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Krivenko, A. G.; Kotkin, A. S.; Kurmaz, V. A.; Titov, V. E.; Lopushanskaya, V. A.; Koshechko, V. G.

doi:10.1023/a:1005216511206

Cited by 4 publications

(20 citation statements)

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“…-0.58 ± 0.03 V; see also [96,111]. Note that the last value coincides well enough with calculations [65] from a thermodynamic cycle as well as with that calculated by the authors of [1,106] for aqueous solutions (-0.43 V) from the shift of Tafel plots for the irreversible electroreduction of radical relative to the reference intermediate ( ) at W R (E) = 10 4 s -1 (see above) with allowance made for the shift of TP upon going [5] from water to aprotic solvents.…”

Section: Combined Methods: Combination Of the Nonelectrochemical (Or mentioning

confidence: 84%

“…The data on the redox potentials of pairs RX / and RX / [37], RX n -/ RX ( n -1)and RX n + / (for example, / RX 2- [38]), and R -/ R + [39,40] are of individual interest and will not be considered here. More detailed information can be found in monographs and reviews [1, 3, 5-8, 13-15, 17, 21, 30, 41, 42].…”

Section: Brief Description Of Methods Suitable For the Determination mentioning

confidence: 99%

“…A group of methods of laser photoemission (LPE), 2 which were designed in the 1960s to 1990s (see, for example, [1,33,85,86,89]) and the references presented there, getting technically ever more perfect [1,32,39,40,83,, continues to be actively used for both the investigation of irreversible and quasi-reversible electrode reactions involving intermediates in aprotic and protogenic media [1,39,40,84,87,88,[98][99][100][101][102][103][104][105][106][107][108][109][110][111] and the investigation of redox properties of intermediates in aprotic media [1,[94][95][96][97].…”

Section: Combined Methods: Combination Of the Nonelectrochemical (Or mentioning

confidence: 99%

“…In so doing, the data on W(E), obtained from measurements of kinetics in a coulostatic regime, were constructed in the said coordinates simply by substituting Ω for W and E for E 1/2 . Figure 4b also presents a calculated E 1/2 ,Ω curve in the ,E 1/2 coordinates for this radical (curve 3), with the calculation procedure rendered in detail in [96,97,111]. Vertical dashed lines mark the region of scatter of E 0 : according to [96,97,111], the deviation of E 0 from the most positive values of E 1/2 (Ω) into the anodic region may amount to as much as 0.025-0.075 V. The complicated character of the dependence and the considerable range of variations in Ω apart, there is observed satisfactory agreement between calculation and experiment.…”

Section: Combined Methods: Combination Of the Nonelectrochemical (Or mentioning

confidence: 99%

“…(a) Tafel plots for irreversible reduction of (1) trifluoromethyl ( ) radical (data of[96,106,111]) and (2) β-hydroxyethyl radical (data of[100]); supporting electrolyte-aqueous solution of 0.5 M KCl with addition of buffer solutions, with the following values of pH: (1) 4.8-9.6 and (2) 3.6; an Hg electrode; and (b) the E 1/2 ,Ω dependences for a trifluoromethyl radical, obtained (1, 2, 2') experimentally and(3)calculated: (1) data of measurements of kinetics in a coulostatic regime and (2, 2') data of TRV; calculation parameters: W d = 10 3 s -1 , = 10 9 s -1 , τ R = 10 -3 s, and τ X = 10 -2 s; points 2 and 2' correspond to different experimental series; DMSO or DMF + 0.4 M LiClO 4 ; an Hg electrode; vertical dashed lines mark the range of scatter of E 0 (see text for explanations).…”

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confidence: 99%

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Thermodynamic and kinetic characteristics of intermediates of electrode reactions: Determination by direct and combined electrochemical methods

2005

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The potentialities of electrochemical and combined methods for the determination of thermodynamic characteristics and kinetic parameters of intermediates are analyzed. The electrochemical methods include polarography, versions of voltammetry, and chronopotentiometry. The combined methods combine nonelectrochemical (or indirect) generation of intermediates with electrochemical methods of their subsequent investigation: photomodulation voltammetry, method of polarography of pulsed-radiolysis products, method of indirect electrolysis, electrochemiluminescence, and a group of laser photoemission methods. Theoretical foundations and basic advantages and disadvantages of the laser photoemission methods (the measurement of photocurrents in potentiostatic conditions-method of time resolved voltammograms obtained under chopped illumination and the measurement of the kinetics of variations in the potential of an electrode after illuminating it by a pulsed laser-in coulostatic conditions) are described in detail. The potentialities of the laser photoemission methods for the determination of thermodynamic (standard potentials E 0 of redox pairs / R -, standard adsorption free energies) and kinetic (values of rate constants W 0 at an equilibrium potential, bulk lifetime of radicals and products of their reduction R -) characteristics of intermediates are demonstrated by studying a trifluoromethyl radical.

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Section: Combined Methods: Combination Of the Nonelectrochemical (Or mentioning

confidence: 84%

Section: Brief Description Of Methods Suitable For the Determination mentioning

confidence: 99%

Section: Combined Methods: Combination Of the Nonelectrochemical (Or mentioning

confidence: 99%

Section: Combined Methods: Combination Of the Nonelectrochemical (Or mentioning

confidence: 99%

mentioning

confidence: 99%

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Thermodynamic and kinetic characteristics of intermediates of electrode reactions: Determination by direct and combined electrochemical methods

2005

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Nanomaterials‐Induced Redox Imbalance: Challenged and Opportunities for Nanomaterials in Cancer Therapy

Wu,

Zhou,

et al. 2024

Advanced Science

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Cancer cells typically display redox imbalance compared with normal cells due to increased metabolic rate, accumulated mitochondrial dysfunction, elevated cell signaling, and accelerated peroxisomal activities. This redox imbalance may regulate gene expression, alter protein stability, and modulate existing cellular programs, resulting in inefficient treatment modalities. Therapeutic strategies targeting intra‐ or extracellular redox states of cancer cells at varying state of progression may trigger programmed cell death if exceeded a certain threshold, enabling therapeutic selectivity and overcoming cancer resistance to radiotherapy and chemotherapy. Nanotechnology provides new opportunities for modulating redox state in cancer cells due to their excellent designability and high reactivity. Various nanomaterials are widely researched to enhance highly reactive substances (free radicals) production, disrupt the endogenous antioxidant defense systems, or both. Here, the physiological features of redox imbalance in cancer cells are described and the challenges in modulating redox state in cancer cells are illustrated. Then, nanomaterials that regulate redox imbalance are classified and elaborated upon based on their ability to target redox regulations. Finally, the future perspectives in this field are proposed. It is hoped this review provides guidance for the design of nanomaterials‐based approaches involving modulating intra‐ or extracellular redox states for cancer therapy, especially for cancers resistant to radiotherapy or chemotherapy, etc.

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Thermodynamic and kinetic characteristics of intermediates of electrode reactions: A comparative investigation of a number of alkylaryl and alkyl halide radicals by the laser photoemission methods

2005

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A comparative investigation of thermodynamic and kinetic properties of a number of alkylaryl intermediates (benzyl and benzhydryl radicals) and alkyl halide intermediates (chloromethyl, dichloromethyl, and trifluoromethyl radicals) is performed by methods of laser photoemission. Techniques, aimed at the determination of thermodynamic and kinetic properties of intermediates (standard potentials E 0 of redox pairs / R -, standard adsorption free energies -∆ , values of rate constants W 0 at an equilibrium potential, as well as lifetimes (times of death in the bulk) τ R of radicals and τ X of products of their reduction R -) from a comparison of Tafel plots for quasi-reversible reduction of intermediates with calculated ones and standard potentials E 0 -from Tafel plots for irreversible electroreduction of intermediates, are presented. The transition from irreversible to quasi-reversible reduction in aprotic solvents at E ~ E 0 is observed only in the case of benzyl, benzhydryl, and trifluoromethyl radicals, for which this particular collection of thermodynamic and kinetic properties is obtained, and is not observed for the chloromethyl and dichloromethyl radicals. In this case redox characteristics of intermediates ( E 0 , W 0 ) are estimated from absolute values of rates of their electroreduction. Possible reasons for the differences in the probability of a reversible electron transfer are discussed for the systems studied.

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Cited by 4 publications

References 8 publications

Thermodynamic and kinetic characteristics of intermediates of electrode reactions: Determination by direct and combined electrochemical methods

Thermodynamic and kinetic characteristics of intermediates of electrode reactions: Determination by direct and combined electrochemical methods

Nanomaterials‐Induced Redox Imbalance: Challenged and Opportunities for Nanomaterials in Cancer Therapy

Thermodynamic and kinetic characteristics of intermediates of electrode reactions: A comparative investigation of a number of alkylaryl and alkyl halide radicals by the laser photoemission methods

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