Identical Functional Groups Research Articles

One-step microwave-assisted synthesis of metal-free heteroatom-doped carbon catalyst for H2O2 electrosynthesis

This study reports on a one-step conversion of polyaniline into a metal-free heteroatom-doped carbon electrocatalyst through microwave heating. A high surface area carbonaceous structure forms after a total synthesis time of only 140 s, with the presence of nitrogen and oxygen functional groups, as confirmed by thorough spectroscopic analysis. This catalyst exhibits high activity (onset potential of 0.73 V vs. RHE), selectivity (82 %), and stability (over a 7.5-hour test period) for the electrochemical oxygen reduction reaction towards hydrogen peroxide in alkaline media. Microwave synthesis reduces heating time by 29-fold and energy consumption by 77-fold, while producing materials with high electrocatalytic efficiency comparable to those conventionally prepared at 700°C. The microwave and the conventionally synthesized heteroatom-doped carbon catalysts show similar electrochemical performances, which can be attributed to the presence of nearly identical nitrogen functional groups and surface area in the two samples. In contrast, the microwave and conventionally synthesized samples exhibit significant variations in their oxygen functional groups. These results suggest that nitrogen functional groups are the main active sites for alkaline hydrogen peroxide formation, while oxygen functional groups play a minor role in the catalytic activity. Our work brings a solid contribution to the debate regarding the active centers for hydrogen peroxide formation.

Investigating Bael Fruit Gum Powder as Natural Polymer for Pharmaceutical Drug Delivery

Nowadays, the use of natural products is crucial in pharmaceuticals. Currently, natural products made with natural polymer offer various biomedical applications. The objective of the present research was to characterize the bael fruit gum (Aegle marmelos L.) as a natural polymer and investigate its potential in pharmaceutical drug delivery. Extraction of bael fruit gum was carried out by simple maceration technique. Further, the extract was subjected to different phytochemical analysis. The characterization part was studied with sophisticated techniques such as fourier-transform infrared (FTIR) and X-ray diffraction (XRD). Additionally, swelling and viscosity behavior were estimated as per the reported methods. Phytochemical analysis confirms the existence of major secondary metabolites like tannins, flavonoids, saponins, alkaloids, and triterpenoids. FTIR results showed identical peaks of phytochemicals, which confirmed the presence of identical functional groups. XRD study indicates that extract nature is amorphous. The swelling behavior and viscosity study resulted in the rheological performance at an optimum and desired level. In conclusion, this research indicates the potential of bael fruit gum as a natural polymer for pharmaceutical applications, contributing to the discovery of new natural products and promoting their industrial use.

Thorium Complexation with Aliphatic and Aromatic Hydroxycarboxylates: A Combined Experimental and Theoretical Study.

Hydroxycarboxylic acids, viz., α-hydroxyisobutyric acid (HIBA) and mandelic acid (MA), have been widely employed as eluents for inner transition metal separation studies. Both extractants have identical functional groups (OH and COOH) with different side-chains. Despite their similarities in binding motifs, they show different retention behaviors for thorium and uranium in liquid chromatography. To understand the mechanism behind the trend, a detailed study on the aqueous phase interaction of thorium with both extractants is carried out by speciation, spectroscopy, and density functional theory-based calculations. Potentiometric titration experiments are carried out to reveal the stability and species formed. Electrospray ionization mass spectrometry is performed to identify the formation of different species by Th with both HIBA and MA. It is seen that for Th-HIBA and Th-MA, the dominating species are ML3 and ML4, respectively. A similar pattern observed in potentiometric speciation analysis supports the tendency of Th to form higher stoichiometric species with MA than with HIBA. The difference in the dominating species thus helps in explaining the reversal in the retention behavior of uranium and thorium in the reverse-phase liquid chromatographic separation. The results obtained are corroborated with extended X-ray absorption fine structure spectroscopic measurements and density functional theory (DFT) calculations.

Adjusting the pH of sizing agents to achieve superior interfacial and mechanical properties of carbon fiber reinforced epoxy composites

Interfacial properties were crucial in determining the mechanical properties of carbon fiber reinforced polymer composites (CFRPs). Applying appropriate sizing agents could effectively improve the interfacial properties of CFRPs. However, the influence of the pH of the sizing agents on the interfacial properties of CFRPs was still unclear. In this work, the above issues were elucidated by adjusting the pH of the diethanolamine-modified E51 (E51@DEA) sizing agent to investigate its impact on the interfacial properties of CFRPs. The molecular weight and emulsion particle diameter of E51@DEA increased with increasing pH of the sizing agent, despite the presence of identical chemical functional groups. E51@DEA-pH 7 showed the best interfacial enhancement. It exhibited ILSS and IFSS values of 102.24 and 113.45 MPa, respectively. This showed an increase of 76 % and 37 % when compared with T700. Additionally, the compressive and tensile strength of T700/E51@DEA-pH 7 also improved by approximately 13 % and 30 %, respectively. The suitable molecular chain length of the sizing agent and the high roughness of the surface of CFs were regarded as the contributing factors. This work further provided an effective and simple strategy for adjusting sizing agents to better improve the interfacial properties of CFRPs.

Predicted Separation of Acid Gases from Gas Mixtures by Functionalized Porous Aromatic Frameworks.

The selective adsorption of target acid gas molecules from binary gas mixtures by porous aromatic frameworks (PAFs) with two identical functional groups per aromatic ring (PAF-R2) was computationally investigated using grand canonical Monte Carlo simulations. PAF-R2 adsorption was considered for three binary mixtures of small molecular concentrations of acid gas and abundant nitrogen gas (CO2/N2, SO2/N2, and H2S/N2). The results indicate that additional functional groups enhance acid gas loadings and selectivity, compared with pristine PAF and single-functionalized PAFs. Low pressures yield linearly increasing gas loadings and constant selectivity, while high pressures yield much higher adsorption and selectivity. In particular, SO2 loading and selectivity under high pressures are heavily influenced by the PAF's maximum adsorption limit, which can be linked back to the functional groups and their configuration. In summary, PAF-(3,5)-(COOH)2 (nomenclature of PAFs is provided in the Appendix in the Supporting Information) and many other PAF with the same two electron-withdrawing groups are predicted to have great acid gas adsorption and selectivity from gas mixtures, while PAF-(3,5)-(OH)2 (one of PAFs with two identical electron-donating groups) is predicted to have good adsorption and selectivity, especially under elevated pressures. The results of this work can provide insights into various types of PAFs with great selective adsorption ability and their corresponding conditions. The simulation procedures and results may inspire the exploration and screening of other types of PAFs or porous materials, for acid gas absorption.

Microstructural and Optical Properties of Green-Synthesized rGO Utilizing <i>Amaranthus viridis</i> Extract

Research of green-synthesized reduced graphene oxide (rGO) using Amaranthus viridis (AV) extract has been successfully conducted. The modified Hummers method was used to synthesize graphene oxide (GO), then reduced using hydrazine hydrate and AV extract to obtain rGO. The X-ray diffraction results illustrate the change in crystalline structure from graphite to rGO. Peaks at 2θ angles of 26.5°, 9.1°, and 24.1° indicate the characteristics of graphite, GO, and rGO, respectively. The transmission electron microscopy image shows the formation of 2D nanosheet morphology with slight wrinkles. The fourier transform infrared spectrum represents six peaks of identical functional groups in the graphene-based nanomaterials. Meanwhile, GO has two additional oxygen groups (carboxyl and hydroxyl) at wavenumbers of 1720 cm-1 and 1217 cm-1, respectively. Furthermore, the UV-Vis analysis data shows the typical absorption of GO at 232 nm and 301 nm, while at 266 nm and 278 nm, it belongs to graphite and rGO. The bandgap energy of nanomaterials is 0–3.58 eV, which describes the difference in their optical properties. These promising results reveal the potential of AV as a green-reducing agent to minimize the use of chemicals in the synthesis of rGO for various applications.

Biosynthesis and characterization of silver nanoparticles synthesized using extracts of Agrimonia eupatoria L. and in vitro and in vivo studies of potential medicinal applications.

This research explores the synthesis, characterization, and biological activities of silver nanoparticles (AgNPs) derived from acetone (AgNPs-acetone) and aqueous (AgNPs-H2O) extracts of Agrimonia eupatoria. The nanoparticles exhibit isometric morphology and uniform size distribution, as elucidated through Transmission Electron Microscopy (TEM) and high-resolution TEM (HRTEM) analyses. The utilization of Scanning Transmission Microscopy (STEM) with High-Angle Annular Dark-Field (HAADF) imaging and energy dispersive spectrometry (EDS) confirms the crystalline nature of AgNPs. Fourier Transform Infrared (FTIR) analysis reveals identical functional groups in the plant extracts and their corresponding AgNPs, suggesting the involvement of phytochemicals in the reduction of silver ions. Spectrophotometric monitoring of the synthesis process, influenced by various parameters, provides insights into the kinetics and optimal conditions for AgNP formation. The antioxidant activities of the plant extracts and synthesized AgNPs are evaluated through DPPH and ABTS methods, highlighting AgNPs-acetone as a potent antioxidant. Third-instar larvae exposed to the extracts have differential effects on DNA damage, with the acetone extract demonstrating antigenotoxic properties. Similarly, biosynthesized AgNPs-acetone displays antigenotoxic effects against EMS-induced DNA damage. The genotoxic effect of water extract and AgNPs-acetone was dose-dependent. Hemolytic potential is assessed on rat erythrocytes, revealing that low concentrations of AgNPs-acetone and AgNPs-H2O had a nontoxic effect on erythrocytes. Cytotoxicity assays demonstrate time-dependent and dose-dependent effects, with AgNPs-acetone exhibiting superior cytotoxicity. Proapoptotic activity is confirmed through apoptosis induction, emphasizing the potential therapeutic applications of AgNPs. The antimicrobial activity of AgNPs reveals concentration-dependent effects. AgNPs-H2O display better antibacterial activity, while antifungal activities are comparable between the two nanoparticle types.

Isolation of curcumin compounds in Temulawak Rhizome (Xanthorrhiza Roxb)

The curcumin compounds in Temulawak Rhizome have been isolated and identified.. This study aims to identify curcumin compounds in temulawak rhizome by modifying methods that pay attention to the efficiency of funds and the use of materials. In general, the method of isolation and identification is carried out. The methods used are (1) Extraction, (2) Thin Layer Chromatography, (3) Column Chromatography and (4) Infrared (IR) Testing. Based on comparing the sample's Retention Factor (RF) value with the standard curcumin compound, the results were identical, and the positive sample contained a curcumin compound. The results of the Infrared spectrum can be assumed that the sample is a flavanols group, which can be seen from the wavelength range of identical functional groups in curcumin compounds.

The construction of highly selective surface molecularly imprinted polymers based on Cu(II) coordination for the detection of bisphenol A

Herein, we designed and constructed a highly selective MIPs for bisphenol A (BPA) named Cu-MIPs@CS based on Cu(II) coordination. The synthesis of Cu-MIPs@CS employed a dummy template strategy and surface imprinting technology, with chitosan (CS) as the substrate linked to imprinted layers via Cu2+ bridging. 4-vinylpyridine acted as the functional monomer, capable of forming a complex with the template ketoprofen, while ethylene glycol dimethacrylate served as the cross linker. Cu-MIPs@CS exhibited a significantly enhanced imprinting factor of 14.78 for BPA, which was approximately 6.6 times higher than that of imprinted materials without Cu2+ (MIPs@CS). Cu-MIPs@CS exhibited a selective factor of 12.74 towards resorcinol, which possessed identical functional groups but a smaller size than BPA, representing an enhancement of selectivity by 12.25-fold compared to MIPs@CS. More importantly, Cu-MIPs@CS exhibited a superior discrimination ability between BPA and its structural analogue, diphenolic acid, with an excellent selective factor of 2.93, highlighting its significance in distinguish the structural analogue of BPA. In contrast, MIPs@CS lack sufficient selectivity to differentiate between them. Through exploration of adsorption mechanism of Cu-MIPs@CS, it was demonstrated that the incorporation of Cu2+ significantly reduced nonspecific adsorption, but also facilitated the creation of more selective imprinted cavities by introducing metal coordination, thereby notably enhancing the selectivity of Cu-MIPs@CS. Finally, the developed Cu-MIPs@CS were applied as the solid phase extraction adsorbent and combined with HPLC-DAD detection to establish an analytical method towards BPA in drinking water samples. The limit of detection of the method was 0.14 μg L−1 and recoveries ranged from 95.6 % to 101 %. This work provided broad prospects for construction of highly selective MIPs and accurate quantification of trace amounts of BPA.

Micellar Mechanisms for Desymmetrization Reactions in Aqueous Media.

Water-mediated organic reactions significantly contribute to the protection of the environment. Desymmetrization reactions, which convert only one of the identical functional groups within one molecule, are cost-effective because of the low cost of the starting materials. In combination with these two merits, highly efficient and practical selective monohydrolysis reactions of symmetric diesters were previously reported. The products of these reactions are versatile building blocks. The mechanisms of this reaction are hypothesized to proceed through micellar aggregates in which the hydrophilic carboxylate anions formed by monohydrolysis are directed outward and the remaining hydrophobic groups are directed inward in governing the selectivities. Here, dynamic light scattering and electrophoretic light scattering experiments were performed for detection of the key intermediates in the reaction. These experiments revealed the existence of aggregates with negative charges on the surface in the mainly aqueous media, supporting the reaction mechanisms that control the high selectivities.

Structural Isomer of Fluorinated Ruddlesden-Popper Perovskites Toward Efficient and Stable 2D/3D Perovskite Solar Cells.

Defect passivation using two-dimensional (2D)-layered perovskites with organic spacers on 3D bulk perovskites has been proposed as an effective strategy to improve perovskite solar cell stability and efficiency. Specifically, fluorination of the organic spacers has been employed due to the resulting hydrophobic nature and the defect passivation characteristics. In addition to the type of functional groups attached to the spacer molecules, conformational changes of fluorine isomers on layered perovskites can provide an extended strategy to control a variety of opto-electrical properties related to the interlayer spacing. As a model system for the structural isomer of fluorinated spacers, meta-CF3 and para-CF3 groups anchored to phenethylammonium iodide (PEAI) spacer molecules are employed to synthesize 2D perovskites and to investigate their full potential as an interfacial modifier for perovskite solar cells. The fluorination position change leads to altered opto-electrical characteristics in layered perovskites. Although they possess identical functional groups, the different orientations of the functional groups used in the perovskite layer deposited on the 3D perovskite absorber result in distinct electrical properties of 2D/3D heterostructures due to dissimilar intermolecular interactions. The 2D perovskite with meta-CF3-PEAI spacers exhibits an enhancement of the charge transport in the out-of-plane orientation and an improved suppression of the trap states of 3D perovskites while also providing a more favorable energy alignment for efficient charge transfers. Theoretical simulations are consistent with the experimental results. The structural isomers of fluorination anchoring to spacer cations alter the structural configuration of the spacer as well as the interlayer spacing that can improve the performance and the stability of 2D/3D perovskite solar cells.

Functional group differentiation of isomeric solvents enables distinct zinc anode chemistry

Electrolytes hold the key to realizing reliable zinc (Zn) anodes. Divergent organic molecules have been proven effective in stabilizing Zn anodes; however, irrational comparisons exist due to the uncontrolled molecular weights and functional group amounts. In this work, two “isomeric molecules”: 1,2-dimethoxyethane (DME) and 1-methoxy-2-propanol (PM), with identical molecular weights but different functional groups, have been studied as co-solvents in electrolytes, which have delivered distinct electrochemical performance. Experimental and simulative study indicates the dipole moment induced by the hydroxyl groups in PM (higher molecular polarity than ether groups in DME) reconstructs the space charge region, enhances the concentration of Zn²⁺ in the vicinity of Zn anodes, and <em>in-situ</em> derives different solid electrolyte interphase (SEI) models and electrode–electrolyte interfaces, resulting in exceptional cycling stability. Remarkably, the Zn||Cu cell with PM worked over 2000 cycles with high Coulombic efficiency (CE) of 99.7%. The Zn||Zn symmetric cell cycled over 2000 h at 1 mA·cm⁻², and showed excellent stability at an ultrahigh current density of 10 mA·cm⁻² and capacity of 20 mAh·cm⁻² over 200 h (depth of discharge, DOD of 70%). The Zn||sodium vanadate pouch cell with a high mass loading of 6.3 mg·cm⁻² and a high capacity of 24 mAh demonstrates superior cyclability after 570 h. This work can be a good starting point to provide reliable guidance on electrolyte design for practical aqueous Zn batteries.

Rheological modeling and microstructural evaluation of oily sludge modified bitumen

The disposal of oily sludge (OS) and depletion of crude oil reservoirs has become a global problem for the petroleum industries. The rising cost of bituminous materials is also attributed to the depletion of crude oil reservoirs. Incorporating OS in the production of bitumen can reduce waste generation, thereby ensuring sustainability in petroleum industries. This study carried out a series of physicochemical, rheological and morphological tests to examine the suitability of OS as a bitumen modifier. OS and binders were subjected to Fourier transform infrared spectroscopy (FTIR) and atomic force microscopy (AFM) to characterize their morphological and chemical configuration. Using a dynamic shear rheometer (DSR) and response surface methodology (RSM), the performance characteristics of binders were analyzed and modeled. FTIR showed the identical functional groups responsible for the compatibility of OS and bitumen. Fit statistics and diagnostic graphs showed the significance and adequacy of the quadratic model for rutting and fatigue factors. Response surface plots showed that OS improved the fatigue resistance of bitumen. The OS up to 8 % addition improves fatigue resistance while keeping the performance grade (PG) identical to that of base bitumen.

Synthesis of nanoscale zero-valent iron doped carbonized zeolitic imidazolate framework-8 for methylene blue removal in water

Abstract Nanoscale zero-valent iron-doped carbonized zeolitic imidazolate framework-8 (nZVI/CZIF-8) was prepared by carbonation of ferric nitrate and ZIF-8 at 800 °C and used as an adsorbent to remove methylene blue (MB) from water. The synthesized nZVI/CZIF-8 has a specific surface area of 806.9 m2/g, a pore volume of 0.86 cm3/g and an nZVI content of 1.35%, respectively. Both the nZVI/CZIF-8 and CZIF-8 have identical functional groups of O-H, C-H and C=C. With the increase of CZIF-8 size, MB removal rate increased. The doping of nZVI increased the MB removal percentage from 74.5% for ZIF-8 to 96.2% within 80 min for nZVI/CZIF-8. The MB removal percentage increased with the dosage of nZVI/CZIF-8. The MB adsorption with the adsorbents conforms to the Freundlich adsorption isothermal model and the removal rate fitted well to a pseudo-first-order model. The results demonstrate the feasibility of synthesizing high active and stable nZVI/CZIF-8 particles.

Nanoparticles Based on Chondroitin Sulfate from Tuna Heads and Chitooligosaccharides for Enhanced Water Solubility and Sustained Release of Curcumin.

This study aimed to separate chondroitin sulfate (CS) from the heads of skipjack tuna (Katsuwonus pelamis) and yellowfin tuna (Thunnus albacares), by-products derived from canned tuna processing, via a biological process. The use of 1% w/w papain and an incubation time of 48 h resulted in a degree of hydrolysis of 93.75 ± 2.94% and a CS content of 59.53 ± 1.77 mg/100 g. The FTIR spectra of extracted CS products exhibited identical functional groups found in commercially available CS. The molecular weights of CS extracted from skipjack and yellowfin tuna heads were 11.0 kDa and 7.7 kDa, respectively. Subsequently, a CH:CS ratio of 3:2 for CS and chitooligosaccharides (CH) was chosen as the optimal ratio for the preparation of spherical nanoparticles, with %EE, mean particle size, PDI, and zeta potential values of 50.89 ± 0.66%, 128.90 ± 3.29 nm, 0.27 ± 0.04, and -12.47 ± 2.06, respectively. The CU content was enhanced to 127.21 ± 1.66 μg/mL. The release of CU from this particular nanosystem involved mainly a drug diffusion mechanism, with a burst release in the first 3 h followed by a sustained release of CU over 24 h. The DPPH and ABTS scavenging activity results confirmed the efficient encapsulation of CU into CHCS nanoparticles. This study will provide a theoretical basis for CS derived from tuna head cartilages to be used as a functional component with specific functional properties in food and biomedical applications.

Pseudo-multicomponent reactions.

Classical multicomponent reactions (MCRs) are domino-type one-pot processes in which three or more different reactants are combined sequentially in the same reactor to synthesize compounds containing all or almost all atoms coming from the reactants. Besides, pseudo-MCRs are also domino-type one-pot processes involving combinations of at least three reactants but in which at least one of them takes part in two or more reaction steps. In consequence, the products synthesized through pseudo-MCRs contain also all or almost all atoms but coming from two or more identical reactants. Thus, pseudo-MCRs differ from classical MCRs because the first ones appear to involve an assembly of a higher number of different components than those that are being truly assembled. However, pseudo-MCRs are also useful synthetic tools to generate libraries of complex compounds in few experimental steps, and although the repeated reactants may make them appear less diverse than classical MCRs, this can be offset by the higher number of reactants that can participate in this type of reaction. Overall, there are two types of pseudo-MCRs. The first are those in which the duplicated reagents participate in different steps of the corresponding reaction mechanism. The second kind of pseudo-MCRs are those in which one or more components react simultaneously with a main reagent containing two or more identical functional groups. These latter are known as repetitive pseudo-MCRs. Thus, the aim of the present review is to cover for the first time selected works mainly published in the last two decades about pseudo-MCRs and their repetitive versions toward the synthesis of novel, complex, and highly symmetrical molecules, often including their interesting applications in various fields of science and technology. The manuscript has been categorized considering the number of reagents participating in the corresponding pseudo-MCRs, aiming to give readers novel insights for their future investigations.

DTBP‐promoted Passerini‐type reaction of isocyanides with aldehydes: Synthesis of α‐acyloxycarboxamides

AbstractA novel DTBP‐promoted Passerini‐type reaction of isocyanides with two molecular aldehydes has been developed. This reaction is applicable for a wide range of isocyanides and aldehydes and provides an efficient method for the synthesis of α‐acyloxycarboxamides with two identical functional groups in good to high yields in a single step. The experimental results clearly confirmed the role of water and provided a better mechanistic understanding of this reaction.

Site‐Selective Functionalization of Sila‐Adamantane and Its Ensuing Optical Effects

AbstractThe first syntheses of functionalized sila‐adamantanes via site‐selective reactions are described. Mechanistic inquiry into the isomerization of sila‐adamantane revealed new approaches for installing halides at the 2‐position of the cluster. Meanwhile, isomerization via Lewis acid catalysts with non‐nucleophilic counteranions provided access to sila‐adamantane on the gram‐scale, enabling us to discover strategies for substituting its 1‐, 3‐, 5‐, and 7‐positions with identical or distinct functional groups. Optical absorbance and density functional theory studies show that σ‐withdrawing substituents at the 1‐position strongly perturb optical absorbance in sila‐adamantane, whereas substituents at the exocyclic and 2‐position are optically inert. As silicon diamondoids are atomically precise models for silicon nanocrystals, our findings suggest that passivation at tertiary surface sites carries an outsized impact on the optical properties of surface‐functionalized Si nanocrystals.

Site‐Selective Functionalization of Sila‐Adamantane and Its Ensuing Optical Effects

The first syntheses of functionalized sila-adamantanes via site-selective reactions are described. Mechanistic inquiry into the isomerization of sila-adamantane revealed new approaches for installing halides at the 2-position of the cluster. Meanwhile, isomerization via Lewis acid catalysts with non-nucleophilic counteranions provided access to sila-adamantane on the gram-scale, enabling us to discover strategies for substituting its 1-, 3-, 5-, and 7-positions with identical or distinct functional groups. Optical absorbance and density functional theory studies show that σ-withdrawing substituents at the 1-position strongly perturb optical absorbance in sila-adamantane, whereas substituents at the exocyclic and 2-position are optically inert. As silicon diamondoids are atomically precise models for silicon nanocrystals, our findings suggest that passivation at tertiary surface sites carries an outsized impact on the optical properties of surface-functionalized Si nanocrystals.

Ni-electrocatalytic Csp3-Csp3 doubly decarboxylative coupling.

Cross-coupling between two similar or identical functional groups to form a new C-C bond is a powerful tool to rapidly assemble complex molecules from readily available building units, as seen with olefin cross-metathesis or various types of cross-electrophile coupling1,2. The Kolbe electrolysis involves the oxidative electrochemical decarboxylation of alkyl carboxylic acids to their corresponding radical species followed by recombination to generate a new C-C bond3-12. As one of the oldest known Csp3-Csp3 bond-forming reactions, it holds incredible promise for organic synthesis, yet its use has been almost non-existent. From the perspective of synthesis design, this transformation could allow one to agnostically execute syntheses without regard to polarity or neighbouring functionality just by coupling ubiquitous carboxylates13. In practice, this promise is undermined by the strongly oxidative electrolytic protocol used traditionally since the nineteenth century5, thereby severely limiting its scope. Here, we show how a mildly reductive Ni-electrocatalytic system can couple two different carboxylates by means of in situ generated redox-active esters, termed doubly decarboxylative cross-coupling. This operationally simple method can be used to heterocouple primary, secondary and even certain tertiary redox-active esters, thereby opening up a powerful new approach for synthesis. The reaction, which cannot be mimicked using stoichiometric metal reductants or photochemical conditions, tolerates a range of functional groups, is scalable and is used for the synthesis of 32 known compounds, reducing overall step counts by 73%.