Electrodeposited Carbonyl Functional Polymers as Suitable Supports for Preparation of the First-Generation Biosensors.

The aim of this electrochemical study was to ascertain which type of electrochemically deposited carbonyl functionalized polymer represents the most suitable electrode substrate for direct covalent immobilization of biological catalysts (enzymes). For this purpose, a triad of amperometric biosensors differing in the type of conductive polymers (poly-vanillin, poly-trans-cinnamaldehyde, and poly-4-hydroxybenzaldehyde) and in the functioning of selected enzymes (tyrosinase and alkaline phosphatase) has been compared for the biosensing of neurotransmitters (dopamine, epinephrine, norepinephrine, and serotonin) and phenyl phosphates (p-aminophenyl phosphate and hydroquinone diphosphate). The individual layers of the polymers were electrochemically deposited onto commercially available screen-printed carbon electrodes (type C110) using repetitive potential cycling in the linear voltammetric mode. Their characterization was subsequently performed by SEM imaging and attenuated total reflectance FTIR spectroscopy. Molecules of enzymes were covalently bonded to the free carbonyl groups in polymers via the Schiff base formation, in some cases even with the use of special cross-linkers. The as-prepared biosensors have been examined using cyclic voltammetry and amperometric detection. In this way, the role of the carbonyl groups embedded in the polymeric structure was defined with respect to the efficiency of binding enzymes, and consequently, via the final (electro)analytical performance.

Shungite (Mineralized Carbon) as a Promising Electrode Material for Electroanalysis.

In this study, two different types of amorphous carbonaceous Precambrian rock, classified as noble elite shungite and black raw shungite, were tested as possible electrode materials of natural origin. Both types were machined into cylindrical shapes to form the corresponding solid electrodes and their physicochemical and electrochemical properties were compared with the standard glassy carbon electrode (GCE). The raw stones were first subjected to microscopic imaging by using scanning electron microscopy and energy-dispersive X-ray spectroscopy, both of which indicated significant differences in their morphology and in the content of impurities. An electrode prototype manufactured from noble elite shungite (EShE) with a carbon content of about 94% (w/w) has offered a very satisfactory electrochemical performance with a nearly identical heterogeneous electron-transfer rate constant of 7.8 × 10-3 cm s-1 for ferro/ferricyanide redox couple, a slightly narrower potential range (~2.1 V) and a relatively low double-layer capacitance (of ca. 50 µF), resulting in low background currents comparable to those at the GCE. In contrast, the second electrode based on black raw shungite (BShE) with a carbon content of ca. 63% (w/w) exhibited markedly worse electrochemical properties and more than four times higher double-layer capacitance, both of which were probably due to the presence of poorly conductive impurities. The whole study has been completed with three different examples of electroanalytical applications, revealing that the first type, EShE, is a more suitable material for the preparation of electrodes and may represent a cheap alternative to commercially marketed products.

New electroanalytical method for the determination of trans-anethole in spices and sweets.

A completely new method for the determination of trans-anethole (TAN) based on the anodic oxidation of this flavouring substance in pure acetonitrile using differential-pulse voltammetry has been developed. A nonaqueous carbon paste electrode bulk-modified with solid sodium dodecyl sulphate of 40 % (w/w) content was chosen as optimum. To propose TAN electrode reaction mechanism, its electrochemical behaviour was investigated at glassy carbon electrode in nonaqueous media. At optimum working conditions, the current response could be calibrated within a linear range 2-200 µmolL-1 TAN, a coefficient of determination of 0.9971, a sensitivity of 0.1122µALµmol-1, and a detection limit of 0.7 µmolL-1. A satisfactory precision (relative standard deviation of 4 %) has been achieved. The validation performed by analysis of spices and sweets provided comparable results with reference reverse-phase HPLC with spectrophotometric detection, thus confirming the practical use of the developed voltammetric method in food analysis.

Colour-tuneable solid-state fluorescence of crystalline powders formed from push-pull substituted 2,5-diphenyl-stilbenes.

The solid-state fluorescence (SSF) of eight DPA-DPS-EWG derivatives (DPA = diphenylamino, DPS = 2,5-diphenyl-stilbene building block, EWG = electron withdrawing group) was studied. Varying the strength of the EWG enabled the tuning of the LUMO energy within a range broader than 1 eV, while the simultaneous changes of HOMO energy were less than 0.1 eV, according to cyclic voltammetry. The fluorescence maxima in dichloromethane laid between 483 and 752 nm and exhibited monoexponential decay and a photoluminescence quantum yield (PLQY) always higher than 35%. Six derivatives with a SSF PLQY higher than 10% in polycrystalline powder form continuously covered the range from 475 to 733 nm. Three components of SSF multiexponential decay, obtained by time-resolved fluorescence spectroscopy, were ascribed to exciton migration to nonfluorescent traps, and monomer-like and aggregate fluorescence. The character of the emitting aggregates was evaluated by quantum chemical modelling based on time-dependent density functional theory computations, carried out on the dimer arrangements obtained by X-ray diffractometry of the single crystals.

Comparison of mononuclear and dinuclear copper(II) biomimetic complexes: spectroelectrochemical mechanistic study of their catalytic pathways.

Two catecholase-like biomimetic catalysts, namely, two dinuclear copper complexes [Cu2(L1)(OH)(H2O)(EtOH)][ClO4]2 (C1) and [Cu2Ac2O(L1)ClO4] (C2) with the 2,6-bis(4-methyl piperazin-1-yl-methyl)-4-formyl-phenoxy ligand (L1) together with the mononuclear complex Cu(ClO4)2(L2) (C3) containing ligand 1,2-(C5H4N-6-OCH3-2-CHN)2CH2CH2 (L2), were synthesized. Their catalytic pathways were investigated and compared. The evaluation of the catalytic activity of compound C1 (and C2, C3) using the Michaelis-Menten model was represented by values of KM = 272.93 (223.02; 1616) µmol L-1 and Vmax of 0.981 (1.617; 1.689) µmol L-1 s-1. The role of water content in the solvent is also discussed. The dinuclear complexes C1 and C2 were found to be more efficient catalysts than mononuclear complex C3. The mode of catalytic action was characterized via cyclic voltammetry, spectrophotometry, and UV-Vis spectroelectrochemistry. The catalytic mechanism of 3,5-di-tert butyl catechol oxidation in the presence of oxygen was proposed. The reaction circle was proved by the confirmation of the chemical reversibility of complex reduction. The advantage of the in situ spectroelectrochemical measurement enabled to control the reduction of quinone formed by the chemical reaction of catechol with oxygen in solution. At this step, the simultaneous change in the absorption spectrum indicated a change in the copper redox state of the catalyst.

Optimization of gradient reversed phase high performance liquid chromatography analysis of acetaminophen oxidation metabolites using linear and non-linear retention model.

Acetaminophen (paracetamol, APAP) is one of the most widely used drugs worldwide. Unfortunately, its overdose, which is caused by predominant oxidation of APAP, can lead to acute liver injury. In liver, oxidized APAP is conjugated with glutathione, leading to APAP-glutathione conjugate, which is metabolized to APAP-cysteine and APAP-N-acetylcysteine conjugates. Thus, all of those compounds could be used to monitor APAP metabolism in the overdosed patients. To date, only a limited number of rapid and accurate methods have been reported for the assessment of APAP oxidation metabolites using simple instrumentation, and thus this work was aimed at developing a fast and convenient gradient HPLC-UV/MS method. For this purpose, APAP conjugates with glutathione, cysteine, and N-acetylcysteine were synthesized, purified by preparative liquid chromatography, and characterized by NMR and high-resolution mass spectrometry. The gradient elution conditions were optimized using the window diagram approach and the effects of mobile phase composition and additives on separation and detection sensitivity were evaluated using two, i.e., linear and non-linear isocratic retention models. Quantitative parameters of the developed method were evaluated and the effectiveness, sensitivity, and specificity of the method were demonstrated on the analysis of human kidney HK-2 cell lysates, confirming the suitability of the method for routine use in studies on APAP toxicity.

Electrochemical Study and Determination of All-trans-Retinol at Carbon Paste Electrode Modified by a Surfactant.

The oxidation mechanism of all-trans-retinol (vitamin A1) and its several esters in non-aqueous, aqueous organic mixture, and pure aqueous media was investigated by cyclic voltammetry. The oxidation occurred in several irreversible steps. The calculated highest density of electrons in retinoid molecules which are delocalized over carbon atoms of the five conjugated double bonds (C5-C14) was found in the part of the molecule involved in oxidation processes. The most sensitive oxidation peak (at +0.8 V vs. Ag/AgCl) was used for development of new direct voltammetric method based on differential pulse voltammetry for the determination of retinol at carbon paste electrode modified with surfactant sodium dodecyl sulfate (CPE/SDS). The results show that 30% (by mass) of modifier SDS exhibited optimal sensitivity and shape of voltammograms. Compared to commonly used glassy carbon electrode (GCE), the CPE/SDS showed significant progress in the retinol electroanalysis. The linear ranges for retinol determination were 1.5·10-6-1.8·10-4 M for CPE/SDS and 4.4·10-6-7.0·10-4 M for GCE with the detection limits of 1.3·10-6 and 4.6·10-7 M, respectively.

Electrochemical and Reactivity Studies of N→Sn Coordinated Distannynes.

Studies are focused on the redox potentials of N→Sn coordinated distannnynes {L1-3 Sn}2 (L1 =1, L2 =2 and L3 =3, in which L1 is [C6 H3 -2,6-(Me2 NCH2 )2 ]- , L2 is [C6 H2 -2,4-tBu2 -6-(Et2 NCH2 )]- and L3 is [C6 H2 -2,4-tBu2 -6-(DippN=CH)]- ; Dipp=2,6-diisopropylphenyl), containing the tin atom in oxidation state +I. Distannynes 1-3 were used as ligands for transition metals, and complexes [{L1 Sn}2 ⋅Fe(CO)4 ] (4) and [{L2 Sn}2 ⋅Fe(CO)4 ] (5) were prepared. The set of N→Sn coordinated distannynes 1-5 was studied by cyclic voltammetry measurements and the oxidation potentials of tin atoms in 1-5 were determined. The redox potentials are influenced by either ligands L1-3 or SnI →Fe coordination. Oxidation reactions of 1-3 were also studied. The reaction of 2 with (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) provided mixed organotin oxide {(L2 SnO)(L2 )Sn(µ-O)}2 (6) as a consequence of the instability of the expected {L2 Sn⋅TEMPO} complex. To support this proposed mechanism, the N→Ge coordinated digermyne {L2 Ge}2 (7) was prepared. The reaction of 7 with TEMPO provided the expected complex {L2 Ge⋅TEMPO} (8).

Preparation and characterization of novel double-decker rare-earth phthalocyanines substituted with 5-bromo-2-thienyl groups.

BACKGROUND: A series of rare-earth bisphthalocyanines of praseodymium, samarium and gadolinium bearing 5-bromo-2-thienyl substituents were prepared for the first time. RESULTS: Three bis[octakis(5-bromo-2-thienyl)] rare-earth metal(III) bisphthalocyanine complexes (Pr, Sm, Gd) were synthesized for the first time. The new compounds were characterized by UV-vis, NIR, FT-IR, mass spectroscopy and thermogravimetry as well as elementary analysis and electrochemistry. Production of singlet oxygen was also estimated using 9,10-dimethylanthracene method. CONCLUSIONS: The bromine substituent causes significant changes in molecule paramagnetism, singlet oxygen production, HOMO position and spectral characteristics. The compounds in solutions exist in two forms (neutral and/or reduced) depending on the solvent and rare-earth metal. Moreover, the compounds exhibit much increased stability under acid conditions compared with non-brominated derivatives. Graphical abstract Prepared compounds for the study of their chemical and other properties.

Structure-property relationships and third-order nonlinearities in diketopyrrolopyrrole based D-π-A-π-D molecules.

Nine new quadrupolar chromophores based on diketopyrrolopyrrole were designed and prepared by cross-coupling reactions. The property tuning has been achieved by structural variation of the peripheral substituents (donor) and enlargement of the π-system. Fundamental properties of target molecules were studied by differential scanning calorimetry, electrochemistry, and absorption and emission spectra. Nonlinear optical properties were studied by measuring the third harmonic generation. The experimental data were completed by quantum-chemical calculations and structure-property relationships were elucidated.

Homolytic, Heterolytic, Mesolytic - As You Like It: Steering the Cleavage of a HC(sp3 )-C(sp3 )H Bond in Bis(1H-2,1-benzazaborole) Derivatives.

A set of (3,3')-bis(1-Ph-2-R-1H-2,1-benzazaborole) compounds, in which R=tBu (Bab-tBu)2 , R=Dipp (Bab-Dipp)2 or R=tBu and Dipp (Bab-Dipp)(Bab-tBu), was synthesized and fully characterized using 1 H, 11 B, 13 C, and 15 N NMR spectroscopy as well as single-crystal X-ray diffraction analysis. The central HC(sp3 )-C(sp3 )H bond with restricted rotation at the junction of both 1H-2,1-benzazaborole rings displayed an intriguing reactivity. It was demonstrated that this bond is easily mesolytically cleaved using alkali metals to form the respective aromatic 1Ph-2R-1H-2,1-benzazaborolyl anions M+ (THF)n (Bab-tBu)- (M=Li, Na, K) and K+ (THF)n (Bab-Dipp)- . Furthermore, the central HC(sp3 )-C(sp3 )H bond of bis(1H-2,1-benzazaborole)s is also homolytically cleaved either by heating or photochemical means, giving corresponding 1Ph-2R-1H-2,1-benzazaborolyl radicals (Bab-tBu). and (Bab-Dipp). , which rapidly self-terminate. Nevertheless, their formation was unambiguously established by NMR analysis of the reaction mixtures containing products of the self-termination of the radicals after heating or irradiation. (Bab-Dipp). radical was also characterized using EPR spectroscopy. Importantly, it turned out that the essentially non-polarized HC(sp3 )-C(sp3 )H bond in (Bab-tBu)2 is also cleaved heterolytically with 2 equiv of MeLi, giving the mixture of Li+ (SOL)n (Bab-tBu)- (SOL=THF or Et2 O) and lithium methyl-substituted borate complex Li+ (SOL)n (Bab-tBu-Me)- in a diastereoselective fashion.

Organization and intramolecular charge-transfer enhancement in tripodal tris[(pyridine-4-yl)phenyl]amine push-pull molecules by intercalation into layered materials bearing acidic functionalities.

Two new intercalates of tris[4-(pyridin-4-yl)phenyl]amine (TPPA) with zirconium hydrogen phosphate and zirconium 4-sulfophenylphosphonate having formulae Zr(HPO4)2·0.21(C33H24N4)·2.5H2O and Zr(HO3SC6H4PO3)(1.3)(C6H5PO3)(0.7)·0.35(C33H24N4)·2.5H2O were prepared and characterized by thermogravimetry, IR spectroscopy, and powder X-ray diffraction. The TPPA molecule has been selected as a model tripodal push-pull system with three peripheral basic centers that may undergo protonation. Their protonation/quaternization afforded HTPPA/MeTPPA molecules with enhanced intramolecular charge-transfer (ICT), which has been documented by electrochemical measurements, UV-Vis spectra and calculated properties such as the HOMO/LUMO levels and the first and second hyperpolarizabilities. Intercalation of TPPA into layered zirconium hydrogen phosphate and zirconium 4-sulfophenylphosphonate led to its significant organization and protonation as shown by the IR spectra. From the powder X-ray data we can deduce that the TPPA molecules are placed in the interlayer space of both hosts by anchoring two peripheral nitrogen atoms to one host layer and the opposite pyridine-4-yl terminus to the other neighboring host layer. In zirconium 4-sulfophenylphosphonate, the TPPA molecules are oriented perpendicularly, while in zirconium phosphate these molecules are slanted with respect to the layers of the host. On dehydration by heating, the interlayer distance of the intercalate decreases, which indicates a further slanting of the TPPA molecules. It follows from the UV-Vis spectra that TPPA is present in both intercalates in an equilibrium of protonated and non-protonated forms. The described materials represent the first case when a tripodal push-pull system was incorporated into a system with restricted geometry with the aim to influence its optical properties.

Structural characterization of electrochemically and in vitro biologically generated oxidation products of atorvastatin using UHPLC/MS/MS.

Ultrahigh-performance liquid chromatography coupled with high-mass-accuracy tandem mass spectrometry (UHPLC-MS-MS) has been used for elucidation of the structures of oxidation products of atorvastatin (AT), one of the most popular commercially available drugs. The purpose of the study was identification of AT metabolites in rat hepatocytes and comparison with electrochemically generated oxidation products. AT was incubated with rat hepatocytes for 24 h. Electrochemical oxidation of AT was performed by use of a three-electrode off-line system with a glassy carbon working electrode. Three supporting electrolytes (0.1 mol L(-1) H2SO4, 0.1 mol L(-1) HCl, and 0.1 mol L(-1) NaCl) were tested, and dependence on pH was also investigated. AT undergoes oxidation by a single irreversible process at approximately +1.0 V vs. Ag/AgCl electrode. The results obtained revealed a simple and relatively fast way of determining the type of oxidation and its position, on the basis of characteristic neutral losses (NLs) and fragment ions. Unfortunately, different products were obtained by electrochemical oxidation and biotransformation of AT. High-mass-accuracy measurement combined with different UHPLC-MS-MS scans, for example reconstructed ion-current chromatograms, constant neutral loss chromatograms, or exact mass filtering, enable rapid identification of drug-related compounds. ß-Oxidation, aromatic hydroxylation of the phenylaminocarbonyl group, sulfation, AT lactone and glycol formation were observed in rat biotransformation samples. In contrast, a variety of oxidation reactions on the conjugated skeleton of isopropyl substituent of AT were identified as products of electrolysis.

Ferrocene-donor and 4,5-dicyanoimidazole-acceptor moieties in charge-transfer chromophores with π linkers tailored for second-order nonlinear optics.

A series of new nonlinear optical chromophores (1-15) that were comprised of ferrocene-donor and 4,5-dicyanoimidazole-acceptor moieties and various π linkers of different length were synthesized. Support for the presence of significant DA interactions in these NLO-phores was obtained from the evaluation of the quinoid character of the 1,4-phenylene moieties and their electronic absorption spectra, which featured intense high-energy (HE) bands that were accompanied by less-intense low-energy (LE) bands. The redox behavior of these compounds was investigated by cyclic voltammetry (CV) and by rotating-disc voltammetry (RDV); their electrochemical gaps decreased steadily from 2.64 to 2.09 V. In addition to the experimentally obtained data, DFT calculations of their absorption spectra, HOMO/LUMO levels, and second-order polarizabilities (ß) (-2ω,ω,ω) were performed. A structure-property relationship study that was performed by systematically altering the π linker revealed that the intramolecular charge-transfer and nonlinear optical properties of these inorganic-organic hybrid D-π-A systems (1-15) were primarily affected by: 1) The presence of olefinic/acetylenic subunits; 2) the length of the π linker; and 3) the spatial arrangement (planarity) of the π linker.

Imidazole as a donor/acceptor unit in charge-transfer chromophores with extended π-linkers.

Eleven new, stable, push-pull systems that feature 4,5-bis[4-(N,N-dimethylamino)phenyl]imidazole and 4,5-dicyanoimidazole as the donor and acceptor moieties and the systematically extended and varied π-linker were prepared and investigated. Evaluation of the measured UV/Vis spectra, electrochemical data (cyclic voltammetry (CV), rotating-disc voltammetry (RDV), and polarography) and calculated ß and γ polarizabilities showed efficient charge transfer (CT) in biimidazole-type chromophores. Push-pull system 27, which features a planar thiophene-derived π-linker, was revealed to be the most efficient chromophore within the studied series. This chromophore possessed the most bathochromically shifted CT band, the lowest electrochemical gap, and highest ß and γ polarizabilities. The CT transition was most significantly affected by structural features such as π-linker length, planarity, conjugating arrangement, and the presence of olefinic/acetylenic or 1,4-phenylene/thiophene subunits in the π-linker.

New approaches to the characterization of carbon paste electrodes using the ohmic resistance effect and qualitative carbon paste indexes.

In this article, some new approaches to characterize the carbon paste mixtures and the respective carbon paste electrodes (CPEs) are presented, discussed, and critically evaluated. Particular attention has been paid to the changes of the ohmic resistance, relative to the dependence on composition of the CPE, the materials used, the time, and the position of storage. Four types of carbon pastes were examined, and for the interpretation of experimental data, a new simple model of "close-packing of spheres" has been applied. This model resembles the percolation theory for solid matter. In our case, however, it is possible to explain not only the "bent" or "broken" shape of the dependence of the electrode resistance upon the binder:carbon ratio and the corresponding electrochemical current response, but also differences caused by various material used and three various effects observed during the electrode aging. Furthermore, the report presents the significance of practical utilization of the recently introduced carbon paste index (denoted as chi(CPE)), which is a qualitative hitherto unused factor based on the evaluation of cyclic voltammograms for standard redox systems (e.g., [Fe(CN)(6)](3-/4-)) and specifying the electrochemical properties of a CPE. Some problems connected with homogeneity and stability of carbon pastes, their handling, storage, or eventual aging effects are also discussed.