Acid Functional Groups Research Articles

Equilibrium, Kinetic, and Diffusion Mechanism of lead(II) and cadmium(II) Adsorption onto Commercial Activated Carbons.

The adsorption of Pb(II) and Cd(II) on three commercial microporous activated carbons was analysed. Adsorption kinetics and statistics were investigated, and the results were described with different models. The highest values of the correlation coefficient R2 were obtained for the pseudo-second-order kinetics model for all ions tested and all sorbents used. The adsorption process was found to be determined by both diffusion in the liquid layer and intraparticle diffusion. The adsorption equilibrium is very well described by Langmuir, Temkin, Thoth or Jovanovic isotherm models. Based on the values of n from the Freundlich isotherm and KL from the Langmuir isotherm, the adsorption of cadmium and lead ions was found to be favourable. The highest monolayer capacities were obtained during the adsorption of lead ions (162.19 mg/g) and for cadmium (126.34 mg/g) for activated carbon WG-12. This carbon is characterised by the highest amount of acid functional groups and the largest specific surface area. The adsorption efficiency of the tested ions from natural water is lower than that from a model solution made from deionised water. The lowest efficiencies are obtained when the process occurs from highly mineralised water.

Comparative Analysis of the Hydrazine Interaction with Arylene Diimide Derivatives: Complementary Approach Using First Principles Calculation and Experimental Confirmation.

Suitable functional group-engineered π-conjugated aromatic dimides based on perylene (PDI) and naphthyl scaffolds (NDI) demonstrated excellent sensitivity toward different gaseous analytes. However, to date, no methodical analysis has been performed to rationalize molecular-level interactions in the context of optical transduction, which is essential for systematic performance optimization of NDI/PDI-based molecular sensors. Therefore, in this present work, NDI/PDI scaffolds have been designed with amino acid functional groups (alanine, ALA and glutamic acid, GLU) at the terminal positions, and we subsequently compared the efficacy of four different imide derivatives as model hosts for hydrazine adsorption. Specifically, the adsorption of hydrazine at different interaction sites has been thoroughly investigated using ab initio calculations, where the adsorption energy, charge transfer, and recovery time have been emphasized. Theoretical results exhibit that irrespective of host specification the COOH groups offer a primary interaction site for hydrazine through the hydrogen bonding interaction. The presence of more COOH groups and relatively stronger interaction with secondary edge oxygen ensure that GLU functional moieties are a superior choice over ALU for efficient hydrazine binding. The molecular energy spectrum analysis exhibits more favorable HOMO/LUMO gap variations after hydrazine interaction in the case of PDI derivatives irrespective to the nature of the amino acid residues. Therefore, by a combination of both factors, PDI-GLU has been identified as the most suitable host molecule for hydrazine among four derivatives. Finally, the key theoretical predictions has been later experimentally validated by analyzing UV-visible spectroscopy and NMR studies, wherein the mechanism of interaction has also been experimentally verified by EPR analysis and FT-IR studies.

Real-Time Identification of Aerosol-Phase Carboxylic Acid Production Using Extractive Electrospray Ionization Mass Spectrometry.

Comprehensive identification of aerosol sources and their constituent organic compounds requires aerosol-phase molecular-level characterization with a high time resolution. While real-time chemical characterization of aerosols is becoming increasingly common, information about functionalization and structure is typically obtained from offline methods. This study presents a method for determining the presence of carboxylic acid functional groups in real time using extractive electrospray ionization mass spectrometry based on measurements of [M - H + 2Na]+ adducts. The method is validated and characterized using standard compounds. A proof-of-concept application to α-pinene secondary organic aerosol (SOA) shows the ability to identify carboxylic acids even in complex mixtures. The real-time capability of the method allows for the observation of the production of carboxylic acids, likely formed in the particle phase on short time scales (<120 min). Our research explains previous findings of carboxylic acids being a significant component of SOA and a quick decrease in peroxide functionalization following SOA formation. We show that the formation of these acids is commensurate with the increase of dimers in the particle phase. Our results imply that SOA is in constant evolution through condensed-phase processes, which lower the volatility of the aerosol components and increase the available condensed mass for SOA growth and, therefore, aerosol mass loading in the atmosphere. Further work could aim to quantify the effect of particle-phase acid formation on the aerosol volatility distributions.

Electrodeposition of Cu with Amino Acids toward Electrocatalytic Enhancement of CO2 Reduction Reaction

This study investigates the effect of five amino acids on the electrodeposition of Cu to enhance its electrocatalytic performance in CO2 reduction reactions (CO2RR). The amino acids significantly influenced the deposition potential, crystallite size, and surface morphology of the electrodeposited Cu. Electrodeposited Cu with amino acids exhibit significantly smaller crystallites and higher particle density on carbon paper relative to amino acid-free samples. The integration of amino acids into the electrodeposited Cu was confirmed via high-angle annular dark-field scanning transmission electron microscopy, energy dispersive X-ray spectroscopy and hard X-ray photoelectron spectroscopy. All electrodeposited Cu exhibits a higher faradaic efficiency (FE) in the electrochemical reduction of CO2 to CH4 relative to Cu foil (24.2%), regardless of the presence or absence (55.0%) of amino acids when the electrolysis was conducted at −1.27 V vs RHE. Electrodeposited Cu with L-histidine, containing an imidazole group, demonstrates a higher FE of CH4 (67.6%) and effectively suppressed the hydrogen evolution reaction, highlighting the crucial role of amino acid functional groups, particularly imidazole, in augmenting the electrochemical conversion of CO2 to CH4. The study demonstrates the critical influence of specific functional groups in amino acids on the catalytic efficiency of electrodeposited Cu in CO2RR electrocatalysis applications.

Nano structure of CO2-Brine-Kaolinite Interface: Implications for CO2 Geological Sequestration

CO2-Brine-Rock interaction has been identified to govern CO2 multiphase flow and affect the integrity of the underground reservoirs. However, limited investigations address the role of brine salinity, rock mineralogy, and organic matter in CO2 wettability at nano scale. To solve this problem, a molecular dynamics (MD) simulation is performed. The interfacial properties, including density distribution and radial distribution function (RDF, g(r)), are calculated for CO2 saturated high salinity water and CO2 saturated low salinity water. The density distribution profile shows that mineralogy is a critical parameter for CO2 wettability: lowering salinity leads to a more CO2 wet siloxane surface while the aluminol surface becomes less CO2 wet. g(r) reveals that the type of organic matter plays a critical role: base functional group (-N) renders a CO2 wet surface whereas the acid functional group (-COOH) causes a water wet surface. This investigation integrates the effects of brine salinity, mineralogy, and organic matter to evaluate CO2 wettability. This MD simulation reveals the principal factors controlling the CO2 wettability at the nano scale and provides a general paradigm to reduce the leakage risk of CO2 geological sequestration.

Selective Modifier-Assisted Humic Acid Extraction: Implications for Soil Quality Enhancement.

Efficient use of humic acid (HA) for eco-friendly farming and environmental remediation requires further understanding of how targeted modification of HA affects the chemical structure of HA and thereby its effectiveness in enhancing soil quality. We developed novel selective modifiers (SMs) for extracting HA by codoping sodium and copper elements into the birnessite lattice. The structure of SMs was thoroughly examined, and the HAs extracted using SMs, referred to as SMHs, were subjected to a detailed evaluation of their functional groups, molecular weight, carbon composition, flocculation limits, and effectiveness in saline soil remediation. The results showed that replacing manganese with sodium and copper in SMs alters the valence state and reactive oxygen species. In contrast, SMHs exhibited increased acidic functional groups, a lower molecular weight, and transformed aliphatic carbon. Furthermore, the saline soil was improved through increased salt leaching and an optimized soil aggregate structure by SMHs. This research highlights the importance of targeted modification of HA and demonstrates the potential of these modifiers in improving soil quality for eco-friendly farming and environmental remediation.

Evidences for the influence from key chemical structures of per- and polyfluoroalkyl substances on their environmental behaviors

This study carried out the atmospheric and precipitation observation in Beijing for nearly one year, and firstly simultaneously observed the pollution characteristics of PFASs and their main isomers, focusing on their gas-particle partitioning mechanism and dry and wet deposition characteristics. After deducting PFASs in the aqueous phase of particulate matter, the gas-particle partitioning coefficients (−7.04 to −5.49) were about 3–4 units smaller than before (−2.77 to −1.51), and all were smaller than 0, which indicated that each PFAS and isomer were more distributed in the gas phase. Dry deposition was dominant in the atmospheric deposition of each PFAS and isomer with relative contribution of 66 ± 17%, but the relative contribution of dry deposition was significantly different. It was found that the gas-particle partitioning coefficient can be influenced by key chemical structures such as carbon chain length, functional group type, and isomer structure. Furthermore, the gas-particle partitioning can influence the dry and wet deposition of PFASs. Specifically, PFASs with longer carbon chains, carboxylic acid functional group (compared to sulfonic acid functional group) or PFOA branched chain structures had larger gas-particle partitioning coefficients and can be more distributed in the hydrophobic phase of particulate matter, and their relative contributions of dry deposition were smaller.

The effects of modifiers on electrospray ionization for small-to-medium-sized molecules in comparison with solution-phase ionization.

Modifiers are essential additives in electrospray ionization (ESI) mass spectrometric analysis to enhance the production of ionic species in the gas phase for the detection of small-to-medium-sized molecules in biological and aqueous samples. Therefore, an appropriate modifier, in conjunction with the right ionization polarity, is crucial for sensitive ESI mass spectrometric analysis. However, the charge carried by basic and acidic functional groups in solution is neither quantitatively nor qualitatively reflected in the MS spectrum. For example, adding an acidic modifier will cause sufficient protonation of a basic functional group in solution; however, this may result in inferior positive ESI compared to using a basic modifier. Another example is when the MS spectrum does not reflect the charge distribution of multiply charged molecules in solution. Therefore, this review will summarize and discuss the proposed mechanisms by which modifiers induce and influence ESI. It will also cover molecular characteristics that affect ESI, such as charge state and polarity, which result in a difference between solution-phase ionization and ESI.

Surface functionalized visible light-responsive yttrium orthovanadate for photocatalytic hydrogen production

Yttrium orthovanadate (YVO4), a wide-bandgap photocatalyst was tuned into a visible responsive material by anchoring an organic framework on the surface of YVO4 nanoparticles using polyethyleneimine (PEI). The surface organic framework was identified as the decomposed PEI derivatives with the carbonyl and carboxylic acid functional groups by the FTIR and XPS analyses. The top of the valence band (VB) was raised and the bottom of the conduction band was moved down; hence, the band gap of YVO4 was reduced to absorb the light in the visible region for all three synthesized samples, which was confirmed by DRS UV–Vis analysis. The functional groups facilitated more water molecules on the YVO4 surface via hydrogen bonding; hence, the YVO4 surface acquired superhydrophilicity. Among the three YI, YII, and YIII samples synthesized with three different calcination temperatures of 80, 260 and 400 °C respectively, YII showed many advantageous photocatalytic properties. The optimum loading of organic compounds obtained on YII surface at 260 °C, which improved the surface area, visible light absorption, hydrophilicity, and exciton's life. Hence, YII showed a better performance of 3.75 mmol h−1g−1cat H2 production than YI and YII. This work interestingly revealed the influence of calcination temperature on surface functionalization and the performance of catalytic materials.

Hyaluronic acid functionalized citric acid dendrimer/UiO-66-COOH as a stable and biocompatible platform for daunorubicin delivery

This work aimed to prepare a new system for daunorubicin (DNR) delivery to improve therapeutic efficiency and decrease unwanted side effects. Typically, at first, a carboxylic acid functional group containing metal-organic framework (UiO-66-COOH) was synthesized in a simple way. Then, a third generation of citric acid dendrimer (CAD G3) was grown on it (UiO-66-COOH-CAD G3). Finally, the system was functionalized with pre-modified hyaluronic acid (UiO-66-COOH-CAD-HA). SEM analysis displayed that the synthesized particles have a spherical shape with an average particle size ranging from 260 to 280 nm. An increase in hydrodynamic diameter from 223 nm for UiO-66-COOH to 481 nm for UiO-66-COOH-CAD-HA is a sign of success in the performed reactions. Also, the average pore size was calculated at about 4.04 nm. The DNR loading efficiency of UiO-66-COOH-CAD-HA was evaluated at ∼74 % (DNR@UiO-66-COOH-CAD-HA). It was observed that the drug release rate at a lower pH is more than higher pH. The maximum hemolysis of <3 % means that the UiO-66-COOH-CAD-HA is hemocompatible. The use of DNR-loaded UiO-66-COOH-CAD-HA led to cell-killing of 77.9 % for MDA-MB 231. These results specified the great potential of UiO-66-COOH-CAD-HA for tumor drug delivery, so it could be proposed as a new carrier for anticancer agents to minimize adverse effects and improve therapeutic efficacy.

Insight into the key factors for the tetracycline removal in biochar-mediated oxidative system

This study prepared pomelo peel biochar (PBC) under different pyrolysis temperatures (T) (300–800 °C) and investigated the removal efficiency of tetracycline (TC) under the oxidative systems established by PBC and oxidants (hydrogen peroxide (H2O2), peroxymonosulfate (PMS), and peroxydisulfate (PDS)). The correlation between the properties of PBC and the removal efficiencies of TC was studied by Pearson analysis to clarify the critical properties of biochar in catalytic processes. The inorganic carbon (IC), ash, pH, basic functional groups (BFG), specific surface area (SSA), microporous surface area (Smicro), pore volume (PV), and graphitization degree (ID/IG) of PBC were positively correlated with the increase of T (p < 0.05). Notably, the SSA and PV of PBC increased from 4.294 m2/g and 0.002 cm3/g to 496.864 m2/g and 0.261 cm3/g as the pyrolysis temperature increased from 300 to 800 °C. In contrast, the yield, organic carbon (OC), and acidic functional groups (AFG) of PBC displayed negatively correlated with the increase of T (p < 0.05). Rad, RPBC/H2O2, RPBC/PMS, and RPBC/PDS represented the removal efficiencies of TC by PBC adsorption, PBC/H2O2, PBC/PMS, and PBC/PDS system. RPBC/H2O2, RPBC/PMS, and RPBC/PDS showed a highly positive correlation to the Rad (r = 0.965, 0.952, 0.946, p < 0.01). Rad, RPBC/H2O2, RPBC/PMS, and RPBC/PDS were positively correlated with K, Mg, ash, pH, BFG, and ID/IG (p < 0.01). There was no statistically significant correlation between persistent free radicals (PFRs) and the removal efficiencies of TC. Furthermore, SSA and PV showed positive relationships with the removal efficiencies of TC in the PBC/PMS and PBC/PDS systems, but no significant correlation with the removal efficiencies of TC in the PBC/H2O2 systems. Moreover, the catalytic behaviors and mechanisms were studied in the PBC-800 based oxidative systems. The quenching experiments and EPR spectra indicated that singlet oxygen (1O2) was the main active species. Except for 1O2, superoxide radical (O2•−) also contributed to TC removal in the oxidative systems. From the changes in used PBC-800, the disordered sp2 hybrid carbon, sp3 C–C, and pyridinic-N were the main active sites in activation.

Proton exchange membranes with functionalized sulfonimide and phosphonic acid groups for next-generation fuel cells operating at 120 °C

Proton exchange membrane fuel cells (PEMFCs) face a significant challenge when operating in high-temperature and low-humidity environments, the hydrocarbon-based polymers that are sulfonated or phosphonated can’t meet the demand for achieving high performance. Modifying perfluorosulfonyl fluoride (PFSF) through meticulous design of side-chain chemical structures and introducing functionalized sulfonimide and phosphonic acid groups. Membranes derived from a perfluorocarbon backbone and polyacid side chain structures exhibit distinct microphase separation. The sulfonimide group exhibits hyper-acidic properties, whereas the phosphonic acid group functions as proton acceptor and donor. These two groups work synergistically to establish a distinct proton transport channel. The robust adsorption between acidic functional groups and water molecules enhances the diffusion of water molecules, resulting in an increase in proton conductivity. Moreover, Density Functional Theory (DFT) calculations reveal that the phosphonic acid group of the side chain has difficulty forming anhydrides. The prepared perfluorosulfonimide-phosphonic acid (PFSNPA) proton exchange membrane demonstrates an impressive conductivity of 263 mS·cm−1 at 120 °C. In H2/Air fuel cell tests, PFSNPA achieves an outstanding output power of 1076.1 mW·cm−2 at 120 °C and 40 % RH. This study introduces a new approach for designing and fabricating proton exchange membrane materials for high-temperature fuel cells.

Role for Carboxylic Acid Moiety in NSAIDs: Favoring the Binding at Site II of Bovine Serum Albumin.

The molecular structures of nonsteroidal anti-inflammatory drugs (NSAIDs) vary, but most contain a carboxylic acid functional group (RCOOH). This functional group is known to be related to the mechanism of cyclooxygenase inhibition and also causes side effects, such as gastrointestinal bleeding. This study proposes a new role for RCOOH in NSAIDs: facilitating the interaction at the binding site II of serum albumins. We used bovine serum albumin (BSA) as a model to investigate the interactions with ligands at site II. Using dansyl-proline (DP) as a fluorescent site II marker, we demonstrated that only negatively charged NSAIDs such as ibuprofen (IBP), naproxen (NPX), diflunisal (DFS), and ketoprofen (KTP) can efficiently displace DP from the albumin binding site. We confirmed the importance of RCOO by neutralizing IBP and NPX through esterification, which reduced the displacement of DP. The competition was also monitored by stopped-flow experiments. While IBP and NPX displaced DP in less than 1 s, the ester derivatives were ineffective. We also observed a higher affinity of negatively charged NSAIDs using DFS as a probe and ultrafiltration experiments. Molecular docking simulations showed an essential salt bridge between the positively charged residues Arg409 and Lys413 with RCOO-, consistent with the experimental findings. We performed a ligand dissociation pathway and corresponding energy analysis by applying molecular dynamics. The dissociation of NPX showed a higher free energy barrier than its ester. Apart from BSA, we conducted some experimental studies with human serum albumin, and similar results were obtained, suggesting a general effect for other mammalian serum albumins. Our findings support that the RCOOH moiety affects not only the mechanism of action and side effects but also the pharmacokinetics of NSAIDs.

Preparation of Activated Biocarbons from Cones and their Potential Application for Adsorption of Antibiotics (Tetracycline).

The pine cones (PC), spruce cones (SC) and fir cones (FC) were used for biocarbons preparation. Chemical activation with sodium hydroxide was applied to prepare activated biocarbons. All the materials under investigation were characterized by the N2 adsorption, scanning electron microscopy (SEM), elemental analysis (CHNS), infrared spectroscopy (ATR FT-IR), and the Boehm's titration method. Moreover, pHpzc (the point of zero charge) was determined. It was shown that cones are a good, cheap precursor from which biocarbons with a developed porous structure, characterized by good adsorption properties, can be obtained. All the obtained adsorbents are characterized mainly by a microporous structure. Moreover, they contain both acidic and basic surface functional groups (acidic ones prevail over basic ones). The tested activated biocarbons have large specific surface area values ranging from 578 to 1182 m2 g-1. The efficacy of selected materials in the adsorption of an essential contaminant of increasing concern, tetracycline (TC), was investigated. The experimental data were described using the Langmuir and Freundlich adsorption isotherm models. The maximum adsorption capacity of the tested biocarbons ranges from 200 to 392 mg g-1. Thermodynamic studies proved that adsorption is a spontaneous and endothermic process. In summary, economical and environmentally friendly adsorbents were obtained.

Removal of antibiotics, bacterial toxicity, and occurrence of antibiotic resistance genes in secondary hospital effluents treated with granular activated carbon and the impact of preceding chlorination

This comprehensive investigation highlighted the complex adsorption behaviors of antibiotics onto granular activated carbon (GAC), the effectiveness of this adsorption in reducing bacterial toxicity, and the reduction of antibiotic resistance genes (ARGs) and antibiotic resistant bacteria (ARB) in hospital wastewater (HWW) effluents. Six GACs were characterized for their physicochemical properties, and their ability to adsorb six antibiotics in the background matrix of actual HWW was evaluated. Coconut shell-derived GAC (Co-U), which had the highest hydrophobicity and lowest content of oxygen-containing acidic functional groups, demonstrated the highest adsorption capacities for the tested antibiotics. Bacterial toxicity tests revealed that GACs could eliminate the bacterial toxicity from antibiotic intermediates present in chlorinated HWW. By contrast, the bacterial toxicity could not be removed by GACs in non-chlorinated HWW due to the greater presence of intermediate components identified by LC-MS/MS. The intraparticle diffusion coefficient of antibiotics adsorbed onto Co-U could be calculated by adsorption kinetics derived from the linear driving force model and the homogenous intraparticle diffusion model associated with the linear adsorption isotherms (0–150 μg/L). Meropenem and sulfamethoxazole exhibited the highest adsorption capacities in a single-solute solution compared to penicillin G, ampicillin, cetazidime, and ciprofloxacin. However, the greater adsorption capacities of meropenem and sulfamethoxazole disappeared in mixed-solute solutions, indicating the lowest adsorption competition. GAC can eliminate most ARGs while also promoting the growth of some ARB. Chlorination (free chlorine residues at 0.5 mg Cl2/L) did not significantly affect the overall composition of ARGs and ARB in HWW. However, the accumulation of ARGs and ARB on GAC in fixed bed columns was lower in chlorinated HWW than in non-chlorinated HWW due to an increase in the adsorption of intermediates.

Production of activated carbon from coal with H3PO4 activation for adsorption of Fe(II) and Mn(II) in acid mine drainage

Acid Mine Drainage (AMD) contains Fe(II) and Mn(II) metals, which can cause environmental pollution. This research aimed to investigate the potency of activated carbon made from coal as an adsorbent in AMD treatment. The carbon was made of coal and activated with H3PO4 in a weight ratio of 40%, 800 °C for 120 minutes while supplying 1.5 L/min of nitrogen during the carbonization process. The result shows that BET surface area, total pore volume, and iodine number were 296.4 m2/g, 0.156 cc/g, and 1205 mg/g, respectively. The surface contained many fractures, channels, and big holes, as evidenced by the FT-IR and SEM investigations, and it also had acidic surface functional groups. The optimum contact time adsorption for AMD treatment was 30 minutes, and the first concentration of Fe(II) and Mn(II) metals affected the adsorption. The optimum removal of Fe(II) in AMD treatment was 95.27% at an initial concentration of 3.51 ppm, while the optimum removal of Mn(II) was 99.82% at an initial concentration of 5.71 ppm. This activated carbon has a considerable potency to be used as the adsorbent in AMD treatment to reduce Fe(II) and Mn(II) levels.

Room-Temperature Copper-Catalyzed Etherification of Aryl Bromides.

We disclose the development of a Cu-catalyzed C-O coupling method utilizing a new N1,N2-diarylbenzene-1,2-diamine ligand, L8. Under optimized reaction conditions, structurally diverse aryl and heteroaryl bromides underwent efficient coupling with a variety of alcohols at room temperature using an L8-based catalyst. Notably, the L8-derived catalyst exhibited enhanced activity when compared to the L4-based system previously disclosed for C-N coupling, namely the ability to functionalize aryl bromides containing acidic functional groups. Mechanistic studies demonstrate that C-O coupling utilizing L8 ⋅ Cu involves rate-limiting alkoxide transmetallation, resulting in a mechanism of C-O bond formation that is distinct from previously described Pd-, Cu-, or Ni-based systems. This lower energy pathway leads to rapid C-O bond formation; a 7-fold increase relative to what is seen with other ligands. The results presented in this report overcome limitations in previously described C-O coupling methods and introduce a new ligand that we anticipate may be useful in other Cu-catalyzed C-heteroatom bond-forming reactions.

Whole soil fatty acid lipidic signature discriminates agriculture intensification in no-till systems

Argentinean farmers are adopting alternative agricultural systems based on diversification and intensification of crop rotations in no-till agriculture in order to improve soil health and recover degraded soils after years of monocropping. This is achieved by reducing fallow periods, increasing the intensity of crop rotations with maize and soybean in summer, and establishing different winter crops, including cover crops. We evaluated whole soil fatty acids (WSFA) signature in agricultural cropping systems with different levels of intensification in three on-farm experiments in Argentinean Argiudolls soils, along an on-field 8-year assay and measuring at 5 and 8 years after the beginning of the intensification. Contrasted treatments were: typical rotation, intensified rotation with cereals and intensified rotation with legumes. They were compared to an implanted pasture, and a pasture converted to intensified rotation. Eight years after the beginning of the trial, the intensified crop rotations were separated from the typical rotation by multivariate analysis of WSFA. This technique was able to distinguish between agricultural treatments with subtle differences in management, separating the intensified rotations, which later showed higher crop productivity. Conversion of pasture back to agriculture showed a delay of three years before changing the lipidic signature according to WSFA-based indicators. The outstanding conclusion is that mono-unsaturated fatty acids (MUFA) are the most relevant fatty acid functional group for land use discrimination, with a similar potency to the whole lipidic pattern. Within the MUFA group, the fatty acids 16:1w5c and 18:1w5c, appeared as potential biomarkers of these alternative agricultural practices.

Room‐Temperature Copper‐Catalyzed Etherification of Aryl Bromides

AbstractWe disclose the development of a Cu‐catalyzed C−O coupling method utilizing a new N1,N2‐diarylbenzene‐1,2‐diamine ligand, L8. Under optimized reaction conditions, structurally diverse aryl and heteroaryl bromides underwent efficient coupling with a variety of alcohols at room temperature using an L8‐based catalyst. Notably, the L8‐derived catalyst exhibited enhanced activity when compared to the L4‐based system previously disclosed for C−N coupling, namely the ability to functionalize aryl bromides containing acidic functional groups. Mechanistic studies demonstrate that C−O coupling utilizing L8 ⋅ Cu involves rate‐limiting alkoxide transmetallation, resulting in a mechanism of C−O bond formation that is distinct from previously described Pd‐, Cu‐, or Ni‐based systems. This lower energy pathway leads to rapid C−O bond formation; a 7‐fold increase relative to what is seen with other ligands. The results presented in this report overcome limitations in previously described C−O coupling methods and introduce a new ligand that we anticipate may be useful in other Cu‐catalyzed C‐heteroatom bond‐forming reactions.

High‐Adhesion, Weather Resistance, Reusable PAM/Gly/Gel/TA/Fe3+ Biopolymer Dual‐Network Conductive Hydrogel for Flexible Bioelectrode

AbstractConductive hydrogel is considered a promising wearable sensor material. Developing flexible conductive hydrogel sensors with stretchability, adhesion, and stability remains challenging. In this study, a transparent, self‐adhesive, antifreeze, anti‐UV, stretchable, conductive, and reusable hydrogel with polyacrylamide/glycerol/gelatin/tannic acid/Fe3+ (PGGT‐Fe3+) structure is successfully constructed through a simple one‐pot polymerization method. The PGGT‐Fe3+ hydrogel is composed of dual networks of polyacrylamide and gelatin for organic cross‐linking, using water/glycerol as the dispersion medium, and incorporates a viscous substance: tannic acid, and a conductive substance: metal ions (Fe3+). Due to the introduction of the abundant amino, carboxylic acid, and hydroxyl functional groups on gelatin and tannic acid, the PGGT‐Fe3+ hydrogel exhibits excellent and repeatable adhesion capabilities on various surfaces (including glass, metal, plastic, and pigskin) with maximum adhesion strength of 98 kPa when attached to pigskin. Furthermore, based on the stable conductive network and high conductivity, the hydrogel not only exhibits strain sensitivity, fast response, and stability but also can stably collect epidermal bio signals. In conclusion, this work provides a new approach to the design and development of next‐generation multifunctional conductive hydrogels and opens up vast possibilities for their applications in the flexible electronics field.