Electrochemically directed biofunctionalization of a lossy-mode resonance optical fiber sensor.

In this work, we present a direct electrochemical biofunctionalization of an indium-tin-oxide-coated lossy-mode resonance optical fiber sensor. The functionalization using a biotin derivative was performed by cyclic voltammetry in a 10 mM biotin hydrazide solution. All stages of the experiment were simultaneously verified with optical and electrochemical techniques. Performed measurements indicate the presence of a poly-biotin layer on the sensor's surface. Furthermore, dual-domain detection of 0.01 and 0.1 mg/mL of avidin confirms the sensor's viability for label-free detection.

Efficient Method for the Concentration Determination of Fmoc Groups Incorporated in the Core-Shell Materials by Fmoc-Glycine.

In this paper, we described the synthesis procedure of TiO2@SiO2 core-shell modified with 3-(aminopropyl)trimethoxysilane (APTMS). The chemical attachment of Fmoc-glycine (Fmoc-Gly-OH) at the surface of the core-shell structure was performed to determine the amount of active amino groups on the basis of the amount of Fmoc group calculation. We characterized nanostructures using various methods: transmission electron microscope (TEM), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) to confirm the modification effectiveness. The ultraviolet-visible spectroscopy (UV-vis) measurement was adopted for the quantitative determination of amino groups present on the TiO2@SiO2 core-shell surface by determination of Fmoc substitution. The nanomaterials were functionalized by Fmoc-Gly-OH and then the fluorenylmethyloxycarbonyl (Fmoc) group was cleaved using 20% (v/v) solution of piperidine in DMF. This reaction led to the formation of a dibenzofulvene-piperidine adduct enabling the estimation of free Fmoc groups by measurement the maximum absorption at 289 and 301 nm using UV-vis spectroscopy. The calculations of Fmoc loading on core-shell materials was performed using different molar absorption coefficient: 5800 and 6089 dm3 × mol-1 × cm-1 for λ = 289 nm and both 7800 and 8021 dm3 × mol-1 × cm-1 for λ = 301 nm. The obtained results indicate that amount of Fmoc groups present on TiO2@SiO2-(CH2)3-NH2 was calculated at 6 to 9 µmol/g. Furthermore, all measurements were compared with Fmoc-Gly-OH used as the model sample.

Optical Detection of Ketoprofen by Its Electropolymerization on an Indium Tin Oxide-Coated Optical Fiber Probe.

In this work an application of optical fiber sensors for real-time optical monitoring of electrochemical deposition of ketoprofen during its anodic oxidation is discussed. The sensors were fabricated by reactive magnetron sputtering of indium tin oxide (ITO) on a 2.5 cm-long core of polymer-clad silica fibers. ITO tuned in optical properties and thickness allows for achieving a lossy-mode resonance (LMR) phenomenon and it can be simultaneously applied as an electrode in an electrochemical setup. The ITO-LMR electrode allows for optical monitoring of changes occurring at the electrode during electrochemical processing. The studies have shown that the ITO-LMR sensor’s spectral response strongly depends on electrochemical modification of its surface by ketoprofen. The effect can be applied for real-time detection of ketoprofen. The obtained sensitivities reached over 1400 nm/M (nm·mg−1·L) and 16,400 a.u./M (a.u.·mg−1·L) for resonance wavelength and transmission shifts, respectively. The proposed method is a valuable alternative for the analysis of ketoprofen within the concentration range of 0.25⁻250 μg mL−1, and allows for its determination at therapeutic and toxic levels. The proposed novel sensing approach provides a promising strategy for both optical and electrochemical detection of electrochemical modifications of ITO or its surface by various compounds.

Aurintricarboxylic acid structure modifications lead to reduction of inhibitory properties against virulence factor YopH and higher cytotoxicity.

Yersinia sp. bacteria owe their viability and pathogenic virulence to the YopH factor, which is a highly active bacterial protein tyrosine phosphatase. Inhibition of YopH phosphatase results in the lack of Yersinia sp. pathogenicity. We have previously described that aurintricarboxylic acid inhibits the activity of YopH at nanomolar concentrations and represents a unique mechanism of YopH inactivation due to a redox process. This work is a continuation of our previous studies. Here we show that modifications of the structure of aurintricarboxylic acid reduce the ability to inactivate YopH and lead to higher cytotoxicity. In the present paper we examine the inhibitory properties of aurintricarboxylic acid analogues, such as eriochrome cyanine R (ECR) and pararosaniline. Computational docking studies we report here indicate that ATA analogues are not precluded to bind in the YopH active site and in all obtained binding conformations ECR and pararosaniline bind to YopH active site. The free binding energy calculations show that ECR has a stronger binding affinity to YopH than pararosaniline, which was confirmed by experimental YopH enzymatic activity studies. We found that ATA analogues can reversibly reduce the enzymatic activity of YopH, but possess weaker inhibitory properties than ATA. The ATA analogues induced inactivation of YopH is probably due to oxidative mechanism, as pretreatment with catalase prevents from inhibition. We also found that ATA analogues significantly decrease the viability of macrophage cells, especially pararosaniline, while ATA reveals only slight effect on cell viability.

Physicochemical properties of ternary oxovanadium(IV) complexes with oxydiacetate and 1,10-phenanthroline or 2,2'-bipyridine. Cytoprotective activity in hippocampal neuronal HT22 cells.

The aim of this work was to find a relationship between physicochemical properties of the oxovanadium(IV) complexes, namely [VO(ODA)(H2O)2], [VO(ODA)(phen)]·1.5H2O and [VO(ODA)(bipy)]·2H2O (ODA = oxydiacetate) as well as [VO(H2O)5](2+), and their biological activity. A potentiometric titration method has been used to characterize the stability of the complexes in aqueous solutions. Furthermore, the reactivity of the complexes towards superoxide free radicals was assessed by employing the NBT assay as well as a cyclic voltammetry (CV) technique. Additionally, the investigations of the antioxidant properties of the complexes were complemented by studying their reactivity towards organic radicals (the ABTS and DPPH tests). Finally, the biological properties of the complexes were investigated in relation to their cytoprotective activity against the oxidative damage generated exogenously by using hydrogen peroxide in the Hippocampal neuronal cell line HT22 (the MTT and LDH tests). The obtained results showed that all the compounds under study display antioxidant properties but a concentration-depended protective effect against the oxidative damage was found for [VO(ODA)(bipy)]·2H2O only.

Unlocking the electrochemical performance of glassy carbon electrodes by surface engineered, sustainable chitosan membranes.

Chitosan coatings, derived from crustacean shell waste, possess inherent biocompatibility and biodegradability, rendering them suitable for various biomedical and environmental applications, including electrochemical biosensing. Its amine and hydroxyl functional groups offer abundant sites for chemical modifications to boost the charge transfer kinetics and provide excellent adhesion, enabling the construction of robust electrode-coating interfaces for electroanalysis. This study explores the role of electrostatically-driven chemical interactions and crosslinking density originating from different chitosan (Cs) and glutaraldehyde (Ga) concentrations in this aspect. Studying anionic ([Fe(CN)6]3-/4-), neutral (FcDM0/+), and cationic ([Ru(NH3)6]2+/3+) redox probes highlights the influence of Coulombic interactions with chitosan chains containing positively-charged pathways, calculated by DFT analysis. Our study reveals how a proper Ch-to-Ga ratio has a superior influence on the cross-linking efficacy and resultant charge transfer kinetics, which is primarily boosted by up to 20× analyte preconcentration increase, due to electrostatically-driven migration of negatively charged ferrocyanide ions toward positively charged chitosan hydrogel. Notably the surface engineering approach allows for a two-orders of magnitude enhancement in [Fe(CN)6]4- limit of detection, from 0.1 µM for bare GCE down to even 0.2 nM upon an adequate hydrogel modification.

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.

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.

1-(Piperidin-1-yl)-9,10-anthraquinone.

In the title compound, C(19)H(17)NO(2), the piperidine ring adopts a chair conformation. The mean planes of the piperidine ring and the anthracene ring system are inclined at a dihedral angle of 38.7 (1)°. In the crystal, adjacent mol-ecules are linked through C-H⋯π and π-π [centroid-centroid distance = 3.782 (1) Å] inter-actions, forming a layer parallel to the bc plane.

Controlled Silanization of Transparent Conductive Oxides as a Precursor of Molecular Recognition Systems.

The search for new molecular recognition systems has become the goal of modern electrochemistry. Creating a matrix in which properties can be controlled to obtain a desired analytical signal is an essential part of creating such tools. The aim of this work was to modify the surface of electrodes based on transparent conductive oxides with the use of selected alkoxysilanes (3-aminopropyltrimethoxysilane, trimethoxy(propyl)silane, and trimethoxy(octyl)silane). Electrochemical impedance spectroscopy and cyclic voltammetry techniques, as well as contact angle measurements, were used to determine the properties of the obtained layers. Here, we prove that not only was the structure of alkoxysilanes taken into account but also the conditions of the modification process-reaction conditions (time and temperature), double alkoxysilane modification, and mono- and binary component modification. Our results enabled the identification of the parameters that are important to ensure the effectiveness of the modification process. Moreover, we confirmed that the selection of the correct alkoxysilane allows the surface properties of the electrode material to be controlled and, consequently, the charge transfer process at the electrode/solution interface, hence enabling the creation of selective molecular recognition systems.

Electrocatalytic performance of oxygen-activated carbon fibre felt anodes mediating degradation mechanism of acetaminophen in aqueous environments.

Carbon felts are flexible and scalable, have high specific areas, and are highly conductive materials that fit the requirements for both anodes and cathodes in advanced electrocatalytic processes. Advanced oxidative modification processes (thermal, chemical, and plasma-chemical) were applied to carbon felt anodes to enhance their efficiency towards electro-oxidation. The modification of the porous anodes results in increased kinetics of acetaminophen degradation in aqueous environments. The utilised oxidation techniques deliver single-step, straightforward, eco-friendly, and stable physiochemical reformation of carbon felt surfaces. The modifications caused minor changes in both the specific surface area and total pore volume corresponding with the surface morphology. A pristine carbon felt electrode was capable of decomposing up to 70% of the acetaminophen in a 240 min electrolysis process, while the oxygen-plasma treated electrode achieved a removal yield of 99.9% estimated utilising HPLC-UV-Vis. Here, the electro-induced incineration kinetics of acetaminophen resulted in a rate constant of 1.54 h-1, with the second-best result of 0.59 h-1 after oxidation in 30% H2O2. The kinetics of acetaminophen removal was synergistically studied by spectroscopic and electrochemical techniques, revealing various reaction pathways attributed to the formation of intermediate compounds such as p-aminophenol and others. The enhancement of the electrochemical oxidation rates towards acetaminophen was attributed to the appearance of surface carbonyl species. Our results indicate that the best-performing plasma-chemical treated CFE follows a heterogeneous mechanism with only approx. 40% removal due to direct electro-oxidation. The degradation mechanism of acetaminophen at the treated carbon felt anodes was proposed based on the detected intermediate products. Estimation of the cost-effectiveness of removal processes, in terms of energy consumption, was also elaborated. Although the study was focussed on acetaminophen, the achieved results could be adapted to also process emerging, hazardous pollutant groups such as anti-inflammatory pharmaceuticals.

1-Dimethyl-amino-9,10-anthraquinone.

In the crystal structure of the title compound, C(16)H(13)NO(2), adjacent mol-ecules are linked through C-H⋯π and π-π [centroid-centroid distances = 3.844 (2) Å] contacts. The anthracene ring system and dimethyl-amino group are oriented at a dihedral angle of 38.4 (1)°. In the crystal, the mean planes of adjacent anthracene units are inclined at angles of 59.3 (1), 75.7 (1) and 76.0 (1)°.

Functionalized Fe3O4 Nanoparticles as Glassy Carbon Electrode Modifiers for Heavy Metal Ions Detection-A Mini Review.

Over the past few decades, nanoparticles of iron oxide Fe3O4 (magnetite) gained significant attention in both basic studies and many practical applications. Their unique properties such as superparamagnetism, low toxicity, synthesis simplicity, high surface area to volume ratio, simple separation methodology by an external magnetic field, and renewability are the reasons for their successful utilisation in environmental remediation, biomedical, and agricultural applications. Moreover, the magnetite surface modification enables the successful binding of various analytes. In this work, we discuss the usage of core-shell nanoparticles and nanocomposites based on Fe3O4 for the modification of the GC electrode surface. Furthermore, this review focuses on the heavy metal ions electrochemical detection using Fe3O4-based nanoparticles-modified electrodes. Moreover, the most frequently used electrochemical methods, such as differential pulse anodic stripping voltammetry and measurement conditions, including deposition potential, deposition time, and electrolyte selection, are discussed.

Adhesion as a component of retention force of overdenture prostheses-study on selected Au based dental materials used for telescopic crowns using atomic force microscopy and contact angle techniques.

Contemporary prosthetic materials are characterized by highly specific preparation for a given application. This means that at the stage of their creation, not only their function is taken into account, but also the long-term behavior of this material during use. In the case of telescopic crowns, an important factor not yet appearing in the research is the aspect of adhesion force and its dependence on the type of biomaterial, but also the properties of human saliva. The use of artificial saliva, which creates a lubricating layer, reduces the wear on the surface of the telescopic crowns by reducing friction. The impact of artificial saliva on the formation of chemical bonds between prosthetic elements, thus contributing to the so-called retention force has not yet been studied. In this work, two types of measurements of gold telescopic crown materials in the aspect of the adhesion process are presented. Obtained results allowed to fully characterize this phenomenon. We modeled the load force between the microcircuit and the surface under study to suit the conditions between the primary and secondary crowns in the patient's mouth.

Ultrasensitive electrochemical determination of the cancer biomarker protein sPD-L1 based on a BMS-8-modified gold electrode.

This work describes the modification of a gold electrode with the BMS-8 compound that interacts with the Programmed Death-Ligand 1 (PD-L1), an immune checkpoint protein. The results show that we can confirm the presence of the sPD-L1 in the concentration range of 10-18 to 10-8 M using electrochemical impedance spectroscopy (EIS) with a limit of detection (LOD) of 1.87 × 10-14 M for PD-L1 (S/N = 3.3) and at a concentration of 10-14 M via cyclic voltammetry (CV). Additionally, high-resolution X-ray photoelectron spectroscopy (XPS), contact angle, and surface free energy measurements were applied to confirm the functionalization of the electrode. We investigated the selectivity of the electrode for other proteins: Programmed Death-1 (PD-1), cluster of differentiation 160 (CD160), and B- and T-lymphocyte attenuator (BTLA) at concentrations of 10-8 M. Differentiation between PD-L1 and PD-1 was achieved based on the analysis of the capacitance effect frequency dispersion at the surface of the modified Au electrode with BMS-8 after incubation at various concentrations of PD-L1 and PD-1 proteins in the range of 10-18 to 10-8 M. Significant differences were observed in the heterogeneity of PD-L1 and PD-1. The results of the quasi-capacitance studies demonstrate that BMS-8 strongly and specifically interacts with the PD-L1 protein.

The influence of protonation on molecular structure and physico-chemical properties of gossypol Schiff bases.

Protonation of gossypol Schiff bases (S1 and S2), possessing different numbers of basic N-atoms, was studied using potentiometric, spectroscopic, ESI MS and PM5 methods. Titration of S1 and S2 with HClO(4), monitored by the FT-IR and (1)H NMR, indicated that the change from the enamine-enamine into the protonated imine-imine tautomeric form occurs at different Schiff base-H(+) ratio. The FT-IR and PM5 results show that for S1 the first protonation step occurs at Schiff base moiety whereas for S2 it is realised at N-atom of the morpholine. The formation of N(+)-HO hydrogen bond between morpholine moieties within S2 contributes to high pK(a(ACN)) = 22.65.

[Selected cases of acute intoxication with metallic mercury]. / Wybrane przypadki zatruc rtecia metaliczna.

We presented six different cases of poisoning with metallic mercury, which were hospitalized between the year 1999 and 2010 in toxicological center in Gdansk. We discussed also the mechanism, method of diagnosis and therapy of this type of intoxication.

Dansyl-Labelled Ag@SiO2 Core-Shell Nanostructures-Synthesis, Characterization, and Metal-Enhanced Fluorescence.

The present work describes synthesis, characterization, and use of a new dansyl-labelled Ag@SiO2 nanocomposite as an element of a new plasmonic platform to enhance the fluorescence intensity. Keeping in mind that typical surface plasmon resonance (SPR) characteristics of silver nanoparticles coincide well enough with the absorption of dansyl molecules, we used them to build the core of the nanocomposite. Moreover, we utilized 10 nm amino-functionalized silica shell as a separator between silver nanoparticles and the dansyl dye to prevent the dye-to-metal energy transfer. The dansyl group was incorporated into Ag@SiO2 core-shell nanostructures by the reaction of aminopropyltrimethoxysilane with dansyl chloride and we characterized the new dansyl-labelled Ag@SiO2 nanocomposite using transmission electron microscopy (TEM) and Fourier-transform infrared spectroscopy (FTIR). Additionally, water wettability measurements (WWM) were carried out to assess the hydrophobicity and hydrophilicity of the studied surface. We found that the nanocomposite deposited on a semitransparent silver mirror strongly increased the fluorescence intensity of dansyl dye (about 87-fold) compared with the control sample on the glass, proving that the system is a perfect candidate for a sensitive plasmonic platform.

Precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans in Arctic and Antarctic marine sediments: Environmental concern in the face of climate change.

Polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/F) and their precursors - pentachlorophenol (PCP) and triclosan (TCS), constitute a group of persistent, highly toxic multimedia pollutants, being easily transported via atmosphere over long distances, thus particularly threatening to the polar areas. The global fate of PCDD/Fs is temperature-dependent, and their transfer and immobilization at the Poles are described by the grasshopper effect and the cold trap phenomenon. The aim of this interdisciplinary study was to perform a preliminary assessment of the present state of pollution of Arctic and Antarctic marine sediments by PCP and TCS along with determination of PCDD/Fs contamination by immunoassay. Sediments from 20 stations were collected during two polar expeditions (2013-2016). The study area covered Hornsund Fjord and the southwest coast of Wedel-Jarlsberg Land (Arctic) - Skodde Bay, Nottingham Bay, Isbjørnhamna Bay and Admiralty Bay (Antarctica) - Suszczewski Cove, Halfmoon Cove and Herve Cove. The studied contaminants were quantified in 60% of the collected sediments, with almost half exceeding the environmentally safe levels according European regulations and worldwide literature. The determined levels of PCP, TCS and PCDD/F in Arctic and Antarctic sediments were to be comparable to those reported in the southern Baltic Sea located in the intense industrialized mid-latitudes. Maximum concentrations were observed in the vicinity of retreating, marine terminating glaciers. This observation confirms reemission of POPs into the global cycle with respect to the worldwide ocean warming. The results of this study should gain attention of the international and regional environmental agencies as well as the main chlorine production decision makers.

n-Butyl 2-(3-chloro-1,2-dihydro-pyrazin-2-yl-idene)-2-cyano-acetate.

The title compound, C(11)H(12)ClN(3)O(2), is essentially planar except for the n-but-oxy group [r.m.s. deviation from the least-squares plane = 0.0131 (1) Šfor 11 non-H atoms]. An intra-molecular N-H⋯O inter-action results in the formation of an S(6) ring. The n-butoxy chain in the molecule is disordered over two sets of sites of equal occupancy.