Electron-donating Capacity Research Articles

D-A structured high efficiency solid luminogens with tunable emissions: Molecular design and photophysical properties

Fabrication of efficient solid luminogens with tunable emission is both fundamentally significant and technically important. Herein, based on our previous strategy for the construction of efficient and multifunctional solid luminogens through the combination of diverse aggregation-induced emission (AIE) units with other functional moieties, a group of luminophores with electron donor-acceptor (D-A) structure and typical intramolecular charge transfer (ICT) characteristics, namely CZ-DCDPP, DPA-DCDPP and DBPA-DCDPP were synthesized and investigated. The presence of twisting and AIE-active 2,3-dicyano-5,6-diphenylpyrazine (DCDPP) moiety endows them highly emissive in the solid states, whereas the introduction of arylamines with varied electron-donating capacity and different conjugation render them with tunable solid emissions from green to red. While CZ-DCDPP and DPA-DCDPP solids exhibit distinct mechanochromism, both DPA-DCDPP and DBPA-DCDPP solids can generate efficient red emission. Owing to their high efficiency, remarkable thermal and morphological stabilities and moreover red emission, they are promising for diverse optoelectronic and biological applications.

Discrepant responses of the electron transfer capacity of soil humic substances to irrigations with wastewaters from different sources

An increasing area of agricultural land is irrigated with wastewater worldwide due to the scarcity of fresh water resources. Whether wastewater irrigations can affect the electron transfer capacity (ETC) of natural organic matter in soils is unclear. In this study, we assess the responses of the electron-accepting capacity (EAC) and electron-donating capacity (EDC) of soil humic substances (HS) to irrigations with wastewaters from different sources. We show that the EAC of soil HS increases and the EDC of soil HS decreases after irrigation with domestic wastewater. Conversely, the EAC of soil HS decreases and the EDC of soil HS increases after irrigation with industrial wastewater. The EAC and EDC of soil HS exert no changes after irrigation with pharmaceutical wastewater. Irrigations with wastewaters from different sources can cause the distinct directions of changes in the activities of lignin peroxidase and laccase by altering the content of labile organic carbon, heavy metals or antibiotics in soils, thereby changing the chemical structures and finally the ETC of HS along different directions. These results can provide insights into the role of HS in environmentally relevant processes in agricultural soils under the context of wastewater irrigations.

Effect of Compositional and Structural Evolution of Size-fractionated Dissolved Organic Matter on Electron Transfer Capacity During Composting

Abstract Ultrafiltration separation and spectrum analysis were employed to investigate the composition and structure evolution of size-fractionated dissolved organic matter (DOM) during chicken manure composting. Electrochemical method was applied to determine electron transfer capacity (ETC). The results showed that protein-like components, which were the main components at the initial stage of composting, were mainly observed in the DOM with molecule weight (MW) 1 kDa. Though humic-like components with different molecular weight changed differently during composting, their content at the end of composting was higher than that at the initial of composting. Electron donating capacity (EDC) was persistently reduced during composting, whereas electron accepting capacity (EAC) of the DOM with the MW 1 kDa was persistently increasing during the composting process, though the EAC of the fraction showed no system change. There was on irregular for the ETC of the DOM with the MW of 1–3 kDa and 3–5 kDa. The EAC value of the size-fractionation DOM was controlled by the content of the aromatic carbon which was derived from lignin degradation, while the EDC value of these DOM did not showed obvious relation with the spectrum parameter.

Increased Electron-Accepting and Decreased Electron-Donating Capacities of Soil Humic Substances in Response to Increasing Temperature.

The electron transfer capacities (ETCs) of soil humic substances (HSs) are linked to the type and abundance of redox-active functional moieties in their structure. Natural temperature can affect the chemical structure of natural organic matter by regulating their oxidative transformation and degradation in soil. However, it is unclear if there is a direct correlation between ETC of soil HS and mean annual temperature. In this study, we assess the response of the electron-accepting and -donating capacities (EAC and EDC) of soil HSs to temperature by analyzing HSs extracted from soil set along glacial-interglacial cycles through loess-palaeosol sequences and along natural temperature gradients through latitude and altitude transects. We show that the EAC and EDC of soil HSs increase and decrease, respectively, with increasing temperature. Increased temperature facilitates the prevalence of oxidative degradation and transformation of HS in soils, thus potentially promoting the preferentially oxidative degradation of phenol moieties of HS or the oxidative transformation of electron-donating phenol moieties to electron-accepting quinone moieties in the HS structure. Consequently, the EAC and EDC of HSs in soil increase and decrease, respectively. The results of this study could help to understand biogeochemical processes, wherein the redox functionality of soil organic matter is involved in the context of increasing temperature.

Predicting reactivity of model DOM compounds towards chlorine with mediated electrochemical oxidation

Chlorine demand of a water sample depends on the characteristics of dissolved organic matter (DOM). It is an important parameter for water utilities used to assess oxidant and/or disinfectant consumption of source waters during treatment and distribution. In this study, model compounds namely resorcinol, tannic acid, vanillin, cysteine, tyrosine, and tryptophan were used to represent the reactive moieties of complex DOM mixtures. The reactivity of these compounds was evaluated in terms of Cl2 demand and electron donating capacity (EDC). The EDC was determined by mediated electrochemical oxidation (MEO) which involves the use of 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) as an electron shuttle. The Cl2 demand of readily oxidizable compounds (resorcinol, tannic acid, vanillin, and cysteine) was found to correlate well with EDC (R2 = 0.98). The EDC values (mol e−/mol C) of the model compounds are as follows: 1.18 (cysteine) > 0.77 (resorcinol) > 0.59 (vanillin) > 0.52 (tannic acid) > 0.36 (tryptophan) > 0.19 (tyrosine). To determine the effect of pre-oxidation on EDC, ozone was added (0.1 mol O3/mol C) into each model compound solution. Ozonation caused a general decrease in EDC (10–40%), chlorine demand (10–30%), and UV absorbance (10–40%), except for tyrosine which showed both increased UV275 and EDC. Before and after ozonation, 24 h disinfection byproduct (DBP) formation potential tests (Cl2 residual = 1.5 mg/L) were conducted to evaluate the use of EDC for DBP formation prediction. The results indicate that there was no significant correlation between the EDC of the model compounds and the formation potentials of adsorbable organic chlorine, trichloromethane, and trichloroacetic acid. This suggests that while EDC correlates with Cl2 demand, chlorine consumption may not directly translate to DBP formation because oxidation reactions may dominate over substitution reactions. Overall, this study provides useful insights on the reactions of ABTS+ and HOCl with model DOM compounds, and highlights the potential application of MEO for rapid determination of Cl2 demand of a water sample.

Quantifying the electron donating capacities of sulfide and dissolved organic matter in sediment pore waters of wetlands.

Electron donating capacity (EDC) values were determined for a set of pore water samples collected from the sediments of four separate wetlands in the Cottonwood Lakes Study Area in Jamestown, ND by mediated electrochemical analysis, reaction with substituted nitro(so)benzenes, and calculation based on measured organic carbon and sulfide concentrations. The samples were taken from four hydrologically connected and increasingly sulfidic wetlands within the study site. Parallel trends in EDC values related to hydrologic conditions and to in situ reduced sulfur content were observed by all three methodologies. In particular, it was found that sulfide and dissolved organic matter (DOM) are the primary and secondary reductants, respectively, in these systems. The efficacy of these reductants in transforming organic contaminants, however, is largely driven by native pore water reduced sulfur content. Manipulation of the systems demonstrate that while DOM is capable of reducing highly oxidized contaminants or reactive intermediates, this likely only occurs once the reducing capacity of the sulfide is exhausted. Sulfide therefore was the dominant electron donor in the pore water samples.

The electron donating capacity of biochar is dramatically underestimated.

Biochars have gathered considerable interest for agronomic and engineering applications. In addition to their high sorption ability, biochars have been shown to accept or donate considerable amounts of electrons to/from their environment via abiotic or microbial processes. Here, we measured the electron accepting (EAC) and electron donating (EDC) capacities of wood-based biochars pyrolyzed at three different highest treatment temperatures (HTTs: 400, 500, 600 °C) via hydrodynamic electrochemical techniques using a rotating disc electrode. EACs and EDCs varied with HTT in accordance with a previous report with a maximal EAC at 500 °C (0.4 mmol(e−).gchar−1) and a large decrease of EDC with HTT. However, while we monitored similar EAC values than in the preceding study, we show that the EDCs have been underestimated by at least 1 order of magnitude, up to 7 mmol(e−).gchar−1 for a HTT of 400 °C. We attribute this existing underestimation to unnoticed slow kinetics of electron transfer from biochars to the dissolved redox mediators used in the monitoring. The EDC of other soil organic constituents such as humic substances may also have been underestimated. These results imply that the redox properties of biochars may have a much bigger impact on soil biogeochemical processes than previously conjectured.

Structure-reactivity relationships between the fluorescent chromophores and antioxidant activity of grain and sweet sorghum seeds.

Polyphenolic structures are the putative cause of a variety of seed functions including bird/insect resistance and antioxidant activity. Structure‐reactivity relationships are necessary to understand the influence of polyphenolic chromophore structures on the tannin content and free radical quenching ability determined by the traditional calorimetric methods. This study investigated the relationships between the structural attributes of fluorescent chromophore and the following seed characterization methods: procyanidin (by acid‐butanol assay) and flavonoid (by vanillin assay) contents, radical quenching (by DPPH assay), electron‐donating capacity (by FeIII reduction), and λ max (by UV/visible spectrophotometry). Distinctively different response was observed for different seed categories: U.S. grain sorghum hybrids, African grain sorghum, and sweet sorghum. The U.S. grain sorghum varieties (low‐tannin to maximize the livestock digestion) responded only to the DPPH assay. For sweet sorghum and African grain sorghum, linear correlation was observed between (1) the antioxidant activity (2) the amounts of procyanidins and flavonoids, and (2) the aromaticity of fingerprint fluorescent structures.

Ligand assisted copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines

Three types of ligands have been developed for copper-catalyzed Ullmann cross coupling reaction of bromaminic acid with amines in aqueous solution. Ligands with large steric hindrance and strong electron-donating capacity were beneficial to the reaction. UV–Vis and CV analyses demonstrated that these ligands had strong coordination with copper(I), implying the effect of ligand coordination ability on the stability and catalytic activity of catalytic system.

Investigating primary sites of damage in photosystem II in response to high temperature

The quick and non-invasive technique of Chlorophyll-a (Chl-a) fluorescence was used to investigate the primary site of damage in photosystem II in response to high temperature stress. Based on the changes observed in several parameters deduced from Chl-a fluorescence curves after giving heat treatment at 40 °C for 2–30 min it was observed that the sequence of events in PS II under heat stress was as follows: inhibition of OEC—decrease in electron donation capacity—increase in thermal dissipation—increase in number of inactive RC—dissociation of LHCII—decrease in the efficiency of primary charge separation, ultimately leading to inhibition of primary photochemistry. Further it was concluded that at 40 °C, the acceptor side of PSII [1–Vj and PHI(Eo)] showed insignificant changes, which indicated that acceptor side of PSII is not a major target site of heat stress.

Theoretical Determination of the pK a Values of Betalamic Acid Related to the Free Radical Scavenger Capacity: Comparison Between Empirical and Quantum Chemical Methods.

Health benefits of dietary phytochemicals have been suggested in recent years. Among 1000s of different compounds, Betalains, which occur in vegetables of the Cariophyllalae order (cactus pear fruits and red beet), have been considered because of reducing power and potential to affect redox-modulated cellular processes. The antioxidant power of Betalains is strictly due to the dissociation rate of the acid moieties present in all the molecules of this family of phytochemicals. Experimentally, only the pK avalues of betanin were determined. Recently, it was evidenced it was evidenced as the acid dissociation, at different environmental pHs, affects on its electron-donating capacity, and further on its free radical scavenging power. The identical correlation was studied on another Betalains family compound, Betalamic Acid. Experimental evidences showed that the free radical scavenging capacity of this compound drastically decreases at pH>5, but pK a values were experimentally not measured. With the aim to justify the Betalamic Acid behavior as free radical scavenger, in this paper we tried to predict in silico the pK a values by means different approaches. Starting from the known experimental pK as of acid compounds, both phytochemicals and small organic, two empirical approaches and quantum-mechanical calculation were compared to give reliable prediction of the pK as of Betalamic Acid. Results by means these computational approaches are consistent with the experimental evidences. As shown herein, in silico, the totally dissociated species, at the experimental pH>5 in solution, is predominant, exploiting the higher electron-donating capability (HOMO energy). Therefore, the computational estimated pK a values of Betalamic Acid resulted very reliable.

Hybrid [polysulfone–Zero Valent Iron] membranes: Synthesis, characterization and application for AsIII remediation

Hybrid polysulfone membranes decorated with Zero Valent Iron (ZVI) nanoparticles were prepared and evaluated for AsIII uptake. The hybrid polysulfone/ZVI membranes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM–EDX), transmission electron microscopy (TEM), mercury intrusion porosity measurements, thermal gravimetric analysis (TGA) and differential thermal analysis (DTA). The membranes are characterized by a macroporous structure with ZVI particles dispersed both inside the pores as well as at their surface. Electron Paramagnetic Resonance (EPR) spectroscopy reveals that the surface sulfide groups of polysulfone are readily accessible by extrinsic CuII cations. Moreover the polysulfone/ZVI membranes have a considerable electron-donating capacity to surface-adsorbed atoms, thus they are able to reduce CuII to CuI, and inhibit oxidation of ZVI from Fe0 to Fe3+. As a result, the Zero Valent Iron particles are stabilized against oxidation by ambient air and show appreciable AsIII adsorption capacity (26.6mgg−1). This renders them a significant stability, thus they can be reused at least four times for AsIII adsorption with a loss less than 1% of their As-uptake capacity. Based on a theoretical Surface Complexation Model we provide a consistent interfacial/structural picture that describes quantitatively all observed phenomena.

Redox Non-innocent Ligand Controls Water Oxidation Overpotential in a New Family of Mononuclear Cu-Based Efficient Catalysts.

A new family of tetra-anionic tetradentate amidate ligands, N1,N1'-(1,2-phenylene)bis(N2-methyloxalamide) (H4L1), and its derivatives containing electron-donating groups at the aromatic ring have been prepared and characterized, together with their corresponding anionic Cu(II) complexes, [(LY)Cu](2-). At pH 11.5, the latter undergoes a reversible metal-based III/II oxidation process at 0.56 V and a ligand-based pH-dependent electron-transfer process at 1.25 V, associated with a large electrocatalytic water oxidation wave (overpotential of 700 mV). Foot-of-the-wave analysis gives a catalytic rate constant of 3.6 s(-1) at pH 11.5 and 12 s(-1) at pH 12.5. As the electron-donating capacity at the aromatic ring increases, the overpotential is drastically reduced down to a record low of 170 mV. In addition, DFT calculations allow us to propose a complete catalytic cycle that uncovers an unprecedented pathway in which crucial O-O bond formation occurs in a two-step, one-electron process where the peroxo intermediate generated has no formal M-O bond but is strongly hydrogen bonded to the auxiliary ligand.

Combination of UV absorbance and electron donating capacity to assess degradation of micropollutants and formation of bromate during ozonation of wastewater effluents

In this study, the changes in UV absorbance at 254 nm (UVA254) and electron donating capacity (EDC) were investigated as surrogate indicators for assessing removal of micropollutants and bromate formation during ozonation of wastewater effluents. To measure the EDC, a novel method based on size exclusion chromatography followed by a post-column reaction was developed and calibrated against an existing electrochemical method. Low specific ozone doses led to a more efficient abatement of EDC than of UVA254. This was attributed to the abatement of phenolic moieties in the dissolved organic matter (DOM), which lose their EDC upon oxidation, but are partially transformed into quinones, which still absorb in the measured UV range. For higher specific ozone doses, the relative EDC abatement was lower than the relative UVA abatement, which can be explained by the oxidation of UV absorbing moieties (e.g. non-activated aromatic compounds), which contribute less to EDC. The abatement of the selected micropollutants (i.e., 17α-ethinylestradiol (EE2), carbamazepine (CBZ), atenolol (ATE), bezafibrate (BZF), ibuprofen (IBU), and p-chlorobenzoic acid (pCBA)) varied significantly depending on their reactivity with ozone in the examined specific ozone dose range of 0–1.45 mgO3/mgDOC. The decrease of EE2 and CBZ with high ozone reactivity was linearly proportional to the reduction of the relative residuals of UVA254 and EDC. The abatement of ATE, BZF, IBU, and pCBA with intermediate to low ozone reactivities was not significant in a first phase (UVA254/UVA254,0 = 1.00–0.70; EDC/EDC0 = 1.00–0.56) while their abatement was more efficient than the degradation of the relative residual UVA254 and much more noticeable than the degradation of the relative residual EDC in a second phase (UVA254/UVA254,0 = 0.70–0.25; EDC/EDC0 = 0.56–0.25) because the partially destroyed UV absorbing and electron donating DOM moieties become recalcitrant to ozone attack. Bromate formation was pronounced for specific ozone doses >0.25 mgO3/mgDOC. At these ozone doses, the residual DOM competes less with bromide for ozone as the electron-rich DOM moieties are almost completely degraded. Overall, these results imply that a combination of the relative residual UVA254 and EDC more truly reflects the intrinsic reactivity of DOM associated with the removal of micropollutants and bromate formation than the single use of the UV absorbance-based surrogate indicators.

Environmental pH and ionic strength influence the electron-transfer capacity of dissolved organic matter

Dissolved organic matter (DOM) plays an important role in the cycling of elements and the transformation of pollutants in the environment due to its electron-transfer capacity (ETC), but ETC may be affected by environmental factors such as pH and ionic strength. This study was aimed to reveal the effects of pH and ionic strength on the ETC of DOM and the possible mechanisms. DOM was prepared into solutions with various pH values (4, 6, 7, 8, and 10) and ionic strength (0.001, 0.01, 0.1, and 0.5 mol/L KCl). ETC of DOM including electron-accepting capacity (EAC) and electron-donating capacity (EDC) was determined with chronoamperometry. Spectroscopic and chromatographic properties of DOM were evaluated to obtain related structural information to explore the possible mechanisms for the ETC changes. Both the EAC and EDC of DOM increased consistently with increasing pH from 4 to 10. EAC and EDC increased with increasing ionic strength, peaked at 0.1 mol/L KCl, and then decreased. Gel permeation chromatogram displayed different molecular size distribution for the DOM in solution with different pH and ionic strength. Environmental pH and ionic strength influence the ETC of DOM by altering the conformation of DOM molecules.

Solvent Effect on the Photolysis of Riboflavin.

The kinetics of photolysis of riboflavin (RF) in water (pH 7.0) and in organic solvents (acetonitrile, methanol, ethanol, 1-propanol, 1-butanol, ethyl acetate) has been studied using a multicomponent spectrometric method for the assay of RF and its major photoproducts, formylmethylflavin and lumichrome. The apparent first-order rate constants (k obs) for the reaction range from 3.19 (ethyl acetate) to 4.61 × 10(-3) min(-1) (water). The values of k obs have been found to be a linear function of solvent dielectric constant implying the participation of a dipolar intermediate along the reaction pathway. The degradation of this intermediate is promoted by the polarity of the medium. This indicates a greater stabilization of the excited-triplet states of RF with an increase in solvent polarity to facilitate its reduction. The rate constants for the reaction show a linear relation with the solvent acceptor number indicating the degree of solute-solvent interaction in different solvents. It would depend on the electron-donating capacity of RF molecule in organic solvents. The values of k obs are inversely proportional to the viscosity of the medium as a result of diffusion-controlled processes.

Arsenite remediation by an amine-rich graphitic carbon nitride synthesized by a novel low-temperature method

Abstract A novel graphitic carbon nitride (GCN) material has been synthesized through a low-temperature solvolysis of sodium cyanide in formamide. The structure and morphology of the so-obtained GCN solid were studied by X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman/Infrared (IR) spectroscopy and thermal gravimetric analysis (TGA). GCN is characterized by a compacted layered structure bearing a high content of pendant amine groups (1.4 mmol g −1 ). Electron Paramagnetic Resonance spectroscopy reveals that the pendant amine groups are readily accessible by extrinsic metal cations. Moreover, GCN has a considerable electron-donating capacity to adsorbed electron accepting ions such as Cu 2+ . GCN shows an appreciable As(III) uptake capacity of 39.7 mg g −1 . Based on theoretical Surface Complexation Model we provide a consistent interfacial/structural picture that describes quantitatively observed phenomena.

Polythiophenes Comprising Conjugated Pendants for Polymer Solar Cells: A Review.

Polythiophene (PT) is one of the widely used donor materials for solution-processable polymer solar cells (PSCs). Much progress in PT-based PSCs can be attributed to the design of novel PTs exhibiting intense and broad visible absorption with high charge carrier mobility to increase short-circuit current density (Jsc), along with low-lying highest occupied molecular orbital (HOMO) levels to achieve large open circuit voltage (Voc) values. A promising strategy to tailor the photophysical properties and energy levels via covalently attaching electron donor and acceptor pendants on PTs backbone has attracted much attention recently. The geometry, electron-donating capacity, and composition of conjugated pendants are supposed to be the crucial factors in adjusting the conformation, energy levels, and photovoltaic performance of PTs. This review will go over the most recent approaches that enable researchers to obtain in-depth information in the development of PTs comprising conjugated pendants for PSCs.

A two-electron-shell game: intermediates of the extradiol-cleaving catechol dioxygenases

Extradiol-cleaving catechol dioxygenases function by binding both the organic substrate and O2 at a divalent metal center in the active site. They have proven to be a particularly versatile group of enzymes with which to study the O2 activation process. Here, recent studies of homoprotocatechuate 2,3-dioxygenase are summarized, showing how nature can utilize the enzyme structure and the properties of the metal and the substrate to select among many possible chemical paths to achieve both specificity and efficiency. Possible intermediates in the mechanism have been trapped by swapping active-site metals, introducing active-site amino acid substituted variants, and using substrates with different electron-donating capacities. Although each of these intermediates could form part of a viable reaction pathway, kinetic measurements significantly limit the likely candidates. Structural, kinetic, spectroscopic, and computational analyses of the various intermediates shed light on how catalytic efficiency can be achieved.

Influence of chemical and structural evolution of dissolved organic matter on electron transfer capacity during composting

Dissolved organic matter (DOM) can mediate electron transfer and change chemical speciation of heavy metals. In this study, the electron transfer capability (ETC) of compost-derived DOM was investigated through electrochemical approaches, and the factors influencing the ETC were studied using spectral and elemental analysis. The results showed that the electron accepting capacity (EAC) and electron donating capacity (EDC) of compost-derived DOM were 3.29–40.14μmole− (gC)−1 and 57.1– 346.07μmole− (gC)−1, respectively. Composting treatment increased the fulvic- and humic-like substance content, oxygenated aliphatic carbon content, lignin-derived aromatic carbon content, molecule weight, and N and S content of DOM, but decreased the aliphatic carbon content and the C and H content. This conversion increased the EDC and EAC of the DOM during composting.