Cyclic Voltammetry of Hexachloroiridate(IV): An Alternative to the Electrochemical Study of the Ferricyanide Ion

An instrumental analysis experiment on the cyclic voltammetry of hexachloroiridate(IV) is described in this paper. The hexachloroiridate(IV)/hexachloroiridate(III) redox couple allows the analytical chemistry student to study the behavior of electrochemically reversible electron transfer with no complications. The cyclic voltammetric response of hexachloroiridate(IV)/hexachloroiridate(III) is compared with the ferricyanide/ ferrocyanide redox couple, which has been known to exhibit quasireversible electron transfer as a result of film formation on the electrode surface. Considerations regarding the stability of the hexachloroiridate(IV) ion in 0.1 M KNO₃ are also addressed.     

蒽醌、甲基紫精、N,N-二乙基苯胺与金丝桃蒽酮素光致电子转移的研究

金丝桃蒽酮素(HYP)是有多个羟基的醌类衍生物。在极性溶剂乙腈中,电子给体N,N-二乙基苯胺和电子受体甲基紫精、蒽醌均能有效猝灭其荧光。说明它既具有酚羟基的给电子性能,又有醌类化合物的受电子性能。HYP与平面构型的蒽醌可能形成基态复合物,以不同的方式与其发生光致相互作用。     

Activation of Electron‐Deficient Quinones through Hydrogen‐Bond‐Donor‐Coupled Electron Transfer

Quinones are important organic oxidants in a variety of synthetic and biological contexts, and they are susceptible to activation towards electron transfer through hydrogen bonding. Whereas this effect of hydrogen bond donors (HBDs) has been observed for Lewis basic, weakly oxidizing quinones, comparable activation is not readily achieved when more reactive and synthetically useful electron‐deficient quinones are used. We have successfully employed HBD‐coupled electron transfer as a strategy to activate electron‐deficient quinones. A systematic investigation of HBDs has led to the discovery that certain dicationic HBDs have an exceptionally large effect on the rate and thermodynamics of electron transfer. We further demonstrate that these HBDs can be used as catalysts in a quinone‐mediated model synthetic transformation.     

Photochemistry of supramolecular systems containing C60

Fullerenes have been used successfully in the covalent assembly of supramolecular systems that mimic some of the electron transfer steps of photosynthetic reaction centers. In these constructs C60 is most often used as the primary electron acceptor; it is linked to cyclic tetrapyrroles or other chromophores which act as primary electron donors in photoinduced electron transfer processes. In artificial photosynthetic systems, fullerenes exhibit several differences from the superficially more biomimetic quinone electron acceptors. The lifetime of the initial charge-separated state in fullerene-based molecules is, in general, considerably longer than in comparable systems containing quinones. Moreover, photoinduced electron transfer processes take place in non-polar solvents and at low temperature in frozen glasses in a number of fullerene-based dyads and triads. These features are unusual in photosynthetic model systems that employ electron acceptors such as quinones, and are more reminiscent of electron transfer in natural reaction centers. This behavior can be attributed to a reduced sensitivity of the fullerene radical anion to solvent charge stabilization effects and small internal and solvent reorganization energies for electron transfer in the fullerene systems, relative to quinone-based systems.     

Oxygenated edge plane sites slow the electron transfer of the ferro-/ferricyanide redox couple at graphite electrodes.

The electron transfer kinetics of ferrocyanide, potassium hexachloroiridate(III), hexaammineruthenium(III) chloride, and N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) have been examined at basal plane and edge plane pyrolytic graphite electrodes which have been allowed to oxidise in air for various periods of time. It is demonstrated via voltammetric and X-ray photoelectron spectroscopy (XPS) analysis that oxygenated species formed at edge plane sites/defects decrease the electron transfer kinetics of ferrocyanide but that the rates for potassium hexachloroiridate(III), hexaammineruthenium(III) chloride and TMPD are insensitive to the oxygenated species. The behaviour of the ferro-/ferricyanide couple contrasts with that seen on single-walled carbon nanotubes where oxygenation of the tube ends is known to speed up the electron transfer kinetics (A. Chou, T. Bocking, N. K. Singh, J. J. Gooding, Chem. Commun. 2005, 842); the possible reasons for this contrasting behaviour are discussed.     

Reduction of hexachloroiridate (IV) by benzene-1,2-diol in aqueous perchloric acid

The kinetics of the reaction between benzene-1,2-diol(catechol) and hexachloroiridate (IV) have been measured in aqueous acidic perchlorate solutions by the stopped-flow method. The reaction is second order overall, and first order in each reactant. A reverse reaction also occurs, but it is much slower than the forward process. Observed rate constants are dependent on acidity, but the variation can be attributed to activity rather than mechanistic effects. The reaction appears to proceed predominantly by an outer sphere electron transfer mechanism, yielding o-benzoquinone and hexachloroiridate (III), although monoaquopentachloroiridate (III) is formed also at the higher [catechol]/[IrCl₆^2?]ratios.     

Electrochemical approach to the development of a photoelectrode on the basis of photosynthetic reaction centers

Experimental approaches to the coupling of photoinduced charge separation in reaction centers (RCs) of the photosynthetic bacterium Rhodobacter sphaeroides R-26 with electron transfer to an electrode are discussed. Exogenous quinones are used as an electron transfer mediator. With the use of photopolarography it is shown that water-soluble ubiquinone can serve as a diffusionally mobile mediator of electron transfer. Some methods of quinone immobilization at an electrode have been developed to obtain a non-diffusional mediator of electron transfer. Quasi-reversible electrochemical kinetics were observed for aminonaphthoquinone immobilized as a monolayer at a Pt electrode. The ubiquinone-depleted RCs were subjected to affinity immobilization at these chemically modified electrodes probably due to the insertion of the immobilized quinone into the primary quinone Q_A binding site. The quantum efficiency of photocurrent formation was ca. 5% for the photoelectrode obtained. The electrochemical process of the immobilized quinone is shown to be the stage that limits electron transfer from RCs to the electrode.     

CHLOROPHYLL PHOTOCHEMISTRY IN CONDENSED MEDIA—II. TRIPLET STATE QUENCHING AND ELECTRON TRANSFER TO QUINONE IN LIPOSOMES*

The fate of excitation energy and electron transfer to quinones within Chl-a-containing phosphatidyl choline liposomes has been investigated. The bilayer membrane of the liposome stabilizes the Chl triplet state, as evidenced by a three-fold increase in the lifetime over that observed in ethanol solution. The relative triplet yield follows the relative fluorescence yield, indicative of quenching at the singlet level. Triplet state lifetimes are markedly shortened as the Chl concentration is increased, demonstrating that quenching occurs at the triplet level as well. This process is shown to be due to a collisional de-excitation. In the presence of quinones, the Chl triplet reduces the quinone resulting in production of long-lived electron transfer products. The percent conversion of Chl triplet to cation radical when benzoquinone is employed as acceptor is approximately 60 ± 10%, which is slightly less than in ethanol solution (70 ± 10%). The lifetime of the radical, however, can be as much as 1900 times longer. With respect to potentially useful photochemical energy conversion, the magnitude of this increased lifetime is far more significant than is the decreased radical yield.     

An Unexpected α‐Oxidation of Cyclic Ketones with 1,4‐Benzoquinone by Enol Catalysis

The first direct and asymmetric α‐aryloxylation of cyclic ketones via enol catalysis has been achieved using quinones as the reaction partners. Catalytic amounts of a phosphoric acid promote the exclusive formation of α,α‐disubstituted ketones from the corresponding α‐substituted ketones in good yields and enantioselectivities (up to 96.5:3.5 er). Preliminary mechanistic experiments suggest that this reaction proceeds via a proton‐coupled electron transfer (PCET) followed by radical recombination.     

几种醌类化合物与三乙胺电子转移反应过程的ESR研究

用ESR研究了菲醌(PQ)、四氟对寒醌(TClQ)、2,3-二氯-5,6-二氰苯醌(DDQ)和苯醌(BQ)与三乙胺、(Et₃bN)的电子转移反应过程。实验结果表明,醌上取代基吸电子能力越强,越易与Et₃N反应,但所形成半醌负离子自由基的稳定性,则并未有此规律,而是由自由基终止机理所决定。由实验得到了DDQ与Et₃N的表变曲线。本文讨论了DDQ与Et₃N反应的机理,并得其反应的微分方程,用实验拟合曲线确定速率常数。然后,对该方程求解,与实验曲线比较初步确定了该反应的历程。     

On the pH-dependent quenching of quantum dot photoluminescence by redox active dopamine

We investigated the charge transfer interactions between luminescent quantum dots (QDs) and redox active dopamine. For this, we used pH-insensitive ZnS-overcoated CdSe QDs rendered water-compatible using poly (ethylene glycol)-appended dihydrolipoic acid (DHLA-PEG), where a fraction of the ligands was amine-terminated to allow for controlled coupling of dopamine-isothiocyanate onto the nanocrystal. Using this sample configuration, we probed the effects of changing the density of dopamine and the buffer pH on the fluorescence properties of these conjugates. Using steady-state and time-resolved fluorescence, we measured a pronounced pH-dependent photoluminescence (PL) quenching for all QD-dopamine assemblies. Several parameters affect the PL loss. First, the quenching efficiency strongly depends on the number of dopamines per QD-conjugate. Second, the quenching efficiency is substantially increased in alkaline buffers. Third, this pH-dependent PL loss can be completely eliminated when oxygen-depleted buffers are used, indicating that oxygen plays a crucial role in the redox activity of dopamine. We attribute these findings to charge transfer interactions between QDs and mainly two forms of dopamine: the reduced catechol and oxidized quinone. As the pH of the dispersions is changed from acidic to basic, oxygen-catalyzed transformation progressively reduces the dopamine potential for oxidation and shifts the equilibrium toward increased concentration of quinones. Thus, in a conjugate, a QD can simultaneously interact with quinones (electron acceptors) and catechols (electron donors), producing pH-dependent PL quenching combined with shortening of the exciton lifetime. This also alters the recombination kinetics of the electron and hole of photoexcited QDs. Transient absorption measurements that probed intraband transitions supported those findings where a simultaneous pronounced change in the electron and hole relaxation rates was measured when the pH was changed from acidic to alkaline.     

Cellobiose dehydrogenase modified electrodes: advances by materials science and biochemical engineering

The flavocytochrome cellobiose dehydrogenase (CDH) is a versatile biorecognition element capable of detecting carbohydrates as well as quinones and catecholamines. In addition, it can be used as an anode biocatalyst for enzymatic biofuel cells to power miniaturised sensor–transmitter systems. Various electrode materials and designs have been tested in the past decade to utilize and enhance the direct electron transfer (DET) from the enzyme to the electrode. Additionally, mediated electron transfer (MET) approaches via soluble redox mediators and redox polymers have been pursued. Biosensors for cellobiose, lactose and glucose determination are based on CDH from different fungal producers, which show differences with respect to substrate specificity, pH optima, DET efficiency and surface binding affinity. Biosensors for the detection of quinones and catecholamines can use carbohydrates for analyte regeneration and signal amplification. This review discusses different approaches to enhance the sensitivity and selectivity of CDH-based biosensors, which focus on (1) more efficient DET on chemically modified or nanostructured electrodes, (2) the synthesis of custom-made redox polymers for higher MET currents and (3) the engineering of enzymes and reaction pathways. Combination of these strategies will enable the design of sensitive and selective CDH-based biosensors with reduced electrode size for the detection of analytes in continuous on-site and point-of-care applications.     

Azole-linked coumarin dyes as fluorescence probes of domain-forming polymers.

The binding of 7-aminocoumarins, substituted in the 3-position with heterocyclic benzimidazole or benzothiazole groups by domain-forming polymers in water has been studied. The acrylic polyelectrolyte, poly(methacrylic) acid (PMAA) was used as a solubilizing agent for coumarin dyes 6, 7, and 30 in water. The acid-base properties of these bound coumarin dyes were monitored spectroscopically on titration of aqueous solutions. Alterations in the fluorescence wavelength and intensity, quantum yields, lifetimes, and polarization are consistent with the preferential binding of the dyes in compact hydrophobic domains that form at a pH regime in which the polymer is in its protonated (uncharged) state. In this pH range (<4.0), coumarins 7 and 30 are bound as monocations, whereas coumarin 6 remains in its neutral form. Reduced quantum yields and lifetimes of fluorescence for cationic coumarins can be understood in terms of the imposition of a low-lying electron transfer state, an example of a twisted intramolecular charge transfer (TICT) intermediate. Effects of polymer microenvironment on the rate of TICT state decay (a reverse electron transfer) are observed. Coumarins of the azole type may find use as fluoroprobes of the microenvironments of proteins and other biological macromolecules and as agents for pH sensing.     

FREE ENERGY DEPENDENCE OF THE QUENCHING OF CHLOROPHYLL a FLUORESCENCE BY SUBSTITUTED QUINONES*

The quenching of chlorophyll a (Chl a) fluorescence hy a series of substituted benzoquinones. naphthoquinones and anthraquinones has been examined employing ethanol and acetonitrile as solvents. All quinones are good quenchers of fluorescence. There is an excellent linear relation between the Stern-Volmer quenching constants, K, and the polarographic half wave potentials (E₁₂) of the quinones, with more oxidizing quinones being better quenchers. The quenching data are consistent with the excited state half wave potential of ?1.31 eV predicted theoretically, demonstrating that the kinetically estimated value of the Chl a excited state reduction potential agrees with that expected on spectroscopic grounds. The results of quenching are not in agreement with the conventional Marcus theory of electron-transfer reactions, as there is no evidence of quenching constant. K_q. decrease vsΔG⁰ even for free energy changes nearly twice that expected for the onset of the Marcus inverted region. However, the kinetically estimated K_q values are in good agreement with the ones calculated by using the Rehm and Weller equation for fluorescence quenching by electron transfer. Our experimental results support the electron transfer mechanism of quenching proposed by Seely.     

Design of synthetic molecular units including quinones towards the construction of artificial photosynthesis

Quinones are essential components in many biological systems, notably in photosynthesis. This is largely due to the characteristic proton-coupled redox chemistry of quinones. This review article overviews the use of quinones in studies on artificial photosynthesis, as one-electron electron acceptors, reversible proton/electron carriers, and replacements for sacrificial oxidant and reductants in photosynthetic chemical conversion. Topics included are the early attempts on intramolecular photoinduced electron transfer involving quinones, subsequent reactions after photoinduced electron transfer between pigments and quinones, photochemistry in molecular assemblies containing quinones, and photochemical quinone/hydroquinone interconversion.     

Formation of aromatic radical-cations by oxidation with electronegatively substituted quinones in acid media; kinetics and mechanism

Electronegatively substituted quinones are shown to oxidize electronrich aromatic molecules to the corresponding radical-cations in acid medium via a reversible two step mechanism. The influence of acid strength on the rate of the reaction suggests that a protonated quinone molecule acts as the primary electron acceptor. The rate of formation of the radical cations depends on the one electron oxidation potential of the parent aromatic molecules in a way typical for endothermic outersphere electrontransfer.     

Electrochemical Oxidation of Catechols in the Presence of Triethyl Phosphite

The mechanism of electrochemical oxidation of catechol and some of its derivatives have been studied in the presence of triethyl phosphite as a nucleophile in aqueous solution. Voltammetric studies indicate that the quinones derived from catechol, and its derivatives, participate in Michael addition reaction with triethyl phosphite. The reaction mechanism consists of electron transfer followed by a chemical reaction which is named as an EC mechanism. The homogeneous rate constants (k_obs) were estimated by comparing the experimental cyclic voltammograms with the digitally simulated voltammograms based on EC mechanism. Also the effects of nucleophile concentration and substituted group of catechols on voltammetric behavior and the rate constants of chemical reactions were examined.     

Chlorination increases the persistence of semiquinone free radicals derived from polychlorinated biphenyl hydroquinones and quinones

Polychlorinated biphenyls (PCBs) comprise a group of persistent organic pollutants that differ significantly in their physicochemical properties, their persistence, and their biological activities. They can be metabolized via hydroxylated and dihydroxylated metabolites to PCB quinone intermediates. We have recently demonstrated that both dihydroxy PCBs and PCB quinones can form semiquinone radicals (SQ(*-)) in vitro. These semiquinone radicals are reactive intermediates that have been implicated in the toxicity of lower chlorinated PCB congeners. Here we describe the synthesis of selected PCB metabolites with differing degrees of chlorination on the oxygenated phenyl ring, e.g., 4,4'-dichloro-biphenyl-2,5-diol, 3,6,4'-trichloro-biphenyl-2,5-diol, 3,4,6,-trichloro-biphenyl-2,5-diol, and their corresponding quinones. In addition, two chlorinated o-hydroquinones were prepared, 6-chloro-biphenyl-3,4-diol and 6,4'-dichloro-biphenyl-3,4-diol. These PCB (hydro-)quinones readily react with oxygen or via comproportionation to yield the corresponding semiquinone free radicals, as detected by electron paramagnetic resonance spectroscopy (EPR alias ESR). The greater the number of chlorines on the (hydro-)quinone (oxygenated) ring, the higher the steady-state level of the resulting semiquinone radical at near neutral pH.     

Novel,Stable Catholyte for Aqueous Organic Redox Flow Batteries: Symmetric Cell Study of Hydroquinones with High Accessible Capacity

Owing to their broad range of redox potential, quinones/hydroquinones can be utilized for energy storage in redox flow batteries. In terms of stability, organic catholytes are more challenging than anolytes. The two-electron transfer feature adds value when building all-quinone flow battery systems. However, the dimerization of quinones/hydroquinones usually makes it difficult to achieve a full two-electron transfer in practical redox flow battery applications. In this work, we designed and synthesized four new hydroquinone derivatives bearing morpholinomethylene and/or methyl groups in different positions on the benzene ring to probe molecular stability upon battery cycling. The redox potential of the four molecules were investigated, followed by long-term stability tests using different supporting electrolytes and cell cycling methods in a symmetric flow cell. The derivative with two unoccupied ortho positions was found highly unstable, the cell of which exhibited a capacity decay rate of ~50% per day. Fully substituted hydroquinones turned out to be more stable. In particular, 2,6-dimethyl-3,5-bis(morpholinomethylene)benzene-1,4-diol (asym-O-5) displayed a capacity decay of only 0.45%/day with four-week potentiostatic cycling at 0.1 M in 1 M H₃PO₄. In addition, the three fully substituted hydroquinones displayed good accessible capacity of over 82%, much higher than those of conventional quinone derivatives.     

Highly efficient and chemoselective reductive bis-silylation of quinones by silyltellurides

Silyltellurides serve as new silicon-based chemoselective reducing agents and reduce quinones to the corresponding bis-silylated hydroquinones. The reaction proceeds under ambient thermal conditions without the need of any additional promoters or catalysts and gives the products in excellent yields. Several control experiments suggest that the reaction is initiated by a single electron transfer from silyltellurides to quinones.