Designing Atomic Interface in Sb2 S3 /CdS Heterojunction for Efficient Solar Water Splitting.

In the emerging Sb2 S3 -based solar energy conversion devices, a CdS buffer layer prepared by chemical bath deposition is commonly used to improve the separation of photogenerated electron-hole pairs. However, the cation diffusion at the Sb2 S3 /CdS interface induces detrimental defects but is often overlooked. Designing a stable interface in the Sb2 S3 /CdS heterojunction is essential to achieve high solar energy conversion efficiency. As a proof of concept, this study reports that the modification of the Sb2 S3 /CdS heterojunction with an ultrathin Al2 O3 interlayer effectively suppresses the interfacial defects by preventing the diffusion of Cd2+ cations into the Sb2 S3 layer. As a result, a water-splitting photocathode based on Ag:Sb2 S3 /Al2 O3 /CdS heterojunction achieves a significantly improved half-cell solar-to-hydrogen efficiency of 2.78% in a neutral electrolyte, as compared to 1.66% for the control Ag:Sb2 S3 /CdS device. This work demonstrates the importance of designing atomic interfaces and may provide a guideline for the fabrication of high-performance stibnite-type semiconductor-based solar energy conversion devices.

Characterization of Germanium Nanoparticles from Arylgermanium Trihydrides.

Germanium is a promising basis for nanomaterials due to its low toxicity and valuable optical and electronic properties. However, germanium nanomaterials have seen little research compared to other group 14 elements due to unpredictable chemical behavior and high costs. Here, we report the dehydrocoupling of o-tolylgermanium trihydride to amorphous nanoparticles. The reaction is facilitated through reflux at 162 °C and can be accelerated with an amine base catalyst. Through cleavage of both H2 and toluene, new Ge-Ge bonds form. This results in nanoparticles consisting of crosslinked germanium with o-tolyl termination. The particles are 2-6 nm in size and have masses above approximately 3500 Da. The organic substituents are promising for further functionalization. Combined with strong absorption up to 600 nm and moderate solubility and air stability, there are numerous possibilities for future applications.

Recent advances in the modification of electrodes for trace metal analysis: a review.

This review paper summarizes the research published in the last five years on using different compounds and/or materials as modifiers for electrodes employed in trace heavy metal analysis. The main groups of modifiers are identified, and their single or combined application on the surface of the electrodes is discussed. Nanomaterials, film-forming substances, and polymers are among the most used compounds employed mainly in the modification of glassy carbon, screen-printed, and carbon paste electrodes. Composites composed of several compounds and/or materials have also found growing interest in the development of modified electrodes. Environmentally friendly substances and natural products (mainly biopolymers and plant extracts) have continued to be included in the modification of electrodes for trace heavy metal analysis. The main analytical performance parameters of the modified electrodes as well as possible interferences affecting the determination of the target analytes, are discussed. Finally, a critical evaluation of the main findings from these studies and an outlook discussing possible improvements in this area of research are presented.

The development of an electropolymerized, molecularly imprinted polymer (MIP) sensor for insulin determination using single-drop analysis.

An electrochemical sensor for the detection of insulin in a single drop (50 µL) was developed based on the concept of molecularly imprinted polymers (MIP). The synthetic MIP receptors were assembled on a screen-printed carbon electrode (SPCE) by the electropolymerization of pyrrole (Py) in the presence of insulin (the protein template) using cyclic voltammetry. After electropolymerization, insulin was removed from the formed polypyrrole (Ppy) matrix to create imprinting cavities for the subsequent analysis of the insulin analyte in test samples. The surface characterization, before and after each electrosynthesis step of the MIP sensors, was performed using atomic force microscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The performance of the developed MIP-SPCE sensor was evaluated using a single drop of solution containing K3Fe(CN)6 and the square-wave voltammetry technique. The MIP-SPCE showed a linear concentration range of 20.0-70.0 pM (R2 = 0.9991), a limit of detection of 1.9 pM, and a limit of quantification of 6.2 pM. The rapid response time to the protein target and the portability of the developed sensor, which is considered a disposable MIP-based system, make this MIP-SPCE sensor a promising candidate for point-of-care applications. In addition, the MIP-SPCE sensor was successfully used to detect insulin in a pharmaceutical sample. The sensor was deemed to be accurate (the average recovery was 108.46%) and precise (the relative standard deviation was 7.23%).

Ex situ bioremediation of diesel fuel-contaminated soil in two different climates.

The petroleum industry is often faced with accidental spills and discharges that pollute valuable natural resources such as soil. The purpose of this study was to assess bioremediation potential of an on-site landfarming unit (LU), a highly economical solution that complies with the zero-waste policy, for bioremediation of the contaminated soil after an actual diesel fuel leakage in a fuel depot. The first aim was to evaluate the effects of different climates on hydrocarbon bioremediation. For this reason, a part of the contaminated soil was moved from the initial location with a sub-Mediterranean climate to an LU at another location with a temperate continental climate. Our results demonstrated that remediation in sub-Mediterranean climate is less effective than the remediation in a temperate continental climate. The second aim of this study was to evaluate the effect of different plant species on the microbial population during bioremediation. For that purpose, 365-day monitoring of phospholipid fatty acids (PLFA) was performed. Our results support the hypothesis that plant-assisted bioremediation can diminish toxic effects of diesel-polluted soil and that the changes in plant species during bioremediation cause changes in the microbial population.

The main objective of this study was to implement a landfarming bioremediation technique after an actual diesel fuel pollution in the sub-Mediterranean climate and diminish toxic effects of pollutants in soil. Since soil bioremediation is performed by soil microorganisms, their communities are primarily affected by the growing vegetation and climatic conditions. For future bioremediation strategies or ex situ approaches, it is crucial to assess the influence of a specific climate on the degradation rate of hydrocarbons in soil and select the most efficient plant species for this purpose.

Bioactive coatings with anti-osteoclast therapeutic agents for bone implants: Enhanced compliance and prolonged implant life.

The use of therapeutic agents that inhibit bone resorption is crucial to prolong implant life, delay revision surgery, and reduce the burden on the healthcare system. These therapeutic agents include bisphosphonates, various nucleic acids, statins, proteins, and protein complexes. Their use in systemic treatment has several drawbacks, such as side effects and insufficient efficacy in terms of concentration, which can be eliminated by local treatment. This review focuses on the incorporation of osteoclast inhibitors (antiresorptive agents) into bioactive coatings for bone implants. The ability of bioactive coatings as systems for local delivery of antiresorptive agents to achieve optimal loading of the bioactive coating and its release is described in detail. Various parameters such as the suitable concentrations, release times, and the effects of the antiresorptive agents on nearby cells or bone tissue are discussed. However, further research is needed to support the optimization of the implant, as this will enable subsequent personalized design of the coating in terms of the design and selection of the coating material, the choice of an antiresorptive agent and its amount in the coating. In addition, therapeutic agents that have not yet been incorporated into bioactive coatings but appear promising are also mentioned. From this work, it can be concluded that therapeutic agents contribute to the biocompatibility of the bioactive coating by enhancing its beneficial properties.

The Effect of Preconditioning Strategies on the Adsorption of Model Proteins onto Screen-Printed Carbon Electrodes.

The preconditioning and modification of the supporting electrode surface is an essential step in every biosensor architecture. In particular, when using screen-printed carbon electrodes (SPEs) as inexpensive and convenient disposable sensor substrates, their somewhat lower electrochemical (surface) reproducibility might represent a complex hurdle. Herein, we investigated the effect of selected preconditioning strategies, such as cyclic voltammetric pretreatment, in H2SO4 and H2O2 and plasma pretreatment with a positive and negative glow discharge, which all improved the electrochemical stability of the unmodified SPEs. Furthermore, we studied the influence of preconditioning strategies on the adsorption kinetics of the two most commonly used building blocks for biosensor preparation, i.e., bovine serum albumin (BSA) and protein A. We observed an advantageous effect of all the examined preconditioning strategies for the modification of SPEs with protein A, being the most effective the negative glow discharge. On the other hand, BSA exhibited a more complex adsorption behavior, with the negative glow discharge as the only generally beneficial preconditioning strategy providing the highest electrochemical stability. Protein A revealed a more substantial impact on the electrochemical signal attenuation than BSA considering their same concentrations in the modification solutions. For both BSA and protein A, we showed that the concentrations of 5 and 10 µg mL-1 already suffice for an electrochemically satisfactorily stable electrode surface after 60 min of incubation time, except for BSA at the positive-plasma-treated electrode.

Addressing the Needs of the Rapidly Aging Society through the Development of Multifunctional Bioactive Coatings for Orthopedic Applications.

The unprecedented aging of the world's population will boost the need for orthopedic implants and expose their current limitations to a greater extent due to the medical complexity of elderly patients and longer indwelling times of the implanted materials. Biocompatible metals with multifunctional bioactive coatings promise to provide the means for the controlled and tailorable release of different medications for patient-specific treatment while prolonging the material's lifespan and thus improving the surgical outcome. The objective of this work is to provide a review of several groups of biocompatible materials that might be utilized as constituents for the development of multifunctional bioactive coatings on metal materials with a focus on antimicrobial, pain-relieving, and anticoagulant properties. Moreover, the review presents a summary of medications used in clinical settings, the disadvantages of the commercially available products, and insight into the latest development strategies. For a more successful translation of such research into clinical practice, extensive knowledge of the chemical interactions between the components and a detailed understanding of the properties and mechanisms of biological matter are required. Moreover, the cost-efficiency of the surface treatment should be considered in the development process.

Natural Hemp-Ginger Extract and Its Biological and Therapeutic Efficacy.

The prevention and treatment of skin diseases remains a major challenge in medicine. The search for natural active ingredients that can be used to prevent the development of the disease and complement treatment is on the rise. Natural extracts of ginger and hemp offer a wide range of bioactive compounds with potential health benefits. This study evaluates the effectiveness of hemp and ginger extract as a supportive treatment for skin diseases. It reports a synergistic effect of hemp and ginger extract. The contents of cannabinoids and components of ginger are determined, with the highest being CBD (587.17 ± 8.32 µg/g) and 6-gingerol (60.07 ± 0.40 µg/g). The minimum inhibitory concentration for Staphylococcus aureus (156.5 µg/mL), Escherichia coli (625.2 µg/mL) and Candida albicans (78.3 µg/mL) was also analyzed. Analysis of WM-266-4 cells revealed the greatest decrease in metabolic activity in cells exposed to the extract at a concentration of 1.00 µg/mL. Regarding the expression of genes associated with cellular processes, melanoma aggressiveness, resistance and cell survival, a significant difference was found in the expression of ABCB5, CAV1 and S100A9 compared with the control (cells not exposed to the extract).

A Review of Recent Advances in the Inhibition of Sweet Corrosion.

This review paper discusses the research work published in the last decade on the use of organic compounds and natural products as corrosion inhibitors for steel in CO2 and CO2 /H2 S coexisting environments. The carbon and mild steel samples tested are mostly immersed in CO2 -saturated NaCl/brine solutions or simulated oilfield waters. The influence of temperature, immersion time, CO2 partial pressure, pre-corrosion, flow rate/rotation speed, and the synergistic effect of other compounds on the corrosion inhibition effectiveness of organic compounds and natural products is presented. Primarily, weight loss and electrochemical techniques were used to evaluate the corrosion inhibition effectiveness of these compounds.

Time-of-flight secondary ion mass spectrometry and X-ray photoelectron spectroscopy study of 2-phenylimidazole on brass.

RATIONALE: This work presents the first surface analysis investigation of 2-phenylimidazole (PhI) as a corrosion inhibitor for brass in a 3 wt.% NaCl solution using time-of-flight secondary ion mass spectrometry (TOF-SIMS) and X-ray photoelectron spectroscopy (XPS). METHODS: A time-of-flight secondary ion mass spectrometer was used to describe the elemental and molecular specific signals on the brass surface. Gas cluster/monoatomic ion beam depth profiling and two-dimensional (2D) imaging showed the surface properties of the PhI surface layer. In addition, detailed XPS was used to describe the element-specific signals on the brass surface. Furthermore, principal component analysis demonstrated the distribution of the different phases of the surface. Finally, the applicability of PhI in hot corrosion studies was suggested by a thermal stability experiment. RESULTS: TOF-SIMS measurements showed an intense positive-ion TOF-SIMS signal for protonated PhI, i.e. C9 H9 N2 + at m/z 145.07. Moreover, there was an intense negative-ion TOF-SIMS signal for deprotonated PhI, i.e. C9 H7 N2 ¯ at m/z 143.06. Gas cluster ion beam sputtering associated with the analysis of the XPS-excited Cu L3 M4,5 M4,5 revealed a connection between Cu(I) and PhI to form organometallic complexes. CONCLUSIONS: The formation of the organometallic complexes with Cu and Zn metal atoms/ions was identified using TOF-SIMS in positive and negative polarity mode: PhI-Cu, PhI-Cu2 , PhI-Zn, and PhI-Zn2 complexes were present on the brass surface. The TOF-SIMS measurements were supported by XPS measurements.

Progressive use of multispectral imaging flow cytometry in various research areas.

Multi-spectral imaging flow cytometry (MIFC) has become one of the most powerful technologies for investigating general analytics, molecular and cell biology, biotechnology, medicine, and related fields. It combines the capabilities of the morphometric and photometric analysis of single cells and micrometer-sized particles in flux with regard to thousands of events. It has become the tool of choice for a wide range of research and clinical applications. By combining the features of flow cytometry and fluorescence microscopy, it offers researchers the ability to couple the spatial resolution of multicolour images of cells and organelles with the simultaneous analysis of a large number of events in a single system. This provides the opportunity to visually confirm findings and collect novel data that would otherwise be more difficult to obtain. This has led many researchers to design innovative assays to gain new insight into important research questions. To date, it has been successfully used to study cell morphology, surface and nuclear protein co-localization, protein-protein interactions, cell signaling, cell cycle, cell death, and cytotoxicity, intracellular calcium, drug uptake, pathogen internalization, and other applications. Herein we describe some of the recent advances in the field of multiparametric imaging flow cytometry methods in various research areas.

Surface analysis and interface properties of 2-aminobenzimidazole corrosion inhibitor for brass in chloride solution.

This work presents a corrosion study of 2-aminobenzimidazole (ABI) as a corrosion inhibitor for brass in chloride solution. Electrochemical, field emission scanning electron microscopy, atomic force microscopy, and contact angle measurements showed that ABI mitigates brass corrosion after short-, medium-, and long-term immersion periods. Next, a detailed surface analysis of the ABI adsorbed on the brass surface was performed using attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS) techniques. XPS imaging was performed in association with principal component analysis to determine the different phases on the surface. In order to describe the in-depth composition of the ABI surface, an angle-resolved XPS analysis was performed. This analysis was further supported by gas cluster ion beam sputtering to gradually remove the ABI surface layer, and XPS analysis was performed after each sputtering cycle. Finally, TOF-SIMS analyses showed the formation of Cu/Cu2-ABI and Zn-ABI compounds, the 2D distribution of ABI-related compounds, and their thermal stability on the brass surface. Graphical abstract.

The Use of Factorial Design and Simplex Optimization to Improve Analytical Performance of In Situ Film Electrodes.

This work presents a systematic approach to determining the significance of the individual factors affecting the analytical performance of in-situ film electrode (FE) for the determination of Zn(II), Cd(II), and Pb(II). Analytical parameters were considered simultaneously, where the lowest limit of quantification, the widest linear concentration range, and the highest sensitivity, accuracy, and precision of the method evidenced a better analytical method. Significance was evaluated by means of a fractional factorial (experimental) design using five factors, i.e., the mass concentrations of Bi(III), Sn(II), and Sb(III), to design the in situ FE, the accumulation potential, and the accumulation time. Next, a simplex optimization procedure was employed to determine the optimum conditions for these factors. Such optimization of the in situ FE showed significant improvement in analytical performance compared to the in situ FEs in the initial experiments and compared to pure in situ FEs (bismuth-film, tin-film, and antimony-film electrodes). Moreover, using the optimized in situ FE electrode, a possible interference effect was checked for different species and the applicability of the electrode was demonstrated for a real tap water sample.

An Advanced Statistical Approach Using Weighted Linear Regression in Electroanalytical Method Development for Epinephrine, Uric Acid and Ascorbic Acid Determination.

In this study, the use of weighted linear regression in the development of electrochemical methods for the determination of epinephrine (EP), ascorbic acid (AA), and uric acid (UA) is presented. The measurements were performed using a glassy carbon electrode and square-wave voltammetry (SWV). All electroanalytical methods were validated by determination of the limit of detection, limit of quantification, linear concentration range, accuracy, and precision. The normal distribution of all data sets was checked using the quantile-quantile plot and Kolmogorov-Smirnov statistical tests. The heteroscedasticity of the data was tested using Hartley's test, Bartlett's test, Cochran's C test, and the analysis of residuals. The heteroscedastic behavior was observed with all analytes, justifying the use of weighted linear regression. Six different weighting factors were tested, and the best weighted model was determined using relative percentage error. Such statistical approach improved the regression models by giving greater weight on the values with the smallest error and vice versa. Consequently, accuracy of the analytical results (especially in the lower concentration range) was improved. All methods were successfully used for the determination of these analytes in real samples: EP in an epinephrine auto-injector, AA in a dietary supplement, and UA in human urine. The accuracy and precision of real sample analysis using best weighted model gave satisfactory results with recoveries between 95.21-113.23% and relative standard deviations between 0.85-7.98%. The SWV measurement takes about 40 s, which makes the presented methods for the determination of EP, AA, and UA a promising alternative to chromatographic techniques in terms of speed, analysis, and equipment costs, as the analysis is performed without organic solvents.

Time-of-flight secondary ion mass spectrometry analysis of chitosan-treated viscose fibres.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was employed to analyse cellulose viscose fibres treated with different chitosan-based solutions. The analysis reports several new features in the TOF-SIMS spectra for systems with various forms of chitosan-treated surfaces. The characteristic positive ion TOF-SIMS signals for chitosan are reported at m/z 147.90, 207.07, and 221.09, and characteristic signals for trimethyl chitosan are present at m/z 58.03 and 102.09. Furthermore, new fragments were suggested to characterise acetylated chitosan molecules. The relative surface concentrations of different species were obtained based on the specific signal ratios (originating from a specific fragment and cellulose). SIMS imaging was then performed in order to investigate the surface distribution of chitosan, trimethyl chitosan, and Na-containing nanoparticles. In order to perform TOF-SIMS imaging, the above-mentioned characteristic signals were employed and m/z 22.99 was used for Na nanoparticles.

Indicator Layers Based on Ethylene-Vinyl Acetate Copolymer (EVA) and Dicyanovinyl Azobenzene Dyes for Fast and Selective Evaluation of Vaporous Biogenic Amines.

The article presents naked-eye methods for fast, sensitive, and selective detection of isopentylamine and cadaverine vapours based on 4-N,N-dioctylamino-4'-dicyanovinylazobenzene (CR-528) and 4-N,N-dioctylamino-2'-nitro-4'-dicyanovinylazobenzene (CR-555) dyes immobilized in ethylene-vinyl acetate copolymer (EVA). The reaction of CR-528/EVA and CR-555/EVA indicator layers with isopentylamine vapours caused a vivid colour change from pink/purple to yellow/orange-yellow. Additionally, CR-555/EVA showed colour changes upon exposure to cadaverine. The colour changes were analysed by ultraviolet⁻visible (UV/VIS) molecular absorption spectroscopy for amine quantification, and the method was partially validated for the detection limit, sensitivity, and linear concentration range. The lowest detection limits were reached with CR-555/EVA indicator layers (0.41 ppm for isopentylamine and 1.80 ppm for cadaverine). The indicator layers based on EVA and dicyanovinyl azobenzene dyes complement the existing library of colorimetric probes for the detection of biogenic amines and show great potential for food quality control.

Reusability of SPE and Sb-modified SPE Sensors for Trace Pb(II) Determination.

In this work, unmodified screen-printed electrode (bare SPE) and Sb-film modified SPE (SbFSPE) sensors were employed for the analysis of trace amounts of Pb(II) in non-deaerated water solutions. The modified electrode was performed in situ in 0.5 mg/L Sb(III) and 0.01 M HCl. The methodology was validated for an accumulation potential of ⁻1.1 V vs. Ag/AgCl and an accumulation time of 60 s. A comparative analysis of bare SPE and SbFSPE showed that the detection and quantification limits decrease for the bare SPE. The method with the bare SPE showed a linear response in the 69.8⁻368.4 µg/L concentration range, whereas linearity for the SbFSPE was in the 24.0⁻319.1 µg/L concentration range. This work also reports the reason why the multiple standard addition method instead of a linear calibration curve for Pb(II) analysis should be employed. Furthermore, the analytical method employing SbFSPE was found to be more accurate and precise compared to the use of bare SPE when sensors were employed for the first time, however this performance changed significantly when these sensors were reused in the same manner. Furthermore, electrochemical impedance spectroscopy was used for the first time to analyse the electrochemical response of sensors after being used for multiple successive analyses. Surface characterisation before and after multiple successive uses of bare SPE and SbFSPE sensors, with atomic force microscopy and field emission scanning electron microscopy, showed sensor degradation. The interference effect of Cd(II), Zn(II), As(III), Fe(II), Na(I), K(I), Ca(II), Mg(II), NO3⁻, Bi(III), Cu(II), Sn(II), and Hg(II) on the Pb(II) stripping signal was also studied. Finally, the application of SbFSPE was tested on a real water sample (from a local river), which showed high precision (RSD = 8.1%, n = 5) and accurate results.

The impact of urban rain on the changes of bare and artificially patinated bronze during 9-year exposure.

Atmospheric pollutants in the air form acid rain which interacts with bronze surfaces exposed in urban outdoor environment. In this study, different types of patinas on bronze were investigated during and after 9 years of exposure to urban environment in moderately polluted continental city. Natural bronze patina and artificial brown sulphide, green chloride, and green-blue nitrate patinas were investigated. Visual assessment was carried out at defined periods. After 9 years of exposure, an electrochemical study was performed to investigate the electrochemical activity of the patinas in artificial urban rain. Additionally, the patinas were characterised using a variety of techniques, including metallographic examination, scanning electron microscopy/energy dispersive X-ray spectroscopy, Raman spectroscopy, X-ray diffraction analysis, X-ray-photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry to analyse the surface morphology, chemical composition, and stratigraphic features of the patinas. Evolution of the patinas was shown to be a result of both, the composition of the acid rain and the hydrophobicity of the patinated surfaces.