Introducing Phosphorus into the Overcrowded Thiele's hydrocarbon Family: Unveiling Contorted Main Group Diradicaloids with Dynamic Redox Behavior.

Thiele's Hydrocarbons (THs) featuring a 9,10-anthrylene core with switchable geometric and electronic configurations offer exciting possibilities in advanced functional materials. Despite significant advances in main group-based diradicaloids in contemporary chemistry, main group THs containing an anthrylene cores have remained elusive, primarily due to the lack of straightforward synthetic strategies and the inherent high reactivity of these species. In this study, we utilize an anthracene-based phosphine synthon to demonstrate, for the first time, a facile and high-yielding synthetic strategy for robust P-functionalized overcrowded ethylenes (OCEs) within the TH family. These OCEs feature a non-symmetric environment, incorporating (thio)xanthyl and phosphaalkene termini. We systematically probe the electronic structures of these derivatives to illustrate the impact of the isolobal phosphaalkene motif on the quinoidal/diradicaloid character. Notably, the compounds exhibit dynamic redox behavior, leading to orthogonally twisted conformational changes upon oxidation, with a kinetically locked redox-couple.

Synthesis, characterization and evaluation of new alternative ruthenium complex for dye sensitized solar cells.

For first time, new innovative ruthenium N3-Dye anchored with selenium (Se) and N3 dye anchored with sulphur atoms were synthesized in a good yield. Dyes are applied and evaluated in performance of dye sensitized solar cell. N3-Se dye showed superior photochemical& electrochemical behavior and high rate electron transfer across anode surface than N3-S dye. The better optical and electrochemical activities would make Se-dye a candidate for applications in solar cells. Half life time of N3-S showed a single exponential decay with an average lifetime of 0.8 ns. For N3-Se dye, decay curve was fitted by sum two exponential functions with 75% and 25% counts have 2.5 ns and 30 ns respectively. Solar cells were fabricated and analyzed to determine their solar-to-electric conversion efficiency under standard AM 1.5 sunlight. Commercial N3 dyes showed current density (Jsc) of 17.813 mA cm-2, open circuit potential (Voc) of 0.678 V, filling factor (FF) of 0.607 and conversion efficiencies (η) of 7.3%. Corresponding values for N3-S dye, Jsc 11.2 mA cm-2, Voc 0.650 V, FF 0.681 and η 5%. Se-N3 dye, showed Jsc = 6.670 mA cm-2, Voc = 0.6004 V, FF = 0.77 and η = 3.09%. Long lifetime of N3-Se caused low practical performance.

Binary metal oxide (NiO/SnO2) composite with electrochemical bifunction: Detection of neuro transmitting drug and catalysis for hydrogen evolution reaction.

The synergetic effect between dual oxides in binary metal oxides (BMO) makes them promising electrode materials for the detection of toxic chemicals, and biological compounds. In addition, the interaction between the cations and anions of diverse metals in BMO tends to create more oxygen vacancies which are beneficial for energy storage devices. However, specifically targeted synthesis of BMO is still arduous. In this work, we prepared a nickel oxide/tin oxide composite (NiO/SnO2) through a simple solvothermal technique. The crystallinity, specific surface area, and morphology were fully characterized. The synthesized BMO is used as a bifunctional electrocatalyst for the electrochemical detection of dopamine (DPA) and for the hydrogen evolution reaction (HER). As expected, the active metals in the NiO/SnO2 composite afforded a higher redox current at a reduced redox potential with a nanomolar level detection limit (4 nm) and excellent selectivity. Moreover, a better recovery rate is achieved in the real-time detection of DPA in human urine and DPA injection solution. Compared to other metal oxides, NiO/SnO2 composite afforded lower overpotential (157 mV @10 mA cm-2), Tafel slope (155 mV dec-1), and long-term durability, with a minimum retention rate. These studies conclude that NiO/SnO2 composite can act as a suitable electrode modifier for electrochemical sensing and the HER.

Tris(boranil) Columnar Liquid Crystalline Fluorophores: pseudo-Triphenylene Boron(III) Complexes with Peripheral N-B-O Linkages.

The borate complexes derived from salicylaldimine ligands, called boranils, possess a wide range of photophysical and electronic characteristics intrinsically. The unique combination of molecular rigidity, rendered by four-coordinate boron bridges, and extended π-conjugation enable them to serve as technically feasible fluorescent materials (dyes). The incorporation of liquid crystallinity in these boron(III) complexes, especially the columnar (Col) mesomorphism, which is overlooked hitherto, would provide a new dimension to these complexes. Herein, we report the first examples of tris(boranil) discotic liquid crystal (LC) dyes that have been readily synthesized by treating tris(N-salicylideneaniline)s, (TSAN)s, with BF3 .Et2 O in the presence of an acid quencher. These C3 -symmetric borate complexes self-assemble into the Col phase, existing over a wide thermal span including room temperature. The 2D periodic order of the Col phases shows dependence on the length of the peripheral tails. The photophysical measurements reveal the fluorescence emission in their two condensed states viz., solid and Col phase, and in solution. Their electrochemical, two-step oxidation process coupled with the aforesaid features upholds their significance in applied research.

Development of a Geochemical Speciation Model for Use in Evaluating Leaching from a Cementitious Radioactive Waste Form.

Cast Stone has been developed to immobilize a fraction of radioactive waste at the Hanford Site; however, constituents of potential concern (COPCs) can be released when in contact with water during disposal. Herein, a representative mineral and parameter set for geochemical speciation modeling was developed for Cast Stone aged in inert and oxic environments, to simulate leaching concentrations of major and trace constituents. The geochemical speciation model was verified using a monolithic diffusion model in conjunction with independent monolithic diffusion test results. Eskolaite (Cr2O3) was confirmed as the dominant mineral retaining Cr in Cast Stone doped with 0.1 or 0.2 wt % Cr. The immobilization of Tc as a primary COPC in Cast Stone was evaluated, and the redox states of porewater within monolithic Cast Stone indicated by Cr are insufficient for the reduction of Tc. However, redox states provided by blast furnace slag (BFS) within the interior of Cast Stone are capable of reducing Tc for immobilization, with the immobilization reaction rate postulated to be controlled by the diffusive migration of soluble Tc in porewater to the surface of reducing BFS particles. Aging in oxic conditions increased the flux of Cr and Tc from monolithic Cast Stone.

Flavin-Helicene Amphiphilic Hybrids: Synthesis, Characterization, and Preparation of Surface-Supported Films.

This work reports on the preparation and structural characterization of flavo[7]helicene 1 (flavin-[7]helicene conjugate), which was subsequently characterized at the molecular level in either an aqueous environment or an organic phase, at the supramolecular level in the form of polymeric layers, and also embedded in a lipidic mesophase environment to study the resulting properties of such a hybrid relative to its parent molecules. The flavin benzo[g]pteridin-2,4-dione (isoalloxazine) was selected for conjugation because of its photoactivity and reversible redox behavior. Compound 1 was prepared from 2-nitroso[6]helicene and 6-methylamino-3-methyluracil, and characterized using common structural and spectroscopic tools: circular dichroism (CD), circularly polarized luminescence (CPL) spectroscopy, cyclic voltammetry (CV), and DFT quantum calculations. In addition, a methodology that allows the loading of 1 enantiomers into an internally nanostructured lipid (1-monoolein) matrix was developed.

Temperature abetted synthesis of novel magnesium stannate nanoparticles assisted for nanomolar level detection of hazardous flavonoid in biological samples.

Fabrication of temperature-influenced nanoparticles over the superficial region of glassy carbon electrode (GCE) stimulates the electrocatalytic activity owing to their morphology, defective sites, and higher active surface area, etc. In this regard, we have fabricated annealed magnesium stannate nanoparticles (Mg2SnO4 NPs) on GCE for nanomolar level detection of hazardous flavoring and pharmaceutical compound Rutin (RT). To analyze the impact of temperature, we have compared annealed Mg2SnO4 NPs with unannealed magnesium stannate hydrate (MgSnO3·3H2O) particles. The physicochemical properties of synthesized materials were characterized with different microscopic and spectroscopic techniques. From these studies, annealed Mg2SnO4 NPs formed purely without any flith and existence of water molecules as compared to unannealed MgSnO3·3H2O. Moreover as fabricated, Mg2SnO4 NPs/GCE outcomes with higher redox behavior compared to other electrodes in presence of RT at optimized working buffer (pH = 7.0). Interestingly, the electrode successfully established a dual wider linear response (0.062-34.8 & 34.8-346.8 µM) with a nanomolar detection limit (1 nM) and higher sensitivity. The practicability analysis of the proposed sensor also affords excellent selectivity, reproducibility, repeatability, reversibility, and storage stability. Furthermore, the real sample analysis was carried out in blood and orange samples fallout with better recovery results.

Synthesis, characterization and cytotoxicity studies of Co(III)-flavonolato complexes.

Hypoxia activated Co(III) complexes as prodrugs may provide with a selective delivery of cytotoxic or antibacterial compounds. Whithin this field sixteen novel Co(III) ternary complexes with the general formula [Co(4N)(flav)](ClO4)2, where 4N = tris(2-aminoethyl)amine (tren) or tris(2-pyridylmethyl)amine (tpa) and flav = deprotonated form of differently substituted flavonols have been synthesized, characterized, and their cytotoxicity assayed under both normoxic and hypoxic conditions. Molecular structures of two free flavonols and seven complexes are also reported. In all the complexes the bioligands exhibited the expected (O,O) coordination mode and the complexes showed a slightly distorted octahedral geometry. Cyclic voltammetric studies revealed that both the substituents of the flavonoles and the type of 4N donor ligands had an impact on the reduction potential of the complex. The ones containing tren demonstrated significantly higher stability than the tpa analogues, making these former compounds promising candidates for the development of hypoxia-activated prodrug complexes. Tpa complexes showed higher activity against both selected human cancer cell lines (A549, A431) than their free ligand flavonols, indicating that the anticancer activity of the bioligand can be enhanced upon complexation. However, slight hypoxia-selectivity was found only for a tren complex (11) with moderate cytotoxicity.

Regulable metal-oxo-bridge configurations as electron transfer bridge to promote Cu(II)/Cu(I) redox behavior for efficient peroxymonosulfate activation.

Constructing metal-oxo-bridge coordination as electron transfer bridge is benefit for the catalysis acceleration towards water pollutants treatment. In this work, regulable Cu-O-C configuration was constructed through tunable ratio of copper aluminum oxide (CuAlxOy) and porous g-C3N4 (p-CN), employed as electron transfer bridge for Cu(II)/Cu(I) redox behavior modulation to realize sufficient peroxymonosulfate (PMS) activation. A series of characterization demonstrated that the composites presents porous structure for p-CN contribution, and the oxygen content plays crucial role in Cu-O-C bonds fabrication. The proper ratio of CuAlxOy and p-CN is conducive to create an oxygen-rich environment, resulting in high dispersed copper atoms connect with oxygen in p-CN matrix. As a result, 2:1 CuAl@p-CN possesses appropriate Cu-O-C configuration, has favorable electron transfer environment for rapid redox behavior of Cu(II)/Cu(I), leading to excellent PMS activation for mirco-polluted veterinary antibiotics elimination. The activated PMS produced active species and followed the priority order of 1O2 > SO4•- > â€¢OH for contaminants degradation, and the specific porous structure reduce the migration distance of active species for efficient catalysis. This study offers a deeper insight into the construction of regulable metal-oxo-bridge configurations for electron transfer towards PMS activation and contributes to an efficient strategy for wastewater remediation.

Structural Stabilization of P2-type Sodium Iron Manganese Oxides by Electrochemically Inactive Mg Substitution: Insights of Redox Behavior and Voltage Decay.

Layered P2-type Na0.8 Mn0.5 Fe0.5 O2 cathode material is a promising candidate for next-generation sodium-ion batteries due to the economical and environmentally benign characteristics of Mn and Fe. The poor cycling stability of the material, however, is still a problem that must be solved. To address the problem, electrochemically inactive Mg2+ was introduced into the structure by substituting some of the Fe ions. It was shown that Mg substitution led to a smoother voltage profile with improved cycling performance and rate capability. These observations were attributed to the suppressed structural changes during electrochemical processes. Detailed redox mechanisms, associated local structural changes, and phase transitions were investigated by X-ray absorption spectroscopy and X-ray diffraction. From the detailed analysis of electrochemical behaviors, it was also identified how the redox reactions and structural disordering occurred in the high- and low-voltage regions and how Mg substitution stabilized the structure.

Core carbo-mer of an Extended Tetrathiafulvalene: Redox-Controlled Reversible Conversion to a carbo-Benzenic Dication.

carbo-Benzene is an aromatic molecule devised by inserting C2 units within each C-C bond of the benzene molecule. By integrating the corresponding carbo-quinoid core as bridging unit in a π-extended tetrathiafulvalene (exTTF), it is shown that a carbo-benzene ring can be reversibly formed by electrochemical reduction or oxidation. The so-called carbo-exTTF molecule was thus experimentally prepared and studied by UV-visible absorption spectroscopy and cyclic voltammetry, as well as by X-ray crystallography and by scanning tunneling microscopy (STM) on a surface of highly oriented pyrolytic graphite (HOPG). The molecule and its oxidized and reduced forms were subjected to a computational study at the density functional theory (DFT) level, supporting carbo-aromaticity as a driving force for the formation of the dication, radical cation, and radical anion. By allowing co-planarity of the dithiolylidene rings and carbo-quinoidal core, carbo-exTTFs present a promising new class of redox-active systems.

Aromatic versus Aliphatic α-Diimine Ligands in Heteroleptic Copper(I) Emitters: Photophysical and Electrochemical Properties.

The electrochemical and photophysical properties of a heteroleptic Cu(I) complex bearing an aliphatic α-diimine ligand, [Cu(dab)(xantphos)]+ (Cu-dab; dab = N,N'-diphenyl-2,3-dimethyl-1,4-diazabutadiene, xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene), were evaluated together with those of complexes [Cu(dmp)(xantphos)]+ (Cu-dmp; dmp = 2,9-dimethyl-1,10-phenanthroline), [Cu(dmbpy)(xantphos)]+ (Cu-dmbpy; dmbpy = 5,5'-dimethyl-2,2'-bipyridine), and [Cu(bq)(xantphos)]+ (Cu-bq; bq = 2,2'-biquinoline), bearing aromatic diimine ligands. Cu-dab exhibited a two-step ligand-centered redox behavior, where the first wave corresponded to an electrochemically reversible one-electron reduction process. Although Cu(I)-aromatic diimine complexes Cu-dmp, Cu-dmbpy, and Cu-bq exhibited obvious luminescence from the metal-to-ligand charge transfer (MLCT) excited state, Cu-dab did not show any luminescence. Computational studies indicated that this non-luminescent property was caused by the large structural relaxation of Cu-dab during photoexcitation.

Electrochemical SERS for in Situ Monitoring the Redox States of PEDOT and Its Potential Application in Oxidant Detection.

In response to recent developments for applying conducting polymers on various biomedical applications, the development of characterization techniques for evaluating the states of conducting polymers in liquids is beneficial to the applications of these materials. In this study, we propose a platform using electrochemical surface-enhanced Raman scattering (EC-SERS) technology, which allows a direct measurement of the redox states of conducing polymers in liquids. A thiophene-based conducting polymer, hydroxymethyl poly(3,4-ethylenedioxythiophene) or poly(EDOT-OH), was used to demonstrate this concept. Poly(EDOT-OH) films were coated on Au nanoparticle-coated ITO glass as SERS-active substrates. Taking the advantage of Raman enhancement, we can in situ and clearly monitor the redox behavior of poly(EDOT-OH) in aqueous solutions. The Raman peak intensity decreases as the poly(EDOT-OH) film is oxidized. Furthermore, we demonstrated our idea to utilize this phenomenon as the sensing mechanism for oxidant detection. The Raman intensity of conducting polymers reduces faster when oxidants exist, and we obtain a quantitative analysis for the detection of oxidants. Moreover, the oxidized poly(EDOT-OH) films can be reused for detection of oxidants simply by applying a reduction potential to activate the poly(EDOT-OH) films. The film stability was also confirmed, and the detection of two other oxidants, namely ammonium persulfate and iron chloride, were also demonstrated. The results show different SERS spectra of poly(EDOT-OH) films oxidized by using different oxidants. Besides, the oxidized films can be easily recovered simply by applying a cathodic potential, which allows repeating usage and makes it possible for continuous monitoring applications. To the best of our knowledge, this is the first time to apply PEDOT's Raman feature for detection purposes.

Chemically synthesized butein and butin: Optical, structure and electrochemical redox functionality at electrode interface.

Progress in the development of phytochemistry has delivered advancement in materials functionality for range of inter/trans-disciplinary application. Here, we investigated the structural functionality of chemically synthesized phytoconstitutent, chalcone (butein) and flavanone (butin). Photoactive and electroactive behavior of butein and butin were comprehensively studied using UV-vis absorbance, photoluminescence and cyclic voltammetric techniques. Surface morphology of the butein and butin powders was characterized from scanning electron microscope at an operating voltage of 10 kV. Significant ultraviolet absorbance property are observed from butein and butin due to the distribution of π → π* and n → π* transitions. Photoluminescence emission spectra of the prepared materials are well resolved at visible region via keto-enol tautomerization and can be influenced by solvent pH. Cyclic voltammetric studies on the prepared materials enabled a direct electron-transfer reaction at gold-screen printed electrode, indicating the feasibility for analytical validation in herbal industries. Existence of multiple electroactive hydroxyl groups makes butein and butin a redox-functional species at electrode interface. Dispersion ability in aqueous and organic solvents makes butein and butin suitable for variety of photochemical applications. This phytochemical material offers new degrees of optical and redox functionality similar to inorganic nanostructures, in addition to inherent bioactivity, that may be advantageous for further biomedical function.

Comparing Isomeric Tridentate Carbazole-Based Click Ligands: Metal Complexes and Redox Chemistry.

Two novel bis(triazolyl)carbazole ligands Hbtc1 (3,6-di(tert-butyl)-1,8-bis[(1-(3,5-di(tert-butyl)phenyl)-1,2,3-triazol-4-yl)]-9H-carbazole) and Hbtc2 (3,6-di(tert-butyl)-1,8-bis[(4-(3,5-di(tert-butyl)phenyl)-1,2,3-triazol-1-yl)]-9H-carbazole), differing in the regiochemistry of triazole attachment, have been synthesized by Cu-catalyzed azide-alkyne cycloaddition, the so-called "click-reactions". Metalation with Ru, Zn, and Ni precursors led to the formation of M(btc)2 complexes (M=Ru, Zn, Ni), with two deprotonated ligands coordinating to the metal center in tridentate fashion, forming almost perfectly octahedral coordination spheres. The redox properties of M(btc)2 complexes have been investigated by cyclic voltammetry, UV/Vis spectroscopy, spectroelectrochemistry, and chemically. The CV of the ruthenium complexes revealed three quasi-reversible one-electron oxidation processes, one assigned as the RuII/III couple and two originating from ligand-based oxidations. The CVs of both Zn and Ni complexes contained only two oxidation waves corresponding to the oxidation of the two ligands. The oxidation potentials of complexes derived from Hbtc1 ligands were found to be 300-400 mV lower than those of the corresponding complexes derived from Hbtc2, reflecting the significant difference in donation through the N(2) or N(3) atom of the triazole moiety.

Electroanalytical tools for antioxidant evaluation of red fruits dry extracts.

Red fruits are rich sources of antioxidant compounds with recognized health benefits. Since they are perishable, dried extracts emerge as more durable products and their quality control must include antioxidant capacity assays. In this study, the redox behavior of commercial dried products obtained from camu-camu, açai, acerola and cranberry red fruits was evaluated by electroanalytical approaches. The antioxidant potential was determined by 2,2-diphenyl-1-picrylhydrazyl free radical assay and the electrochemical index concept. The total phenol content was estimated by using a laccase based biosensor. A significant correlation was found between all methods and literature data. The voltammetric profile (cyclic, differential and square wave) obtained for each type of dried extract showed distinguishable features that were correlated with their main major markers, being also useful for identification purposes. The electrochemical methods were cheaper and more practical for evaluation of antioxidant properties and total phenol content in dried powders obtained from different red fruits.

The role of the equatorial ligands for the redox behavior, mode of cellular accumulation and cytotoxicity of platinum(IV) prodrugs.

The current study aims to elucidate the possible reasons for the significantly different pharmacological behavior of platinum(IV) complexes with cisplatin-, carboplatin- or nedaplatin-like cores and how this difference can be related to their main physicochemical properties. Chlorido-containing complexes are reduced fast (within hours) by ascorbate and are able to unwind plasmid DNA in the presence of ascorbate, while their tri- and tetracarboxylato analogs are generally inert under the same conditions. Comparison of the lipophilicity, cellular accumulation and cytotoxicity of the investigated platinum compounds revealed the necessity to define new structure-property/activity relationships (SPRs and SARs). The higher activity and improved accumulation of platinum(IV) complexes bearing Cl(-) in equatorial position cannot only be attributed to passive diffusion facilitated by their lipophilicity. Therefore, further platinum accumulation experiments under conditions where active/facilitated transport mechanisms are suppressed were performed. Under hypothermic conditions (4°C), accumulation of dichloridoplatinum(IV) complexes is reduced down to 10% of the amount determined at 37°C. These findings suggest the involvement of active and/or facilitated transport in cellular uptake of platinum(IV) complexes with a cisplatin-like core. Studies with ATP depletion mediated by oligomycin and low glucose partially confirmed these observations, but their feasibility was severely limited in the adherent cell culture setting.

Electrochemical behavior and determination of major phenolic antioxidants in selected coffee samples.

The redox behavior of commercial roasted coffee products were evaluated by electroanalysis, whereas high performance liquid chromatography (HPLC) was used for determination of cinnamic acid markers, the total phenolic content (TPC) was achieved by Folin-Ciocalteu assay, and the traditional DPPH (1-diphenyl-2-picrylhydrazyl) method for antioxidant power determination. In turn, an optimized electrochemical index was proposed to estimate the antioxidant power of different samples and it was found a great correlation between all methods. The voltammetric profile of all coffee samples was quite similar, presenting the same number of peaks at the same potential values. Minor differences on current levels were in agreement with the total phenolic and major markers content, as well as, to the antioxidant power. Therefore, the electrochemical methods showed to be practical, low cost and very useful to evaluate the antioxidant properties of coffee samples, which is a relevant quality parameter of this widely consumed beverage.

Flavonoid electrochemistry: a review on the electroanalytical applications

Flavonoids are polyphenolic compounds widespread in vegetal kingdom. They present a C-15 skeleton, which is divided into three units A, B and C. Unit C is an oxygen containing heterocyclic, whose oxidation state and saturation level define major subclasses. Units A and B are aromatic rings, in which four major types of substituents, i. e. hydroxyl, methoxyl, prenyl and glycosides, lead to over 8000 different flavonoids. The great healthy-protecting value of these phytochemical biomarkers has attracted the attention of scientific community. Their main biological actions include anticancer and anti-inflammatory properties, which are strictly linked to antioxidant activities. So that, electroanalysis have been extensively applied on mechanistic studies and also for analytical determinations. This review presents the state of the art regarding the main applications of electroanalysis on the flavonoid research. The approaches on redox behavior characterization leading to a better understanding of structure antioxidant activity relationships are highlighted.