printed electrodes (by 44% and 10% on average for [Ru(NH3)6]Cl2 and K3[Fe(CN)6], respectively). The presented sensing system shows high specificity towards protein D in Hi bacteria, as confirmed by negative controls against potential interference from other pathogens, with an estimated tolerance limit for interference under 12%. The Hi limit of detection by electrochemical impedance spectroscopy was 1 CFU/mL (measured at - 0.13 V vs BDDPE pseudo-reference), which was achieved in under 10 min, including 5 min sample incubation in the presence of the analyte.

Texture or Linker? Competitive Patterning of Receptor Assembly toward Ultra-Sensitive Impedimetric Detection of Viral Species at Gold-Nanotextured Titanium Surfaces.

In this work, we study the electrodes with a periodic matrix of gold particles pattered by titanium dimples and modified by 3-mercaptopropionic acid (MPA) followed by CD147 receptor grafting for specific impedimetric detection of SARS-CoV-2 viral spike proteins. The synergistic DFT and MM/MD modeling revealed that MPA adsorption geometries on the Au-Ti surface have preferential and stronger binding patterns through the carboxyl bond inducing an enhanced surface coverage with CD147. Control of bonding at the surface is essential for oriented receptor assembling and boosted sensitivity. The complex Au-Ti electrode texture along with optimized MPA concentration is a crucial parameter, enabling to reach the detection limit of ca. 3 ng mL-1. Scanning electrochemical microscopy imaging and quantum molecular modeling were performed to understand the electrochemical performance and specific assembly of MPA displaying a free stereo orientation and not disturbed by direct interactions with closely adjacent receptors. This significantly limits nonspecific interceptor reactions, strongly decreasing the detection of receptor-binding domain proteins by saturation of binding groups. This method has been demonstrated for detecting the SARS virus but can generally be applied to a variety of protein-antigen systems. Moreover, the raster of the pattern can be tuned using various anodizing processes at the titania surfaces.

Discriminating macromolecular interactions based on an impedimetric fingerprint supported by multivariate data analysis for rapid and label-free Escherichia coli recognition in human urine.

This manuscript presents a novel approach to address the challenges of electrode fouling and highly complex electrode nanoarchitecture, which are primary concerns for biosensors operating in real environments. The proposed approach utilizes multiparametric impedance discriminant analysis (MIDA) to obtain a fingerprint of the macromolecular interactions on flat glassy carbon surfaces, achieved through self-organized, drop-cast, receptor-functionalized Au nanocube (AuNC) patterns. Real-time monitoring is combined with singular value decomposition and partial least squares discriminant analysis, which enables selective identification of the analyte from raw impedance data, without the use of electric equivalent circuits. As a proof-of-concept, the authors demonstrate the ability to detect Escherichia coli in real human urine using an aptamer-based biosensor that targets RNA polymerase. This is significant, as uropathogenic E. coli is a difficult-to-treat pathogen that is responsible for the majority of hospital-acquired urinary tract infection cases. The proposed approach offers a limit of detection of 11.3 CFU/mL for the uropathogenic E. coli strain No. 57, an analytical range in all studied concentrations (up to 105 CFU/mL), without the use of antifouling strategies, yet not being specific vs other E.coli strain studied (BL21(DE3)). The MIDA approach allowed to identify negative overpotentials (-0.35 to -0.10 V vs Ag/AgCl) as most suitable for the analysis, offering over 80% sensitivity and accuracy, and the measurement was carried out in just 2 min. Moreover, this approach is scalable and can be applied to other biosensor platforms.

Tailoring diamondised nanocarbon-loaded poly(lactic acid) composites for highly electroactive surfaces: extrusion and characterisation of filaments for improved 3D-printed surfaces.

A new 3D-printable composite has been developed dedicated to electroanalytical applications. Two types of diamondised nanocarbons - detonation nanodiamonds (DNDs) and boron-doped carbon nanowalls (BCNWs) - were added as fillers in poly(lactic acid) (PLA)-based composites to extrude 3D filaments. Carbon black served as a primary filler to reach high composite conductivity at low diamondised nanocarbon concentrations (0.01 to 0.2 S/cm, depending on the type and amount of filler). The aim was to thoroughly describe and understand the interactions between the composite components and how they affect the rheological, mechanical and thermal properties, and electrochemical characteristics of filaments and material extrusion printouts. The electrocatalytic properties of composite-based electrodes, fabricated with a simple 3D pen, were evaluated using multiple electrochemical techniques (cyclic and differential pulse voltammetry and electrochemical impedance spectroscopy). The results showed that the addition of 5 wt% of any of the diamond-rich nanocarbons fillers significantly enhanced the redox process kinetics, leading to lower redox activation overpotentials compared with carbon black-loaded PLA. The detection of dopamine was successfully achieved through fabricated composite electrodes, exhibiting lower limits of detection (0.12 µM for DND and 0.18 µM for BCNW) compared with the reference CB-PLA electrodes (0.48 µM). The thermogravimetric results demonstrated that both DND and BCNW powders can accelerate thermal degradation. The presence of diamondised nanocarbons, regardless of their type, resulted in a decrease in the decomposition temperature of the composite. The study provides insight into the interactions between composite components and their impact on the electrochemical properties of 3D-printed surfaces, suggesting electroanalytic potential.

Engineering boron and nitrogen codoped carbon nanoarchitectures to tailor molecularly imprinted polymers for PFOS determination.

Per- and polyfluoroalkyl substances (PFAS) have gained significant attention as emerging contaminants due to their persistence, abundance, and adverse health effects. Consequently, the urgent need for ubiquitous and effective sensors capable of detecting and quantifying PFAS in complex environmental samples has become a priority. In this study, we present the development of an ultrasensitive molecularly imprinted polymer (MIP) electrochemical sensor tailored by chemically vapour-deposited boron and nitrogen codoped diamond-rich carbon nanoarchitectures for the selective determination of perfluorooctanesulfonic acid (PFOS). This approach allows for a multiscale reduction of MIP heterogeneities, leading to improved selectivity and sensitivity in PFOS detection. Interestingly, the peculiar carbon nanostructures induce a specific distribution of binding sites in the MIPs that exhibit a strong affinity for PFOS. The designed sensors demonstrated a low limit of detection (1.2 µg L-1) and exhibited satisfactory selectivity and stability. To gain further insights into the molecular interactions between diamond-rich carbon surfaces, electropolymerised MIP, and the PFOS analyte, a set of density functional theory (DFT) calculations was performed. Validation of the sensor's performance was carried out by successfully determining PFOS concentrations in real complex samples, such as tap water and treated wastewater, with average recovery rates consistent with UHPLC-MS/MS results. These findings demonstrate the potential of MIP-supported diamond-rich carbon nanoarchitectures for water pollution monitoring, specifically targeting emerging contaminants. The proposed sensor design holds promise for the development of in situ PFOS monitoring devices operating under relevant environmental concentrations and conditions.

Improving the Energy Storage of Supercapattery Devices through Electrolyte Optimization for Mg(NbAgS)x(SO4)y Electrode Materials.

Electrolytes are one of the most influential aspects determining the efficiency of electrochemical supercapacitors. Therefore, in this paper, we investigate the effect of introducing co-solvents of ester into ethylene carbonate (EC). The use of ester co-solvents in ethylene carbonate (EC) as an electrolyte for supercapacitors improves conductivity, electrochemical properties, and stability, allowing greater energy storage capacity and increased device durability. We synthesized extremely thin nanosheets of niobium silver sulfide using a hydrothermal process and mixed them with magnesium sulfate in different wt% ratios to produce Mg(NbAgS)x)(SO4)y. The synergistic effect of MgSO4 and NbS2 increased the storage capacity and energy density of the supercapattery. Multivalent ion storage in Mg(NbAgS)x(SO4)y enables the storage of a number of ions. The Mg(NbAgS)x)(SO4)y was directly deposited on a nickel foam substrate using a simple and innovative electrodeposition approach. The synthesized silver Mg(NbAgS)x)(SO4)y provided a maximum specific capacity of 2087 C/g at 2.0 A/g current density because of its substantial electrochemically active surface area and linked nanosheet channels which aid in ion transportation. The supercapattery was designed with Mg(NbAgS)x)(SO4)y and activated carbon (AC) achieved a high energy density of 79 Wh/kg in addition to its high power density of 420 W/kg. The supercapattery (Mg(NbAgS)x)(SO4)y//AC) was subjected to 15,000 consecutive cycles. The Coulombic efficiency of the device was 81% after 15,000 consecutive cycles while retaining a 78% capacity retention. This study reveals that the use of this novel electrode material (Mg(NbAgS)x(SO4)y) in ester-based electrolytes has great potential in supercapattery applications.

Proteomic analysis of sialoliths from calcified, lipid and mixed groups as a source of potential biomarkers of deposit formation in the salivary glands.

Salivary stones, also known as sialoliths, are formed in a pathological situation in the salivary glands. So far, neither the mechanism of their formation nor the factors predisposing to their formation are known despite several hypotheses. While they do not directly threaten human life, they significantly deteriorate the patient's quality of life. Although this is not a typical research material, attempts are made to apply various analytical tools to characterise sialoliths and search for the biomarkers in their proteomes. In this work, we used mass spectrometry and SWATH-MS qualitative and quantitative analysis to investigate the composition and select proteins that may contribute to solid deposits in the salivary glands. Twenty sialoliths, previously characterized spectroscopically and divided into the following groups: calcified (CAL), lipid (LIP) and mixed (MIX), were used for the study. Proteins unique for each of the groups were found, including: for the CAL group among them, e.g. proteins from the S100 group (S100 A8/A12 and P), mucin 7 (MUC7), keratins (KRT1/2/4/5/13), elastase (ELANE) or stomatin (STOM); proteins for the LIP group-transthyretin (TTR), lactotransferrin (LTF), matrix Gla protein (MPG), submandibular gland androgen-regulated protein 3 (SMR3A); mixed stones had the fewest unique proteins. Bacterial proteins present in sialoliths have also been identified. The analysis of the results indicates the possible role of bacterial infections, disturbances in calcium metabolism and neutrophil extracellular traps (NETs) in the formation of sialoliths.

Multiple Reprocessing of Conductive PLA 3D-Printing Filament: Rheology, Morphology, Thermal and Electrochemical Properties Assessment.

Additive manufacturing technologies are gaining more and more attention, resulting in the development or modification of 3D printing techniques and dedicated materials. On the other hand, economic and ecological aspects force the industry to develop material recycling strategies. In this work, the multiple reprocessing of a commercially available PLA conductive composite with carbon black filler, dedicated to 3D printing, was investigated. The effects of extrusion temperature (190 °C and 200 °C) and reprocessing steps (1-5 steps) on the rheology, morphology, thermal and electrochemical properties of the conductive PLA 3D-printing filament were evaluated. The results showed deterioration of the thermal stability and material strength, as well as the influence of reprocessing on the melting point, which increases after initial melting. The electronic conduction mechanism of the composite depends on the percolation paths and it is also affected by the multiple processing. The reversibility of the [Fe(CN)6]3-/4- redox process diminishes with a higher degradation level of the conductive PLA. Importantly, the material fluidity was too high after the multiple reprocessing, which should be considered and suitably corrected during CB-PLA application as a 3D-printed electrode material.

Closing the loop: Upcycling secondary waste materials into nanoarchitectured carbon composites for the electrochemical degradation of pharmaceuticals.

In this study, we demonstrated the application of electrochemical oxidation as a safer and cleaner technology for minimizing the impact of pharmaceuticals in wastewaters, simultaneously mediated by upcycled secondary waste materials (SWMs)-derived electrodes, to further reduce their environmental impact. The modularity, scalability, ease of operation and reliability make electrochemical oxidation an ideal process for the destruction of emerging persistent pollutants; however, their full-scale application is hindered by energy efficiency and the potential release of toxic by-products. Thus, the answer to these issues can be found in the design of tailored multifunctional electrode material. For the first time, SWMs derived from combustion and industrial processes have been employed with the simultaneous dual function of functional fillers, in a polyacrylonitrile fibrous matrix, and as a catalyst for the growth of carbon nanofeatures over the fiber surface, to increase the surface area and charge transfer. Next, the tailored composites were employed as anodes for the electrochemical oxidation of acetaminophen, both in phosphate buffer and in a real wastewater sample. The results suggest that SWMs can substitute costly engineered fillers in carbon-based electrodes and that the absence of reaction by-products (monitored by UHPLC-ESI-MS/MS), together with the low energy consumption, make the tailored fibrous composite electrodes good candidates for the development of safer and cleaner technologies with reduced environmental impact.

Synthesis of Cyano-Benzylidene Xanthene Synthons Using a Diprotic Brønsted Acid Catalyst, and Their Application as Efficient Inhibitors of Aluminum Corrosion in Alkaline Solutions.

Novel cyano-benzylidene xanthene derivatives were synthesized using one-pot and condensation reactions. A diprotic Brønsted acid (i.e., oxalic acid) was used as an effective catalyst for the promotion of the synthesis process of the new starting xanthene-aldehyde compound. Different xanthene concentrations (ca. 0.1-2.0 mM) were applied as corrosion inhibitors to control the alkaline uniform corrosion of aluminum. Measurements were conducted in 1.0 M NaOH solution using Tafel extrapolation and linear polarization resistance (LPR) methods. The investigated xanthenes acted as mixed-type inhibitors that primarily affect the anodic process. Their inhibition efficiency values were enhanced with inhibitor concentration, and varied according to their chemical structures. At a concentration of 2.0 mM, the best-performing studied xanthene derivative recorded maximum inhibition efficiency values of 98.9% (calculated via the Tafel extrapolation method) and 98.4% (estimated via the LPR method). Scanning electron microscopy (SEM) was used to examine the morphology of the corroded and inhibited aluminum surfaces, revealing strong inhibitory action of each studied compound. High-resolution X-ray photoelectron spectroscopy (XPS) profiles validated the inhibitor compounds' adsorption on the Al surface. Density functional theory (DFT) and Monte Carlo simulations were applied to investigate the distinction of the anticorrosive behavior among the studied xanthenes toward the Al (111) surface. The non-planarity of xanthenes and the presence of the nitrile group were the key players in the adsorption process. A match between the experimental and theoretical findings was evidenced.

Enhanced susceptibility of SARS-CoV-2 spike RBD protein assay targeted by cellular receptors ACE2 and CD147: Multivariate data analysis of multisine impedimetric response.

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) enters the cells through the binding of spike protein to the host cell surface-expressing angiotensin-converting enzyme 2 (ACE2) or by endocytosis mediated by extracellular matrix metalloproteinase inducer (CD147). We present extended statistical studies of the multisine dynamic electrochemical impedance spectroscopy (DEIS) revealing interactions between Spike RBD and cellular receptors ACE2 and CD147, and a reference anti-RBD antibody (IgG2B) based on a functionalised boron-doped diamond (BDD) electrode. The DEIS was supported by a multivariate data analysis of a SARS-CoV-2 Spike RBD assay and cross-correlated with the atomic-level information revealed by molecular dynamics simulations. This approach allowed us to study and detect subtle changes in the electrical properties responsible for the susceptibility of cellular receptors to SARS-CoV-2, revealing their interactions. Changes in electrical homogeneity in the function of the RBD concentration led to the conclusion that the ACE2 receptor delivers the most homogeneous surface, delivered by the high electrostatic potential of the relevant docking regions. For higher RBD concentrations, the differences in electrical homogeneity between electrodes with different receptors vanish. Collectively, this study reveals interdependent virus entry pathways involving separately ACE2, CD147, and spike protein, as assessed using a biosensing platform for the rapid screening of cellular interactions (i.e. testing various mutations of SARS-CoV-2 or screening of therapeutic drugs).

Novel composite of Zn/Ti-layered double hydroxide coupled with MXene for the efficient photocatalytic degradation of pharmaceuticals.

In the present study, a hybrid photocatalyst of Zn/Ti layered double hydroxide (LDH) coupled with MXene - Ti3C2 was synthesized for the first time and applied in photocatalytic degradation of acetaminophen and ibuprofen, two commonly present in the natural environment and prone to accumulate in the aquatic ecosystem pharmaceuticals. The effect of MXene content (0.5 wt%, 2.5 wt%, and 5 wt%) on the photocatalytic activity of LDH/MXene composite was investigated. The composite of LDH/MXene containing 2.5 wt% of MXene revealed the highest photocatalytic activity in the degradation of acetaminophen (100% within 40 min) and ibuprofen (99.7% within 60 min). Furthermore, an improvement in acetaminophen and ibuprofen mineralization was observed for the composite material. Meanwhile, the introduction of interfering ions (Na+, Ca2+, Mg2+, Cl-, SO42-) in the model seawater did not affect the removal efficiency of both pharmaceuticals. The photocatalytic experiment performed in the four subsequent cycles, as well as FTIR, TEM, and XPS analyses after the photodegradation process confirmed the excellent stability and reusability of the prepared composite material. In order to evaluate the effect of various reactive oxidizing species (ROS) on the photocatalytic process, the trapping experiment was applied. It was noticed that •O2- had the main contribution in photocatalytic degradation of acetaminophen, while •OH and h+ mainly affected the degradation of ibuprofen. Finally, based on the results of Mott Schottky analysis, bandgap calculation, and ROS trapping experiment, the possible mechanism for pharmaceuticals degradation was proposed. This research illustrates the feasibility and novelty of the treatment of pharmaceuticals by LDH/MXene composites, implying that MXene plays a significant role in the electron-hole separation and thus high photocatalytic activity.

Influence of CeO2 and TiO2 Particles on Physicochemical Properties of Composite Nickel Coatings Electrodeposited at Ambient Temperature.

The Ni-TiO2 and Ni-CeO2 composite coatings with varying hydrophilic/hydrophobic characteristics were fabricated by the electrodeposition method from a tartrate electrolyte at ambient temperature. To meet the requirements of tight regulation by the European Chemicals Agency classifying H3BO3 as a substance of very high concern, Rochelle salt was utilized as a buffer solution instead. The novelty of this study was to implement a simple one-step galvanostatic electrodeposition from the low-temperature electrolyte based on a greener buffer compared to traditionally used, aiming to obtain new types of soft-matrix Ni, Ni-CeO2, and Ni-TiO2 coatings onto steel or copper substrates. The surface characteristics of electrodeposited nickel composites were evaluated by SEM, EDS, surface contact angle measurements, and XPS. Physiochemical properties of pure Ni, Ni-CeO2, and Ni-TiO2 composites, namely, wear resistance, microhardness, microroughness, and photocatalytic activity, were studied. Potentiodynamic polarization, EIS, and ICP-MS analyses were employed to study the long-term corrosion behavior of coatings in a 0.5 M NaCl solution. Superior photocatalytic degradation of methylene blue, 96.2% after 6 h of illumination, was achieved in the case of Ni-TiO2 composite, while no substantial change in the photocatalytic behavior of the Ni-CeO2 compared to pure Ni was observed. Both composites demonstrated higher hardness and wear resistance than pure Ni. This study investigates the feasibility of utilizing TiO2 as a photocatalytic hydrophilicity promoter in the fabrication of composite coatings for various applications.

Tailoring Diffusional Fields in Zwitterion/Dopamine Copolymer Electropolymerized at Carbon Nanowalls for Sensitive Recognition of Neurotransmitters.

The importance of neurotransmitter sensing in the diagnosis and treatment of many psychological illnesses and neurodegenerative diseases is non-negotiable. For electrochemical sensors to become widespread and accurate, a long journey must be undertaken for each device, from understanding the materials at the molecular level to real applications in biological fluids. We report a modification of diamondized boron-doped carbon nanowalls (BCNWs) with an electropolymerized polydopamine/polyzwitterion (PDA|PZ) coating revealing tunable mechanical and electrochemical properties. Zwitterions are codeposited with PDA and noncovalently incorporated into a structure. This approach causes a specific separation of the diffusion fields generated by each nanowall during electrochemical reactions, thus increasing the contribution of the steady-state currents in the amperometric response. This phenomenon has a profound effect on the sensing properties, leading to a 4-fold enhancement of the sensitivity (3.1 to 14.3 µA cm-2 µM-1) and a 5-fold decrease of the limit of detection (505 to 89 nM) in comparison to the pristine BCNWs. Moreover, as a result of the antifouling capabilities of the incorporated zwitterions, this enhancement is preserved in bovine serum albumin (BSA) with a high protein concentration. The presence of zwitterion facilitates the transport of dopamine in the direction of the electrode by intermolecular interactions such as cation-π and hydrogen bonds. On the other hand, polydopamine units attached to the surface form molecular pockets driven by hydrogen bonds and π-π interactions. As a result, the intermediate state of dopamine-analyte oxidation is stabilized, leading to the enhancement of the sensing properties.

Deciphering the Molecular Mechanism of Substrate-Induced Assembly of Gold Nanocube Arrays toward an Accelerated Electrocatalytic Effect Employing Heterogeneous Diffusion Field Confinement.

The complex electrocatalytic performance of gold nanocubes (AuNCs) is the focus of this work. The faceted shapes of AuNCs and the individual assembly processes at the electrode surfaces define the heterogeneous conditions for the purpose of electrocatalytic processes. Topographic and electron imaging demonstrated slightly rounded AuNC (average of 38 nm) assemblies with sizes of ≤1 µm, where the dominating patterns are (111) and (200) crystallographic planes. The AuNCs significantly impact the electrochemical performance of the investigated electrode [indium-tin oxide (ITO), glassy carbon (GC), and bulk gold] systems driven by surface electrons promoting the catalytic effect. Cyclic voltammetry in combination with scanning electrochemical microscopy allowed us to decipher the molecular mechanism of substrate-induced electrostatic assembly of gold nanocube arrays, revealing that the accelerated electrocatalytic effect should be attributed to the confinement of the heterogeneous diffusion fields with tremendous electrochemically active surface area variations. AuNC drop-casting at ITO, GC, and Au led to various mechanisms of heterogeneous charge transfer; only in the case of GC did the decoration significantly increase the electrochemically active surface area (EASA) and ferrocyanide redox kinetics. For ITO and Au substrates, AuNC drop-casting decreases system dimensionality rather than increasing the EASA, where Au-Au self-diffusion was also observed. Interactions of the gold, ITO, and GC surfaces with themselves and with surfactant CTAB and ferrocyanide molecules were investigated using density functional theory.

Conductive printable electrodes tuned by boron-doped nanodiamond foil additives for nitroexplosive detection.

An efficient additive manufacturing-based composite material fabrication for electrochemical applications is reported. The composite is composed of commercially available graphene-doped polylactide acid (G-PLA) 3D printouts and surface-functionalized with nanocrystalline boron-doped diamond foil (NDF) additives. The NDFs were synthesized on a tantalum substrate and transferred to the 3D-printout surface at 200 °C. No other electrode activation treatment was necessary. Different configurations of low- and heavy-boron doping NDFs were evaluated. The electrode kinetics was analyzed using electrochemical procedures: cyclic voltammetry and electrochemical impedance spectroscopy. The quasi-reversible electrochemical process was reported in each studied case. The studies allowed confirmation of the CV peak-to-peak separation of 63 mV and remarkably high heterogeneous electron transfer rate constant reaching 6.1 × 10-2 cm s-1 for 10 k ppm [B]/[C] thin NDF fitted topside at the G-PLA electrode. Differential pulse voltammetry was used for effective 2,4,6-trinitrotoluene (TNT) detection at the studied electrodes with a 87 ppb limit of detection, and wide linearity range between peak current density and the analyte concentration (0.064 to 64 ppm of TNT). The reported electrode kinetic differences originate primarily from the boron-dopant concentration in the diamond and the various contents of the non-diamond carbon phase.