H-bond Formation Research Articles

Quantum Chemical NMR Spectroscopic Structural Analysis in Solution: The Investigation of 3-Indoleacetic Acid Dimer Formation in Chloroform and DMSO Solution.

We present a DFT-PCM NMR study of 3-indoleacetic acid (3-IAA), used as a working example, including explicit solvent molecules, named PCM-nCHCl3, PCM-nDMSO (n = 0, 2, 4, 8, 14, 20, and 25), to investigate the dimer formation in solution. Apart from well-known cyclic (I) and open (II) acetic acid (AA) dimers, two new structures were located on DFT-PCM potential energy surface (PES) for 3-IAA named quasicyclic A (III) and quasicyclic B (IV), the last one having N-H…O hydrogen bond (instead of O-H…O). In addition, four other structures having π-π type interactions named V, VI, VII, and VIII were also obtained completing the sample on the PES. Our theoretical results and experimental 1H NMR data (CDCl3) strongly indicate that 3-IAA should exist in a quasicyclic form (III) in a chloroform solution different from AA. Solute-solvent interactions play a key role in O-H and N-H chemical shifts. The strong H-bond formation between the S=O and O-H and N-H groups produces large chemical shift value THAT masquerades the identification of dimer formation in DMSO solution based on 1H NMR chemical shift changes. However, analysis of 13C NMR and relative energy DFT-PCM-nDMSO results strongly indicate the presence of parallel ring interacting dimer having OH…benzene ring bond (VI). There can be a competition between solute-solute and solute-solvent interactions, and polar DMSO solvent can break the quasicyclic dimers (III and IV) intermolecular O-H…O and N-H…O bonds yielding two solvated monomeric species hydrogen bonded to O=S(CH3)2 groups, what may take place for other organic molecules in solution. However, it did not happen for the π-π interacting dimers and structure VI survived in DMSO solution.

A Unique Case of 'in Situ' Bifluoride Triggered Formation of Supramolecular Organogels Using Isophthalamide Hydrogen Bond Donating Receptors.

A novel isopthalamide based receptor H2L2 featuring two p-benzoic acid units has been synthesised and its anion binding properties analysed by 1H-NMR spectroscopy in DMSO-d6/0.5 % H2O. As expected, in the presence of tetrabutylammonium (TBA) fluoride the deprotonation of the carboxylic acid moieties was observed. However, the deprotonated receptor L22- was able to bind the in situ formed HF2 - via the formation of H-bonds with the amide NHs. When H2L2 was dissolved in THF and 4 equivalents of TBAF were added in CH3CN a unique sol-gel transition occurred giving rise to a stable thixotropic supramolecular gel. Theoretical calculations elucidated the gelation mechanism and strongly support the findings observed experimentally.

Resveratrol-Based Carbamates as Selective Butyrylcholinesterase Inhibitors: Design, Synthesis, Computational Study and Biometal Complexation Capability.

Considering our previous experience in the design of new cholinesterase inhibitors, especially resveratrol analogs, in this research, the basic stilbene skeleton was used as a structural unit for new carbamates designed as potentially highly selective butyrylcholinesterase (BChE) inhibitors with excellent absorption, distribution, metabolism, excretion and toxicity ADMET properties. The inhibitory activity of newly prepared carbamates 1-13 was tested toward the enzymes acetylcholinesterase (AChE) and BChE. In the tested group of compounds, the leading inhibitors were 1 and 7, which achieved excellent selective inhibitory activity for BChE with IC50 values of 0.12 ± 0.09 μM and 0.38 ± 0.01 μM, respectively. Both were much more active than the standard inhibitor galantamine against BChE. Molecular docking of the most promising inhibitor candidates, compounds 1 and 7, revealed that stabilizing interactions between the active site residues of BChE and the ligands involve π-stacking, alkyl-π interactions, and, when the carbamate orientation allows, H-bond formation. MD analysis confirmed the stability of the obtained complexes. Some bioactive resveratrol-based carbamates displayed complex-forming capabilities with Fe3+ ions as metal centers. Spectrophotometric investigation indicated that they coordinate one or two metal ions, which is in accordance with their chemical structure, offering two binding sites: an amine and a carboxylic group in the carbamate moiety. Based on the obtained in silico, experimental and computational results on biological activity in the present work, new carbamates 1 and 7 represent potential selective BChE inhibitors as new therapeutics for neurological disorders.

Competition between C-H⋯S and S-H⋯Cl H-bonds in a CHCl3-H2S complex: a combined matrix isolation IR spectroscopic and quantum chemical investigation.

H-bonded complexes between CHCl3 and H2S have been studied in a cold and inert argon matrix using IR spectroscopy. Both molecules were found to act as both a H-bond donor and acceptor, resulting in two different conformers. The more stable one (binding energy 3.25 kcal mol-1) was bound by a C-H⋯S H-bond, while the less stable one (1.90 kcal mol-1) by a S-H⋯Cl H-bond. The H-bonded complex formation has been confirmed by monitoring the spectral changes in νC-H and νS-H fundamental vibrations. The νC-H mode exhibited red shifts by 22.7 cm-1 upon C-H⋯S H-bond formation, while the formation of a S-H⋯Cl H-bond resulted in 24.2 and 25.4 cm-1 red shifts in the νS-H modes. The barrier for conversion of the less stable conformer to the more stable one was found to be 0.6 kcal mol-1. The rigid matrix environment prevented any detectable population transfer that required significant relative movement of the monomeric moieties. Dispersion interaction was found to significantly contribute to the overall stabilization of both conformers, more so for the S-H⋯Cl H-bonded one.

Extraction Mechanism of Hesperidin from Citrus aurantium L. Using a Novel Deep Eutectic Solvent: Experimental and Theoretical Investigation

In order to extract hesperidin from Citrus aurantium L. through green and efficient ways, a novel method based on deep eutectic solvent (DES) assisted extraction has been developed. Compared to known alkali extraction and acid precipitation or organic solvent (ethanol, methanol) extraction, this new DES system of choline chloride/diethanolamine (DES-14) method exhibited excellent extraction efficiency for hesperidin. Under optimal conditions, the extraction yield of hesperidin reached 6.26 ± 0.05%. Further studies with infrared spectroscopy, 1 H nuclear magnetic resonance, and density functional theory showed the DES-14 was formed mainly through the interaction of H-bond and van der Waals forces. In addition, scanning electron microscopy and density functional theory revealed the strong dissolving capacity, and the H-bond formation between DES-14 and hesperidin, as well as van der Waals forces all contributed to efficient extraction of hesperidin. The results provide a new strategy for efficient extraction and utilization of hesperidin in Citrus.

Efficient and Visual Detention of Ammonia and TNP Vapors by a Sustainable Highly Luminescent 1D Zn(II) Coordination Polymer.

To realize the aim of easy and accurate detection of ammonia and picric acid (PA) in both aqueous and vapor phases based on function-oriented investigation principles, in the present study, we include a luminescent performance with recognition performance, taking into account the application conditions. Zn(II) ions with luminescence qualities and an amine-substituted imidazole moiety with selective recognition properties towards picric acid and ammonia are coupled to generate a novel 1D luminous Zn(II) coordination polymer, Zn-CP [{Zn(II)( 2-ABZ)2(2-BDC)}].MeOH]∞, where 2-ABZ and 2-BDC stand for terephthalic acid and protonated 2 aminobenzimidazole, respectively. Tests for luminescence recognition demonstrate that Zn-CP has potent selectivity, and strong sensitivity to ammonia and PA in both media. In both detection processes, the limit of detection (LOD) values are determined to be 40 nm. Spectroscopic and DFT studies reveal that the detection of Trinitrophenol (TNP) primarily involves a synergistic mechanism of Photoinduced Electron Transfer (PET), Fluorescence Resonance Energy Transfer (FRET), and Charge Transfer (CT). In contrast, the detection of ammonia (NH3) vapor is predominantly driven by hydrogen bonding (H-bonding) formation. The constructed 1D luminous Zn-CP is a new material that guides the development of novel luminous sensors in the future.

Inter- and Intra-Molecular Charge Redistributions in H-Bonded Cyanuric Acid*Melamine (CA*M) Networks: Insight From Core Level Spectroscopy and Natural Bond Orbital Analysis.

In this work, we elucidate the electronic charge redistributions that occur within the cyanuric acid (CA) and melamine (M) molecules upon formation of the triple H-bond between the imide group of CA and the diaminopyridine group of M. To achieve this, we investigated 2D H-bonded assemblies of M, CA and CA*M grown on the Au(111) surface, using X-ray photoemission (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectroscopies. Compared to the homomolecular networks, the spectra of the mixed sample reveal core level shifts in opposite directions for CA and M, indicating a nearly complementary charge accumulation on the CA molecule and a charge depletion on the M molecule. These findings were further confirmed by theoretical simulation of the ionization potentials (IPs), which were computed using unsupported models of the H-bonded networks. A natural bond orbital (NBO) analysis performed on the three systems helped to rationalize the net charge transfer form M to CA. Finally, we observed that intramolecular interactions (electron delocalization effects) contribute progressively to the charge redistributions inside the two molecules when going from the homomolecular to the heteromolecular networks.

Thermal and optical characterization of hydrogen bond liquid crystals: experimental and DFT approach

A novel hydrogen bond liquid crystal (HBLC) homologous series has been isolated from the combination of 1,2,3,4-butanetetra carboxylic acid (BTCA) and 4-n-alkyloxybenzoic acids (nOBA, n = 4–12). FTIR study confirms the formation of cyclic H-bond of the BTCA + nOBA, HBLC complexes by observing the peak at 3582 cm−1. Induced mesogenic phases, transition temperatures and their enthalpy values are analyzed using POM and DSC. The formation of H-bonds and increasing alkyloxy chain length greatly influence the LC parameters in the title complexes. DFT calculations (HOMO-LUMO, MEP, Mulliken charge and RDG) validate the experimentally observed result.

Methylophiopogonanone A Inhibits Ferroptosis in H9c2 Cells: An Experimental and Molecular Simulation Study.

In this study, homoisoflavone methylophiopogonanone A (MOA) was investigated for its inhibitory effect on ferroptosis of H9c2 cells using a set of cellular assays, such as BODIPY-probed and H2DCFDA-probed flow cytometry analyses, cell counting kit-8 analysis (CCK-8), and lactate dehydrogenase (LDH) release analysis. All these cellular assays adopted Fer-1 as the positive control. Subsequently, MOA and Fer-1 were subjected to two antioxidant assays, i.e., 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide radical (PTIO•)-scavenging and 2,2'-azinobis(3-ethylbenzo-thiazoline-6-sulfonic acid radical (ABTS•+)-scavenging. Finally, MOA, along with Fer-1, were systematically analyzed for molecular docking and dynamics simulations using a set of software tools. The experimental results revealed that MOA could inhibit ferroptosis of H9c2 cells but did not effectively scavenge PTIO• and ABTS•+ free radicals. Two molecular simulation methods or algorithms suggested that MOA possessed similar binding affinity and binding free energy (∆Gbind) to Fer-1. Visual analyses indicated various hydrophobic interactions between MOA and one of the seven enzymes, including superoxide dismutase (SOD), dihydroorotate dehydrogenase (DHODH), ferroportin1 (FPN), ferroptosis suppressor protein 1 (FSP1), glutathione peroxidase 4 (GPX4), nicotinamide adenine dinucleotide phosphate (NADPH), and solute carrier family 7 member 11 (SLC7A11). Based on these experimental and molecular simulation results, it is concluded that MOA, a homoisoflavonoid with meta-di-OHs, can inhibit ferroptosis in H9c2 cells. Its inhibitory effect is mainly attributed to the regulation of enzymes rather than direct free radical scavenging. The regulation of enzymes primarily depends on hydrophobic interactions rather than H-bond formation. During the process, flexibility around position 9 allows MOA to adjust to the enzyme binding site. All these findings provide foundational information for developing MOA and its derivatives as potential drugs for myocardial diseases.

A novel g-C3N4/TiO2 heterojunction for ultrasensitive detection of bisphenol A residues

Semiconductor heterojunction with functional integration can be used as an excellent matrix for the ultrasensitive detection of bisphenol A (BPA) with low molecular affinity. Here, a simple, low-cost and sensitive surface-enhanced Raman scattering (SERS) strategy using g-C3N4/TiO2 heterojunction as substrate was presented for detection of BPA residues in foods. The g-C3N4/TiO2 achieved specific chemisorption for target analyte by the formation of intermolecular H-bond between g-C3N4 and BPA. And, a high-efficiency carrier separation in TiO2 induced by heterostructure could be achieved for charge transfer between the substrate and molecule by a “donor-bridge-acceptor” charge-transfer mode. Due to the synergistic/collaborative contributions of two monomers in heterojunction, the SERS enhancement factor was as high as 3.77 × 107. The detection limit of BPA residues in foods (milk, juice and drinking water) was as low as 10−9 mol·L−1, far below the EU standard. The developed substrate also exhibited excellent stability and anti-interference capability.

Experiment-based Abraham model solute descriptors for 2‑[4-(dibutylamino)-2-hydroxybenzoyl]benzoic acid

ABSTRACT Abraham model solute descriptors for 2‑[4-(dibutylamino)-2-hydroxybenzoyl]benzoic acid were determined from the compound’s published solubility data in 10 organic solvents of varying polarity and hydrogen-bonding character. The calculated hydrogen-bond donor descriptor value, A = 0.548, suggests that intramolecular bond formation occurs between the hydrogen atom on the -OH functional group and one of the two lone pairs of electrons on the oxygen atom of the ketone functional group, >C=O, which would result in the formation of a six-membered hydrogen-bonded ring structure. A much larger A-solute descriptor would be expected if the hydrogen atoms of both the -OH and -COOH functional groups were free to engage in intermolecular H-bond formation with surrounding solvent molecules.

Tuning the Protonation Sensitivity of Weak Acidic Groups on a Zwitterionic Dendrimer for Selectively Targeting GD2-Overexpressed Tumor Cells in an Acidic Tumor Microenvironment.

Disialoganglioside (GD2) is one of the most popular overexpressed antigens for tumor cell targeting. However, GD2-specific antibodies often show unintended targeting to GD2-expressing health-maintaining cells due to the comparable binding affinities both at physiological pH and in a slightly acidic tumor microenvironment (TME). In this work, an affinity-switchable zwitterionic PAMAM G5 dendrimer (G5-3S) is developed for selective binding to GD2 only in a slightly acidic TME. It has 3 sulfonic groups, 128 carboxylic groups, and 125 amino groups on the surface. This affinity switch is realized by multiple hydrogen bond (H-bond) formation between protonated carboxylic groups surrounding a sulfonic group and overexpressed GD2 clusters on the tumor cell membrane in the slightly acidic TME, whereas there is no stable H-bond formation at physiological pH. Thus, G5-3S shows superior selectivity to GD2-overexpressed tumor cells over anti-GD2 antibodies by avoiding targeting GD2-expressing health-maintaining cells at physiological pH. This suggests that G5-3S is a promising candidate for GD2-overexpressed cancer treatment.

Photo-activation of Tolane-based Synthetic Ion Channel for Transmembrane Chloride Transport.

While natural channels respond to external stimuli to regulate ion concentration across cell membranes, creating a synthetic version remains challenging. Here, we present a photo-responsive uncaging technique within an artificial ion channel system, which activates the ion transport process from a transport-inactive o-nitrobenzyl-based caged system. From the comparative ion transport screening, 1 b emerged as the most active transporter. Interestingly, its bis(o-nitrobenzyl) derivative, i.e., protransporter 1 b' was inefficient in transporting ions. Detailed transport studies indicated that compound 1 b is an anion selective transporter with a prominent selectivity towards chloride ions by following the antiport mechanism. Compound 1 b' did not form an ion channel, but after the o-nitrobenzyl groups were photocleaved, it released 1 b, forming a transmembrane ion channel. The channel exhibited an average diameter of 6.5±0.2 Å and a permeability ratio of . The geometry-optimization of protransporter 1 b' indicated significant non-planarity, corroborating its inefficient self-assembly. In contrast, the crystal structure of 1 b demonstrates strong self-assembly via the formation of an intermolecular H-bond. Geometry optimization studies revealed the plausible self-assembled channel model and the interactions between the channel and chloride ion.

Cnicus Benedictus roots as a low-cost adsorbent for methylene blue dye removal from aqueous solution: kinetic and equilibrium studies

In this research, Cnicus Benedictus roots powder (CBRP) was utilized as a low-cost adsorbent for removing methylene blue (MB) as a cationic dye from aqueous solution. Characterization of CBRP by Boehm titration method, Fourier transform infrared (FT-IR) and environmental scanning electron microscope (ESEM) indicates the presence of different types of functional groups and a very rough surface filled with cavities, suitable for MB adsorption. The effect of various parameters such as CBRP dose (0.2–2 g/1L), contact time (0–180 min), initial pH (1–10), coexisting anions/cations and the initial MB concentration (100–500 mg L−1) on MB adsorption were examined, the results showed that MB uptake depends on the pH of solution, the electrostatic attraction forces, the formation of H-bonds and π–π interactions are the possible CBRP–MB interaction mechanisms. Adsorption kinetic of MB on CBRP was best represented by linear and non-linear form of the pseudo-second order model. The experimental equilibrium data were best described by linear and non-linear forms of Langmuir and Redlich–Peterson isotherm models (R 2> 0.98) with a maximum MB adsorption capacity of 85.47 mg g−1 at 25 °C, the adsorption efficiency R (%) was greater than 90 (%). MB adsorption-desorption experiments showed the reusability of CBRP for five consecutive cycles. According to the obtained results, CBRP can be used as a natural adsorbent material for cationic dyes removal from aqueous solution.

Investigation on induced smectic phases in double hydrogen bond liquid crystal complexes derived from aromatic carboxylic acids: Experimental and quantum chemical approaches

In the present study, double Hydrogen bond liquid crystal (HBLC) complexes in different mole ratio (1:1 and 1:2) have been isolated from symmetrical aromatic dicarboxylic acid of non-mesogenic compound 1,3-Phenylenediacetic acid (1,3-PDA) and mesogenic compound 4-n-dodecyloxybenzoic acid (12 OBA). Fourier transform infrared Spectroscopy (FTIR) explores the presence of functional groups in the title complexes. Formation of H-bond between 1,3-PDA and 12 OBA is experimentally confirmed by observing the FTIR peak at 3639 cm−1 (1:1 ratio). Induced mesophases and its textures along with transition temperatures are analyzed using polarizing optical microscope (POM) and differential scanning calorimetry (DSC). The layered structures (smectic phases) and their molecular mechanism has been analyzed using density functional theory (DFT). Further, the establishment of H-bond in the title complex has been investigated with the aid of optimized geomentry, molecular electrostatic potential (MEP) and reduced density gradient (RDG) analysis. The band gap energy of title complex (1:1) is calculated by UV–Vis spectrometer and the same has been justified by HOMO-LUMO studies. Maximum absorption in the UV region and moderate bandgap energy (Eg = 4.22 eV) of the title complex clearly indicates its potential application in NLO, optoelectronics and laser tuning devices. In addition to that, LC parameters and its effect on mesophase are reported using experimental and computational methods.

Unveiling the impact of organic cation passivation on structural and optoelectronic properties of two-dimensional perovskites thin films

Several organic cations have been used to passivate perovskite films; however, selecting the optimal cation remains challenging. In this work, we carried out density functional theory calculations to understand the effects induced by 17 different organic cations on the passivation (P-cations) of thin two-dimensional P2 (MAn−1)PbnI3n+1 perovskites films, where n=1 and 2. We found that the interactions between different types of P-cations and the inorganic slab affect the length and angles of the bonds within the inorganic framework (PbI6-octahedra). In general, the binding mechanism includes the interactions of organic cations with the inorganic framework, which leads to the accumulation of electron density within the halides, indicative of Brønsted–Lowry acid–base interactions. Oxygenated groups facilitate additional H-bond formation through -OH and -COOH groups, promoting the localization of the electron density between layers and improving the energetic stability of the system. Based on the results and analysis, we found that three P-cations might have higher potential for real-life applications, namely 4-fluorophenylethylammonium (FPEA), phenylethylammonium (PEA) and butylammonium (BtA).

Hydrogen Bond Strengthens Acceptor Group: The Curious Case of the C-H···O=C Bond.

An H-bond involves the sharing of a hydrogen atom between an electronegative atom to which it is covalently bound (the donor) and another electronegative atom serving as an acceptor. Such bonds represent a critically important geometrical force in biological macromolecules and, as such, have been characterized extensively. H-bond formation invariably leads to a weakening within the acceptor moiety due to the pulling exerted by the donor hydrogen. This phenomenon can be compared to a spring connecting two masses; pulling one mass stretches the spring, similarly affecting the bond between the two masses. Herein, we describe the opposite phenomenon when investigating the energetics of the C-H···O=C bond. This bond underpins the most prevalent protein transmembrane dimerization motif (GxxxG) in which a glycine Cα-H on one helix forms a hydrogen bond with a carbonyl in a nearby helix. We use isotope-edited FT-IR spectroscopy and corroborating computational approaches to demonstrate a surprising strengthening of the acceptor C=O bond upon binding with the glycine Cα-H. We show that electronic factors associated with the Cα-H bond strengthen the C=O oscillator by increasing the s-character of the σ-bond, lowering the hyperconjugative disruption of the π-bond. In addition, a reduction of the acceptor C=O bond's polarity is observed upon the formation of the C-H···O=C bond. Our findings challenge the conventional understanding of H-bond dynamics and provide new insights into the structural stability of inter-helical protein interactions.

Metformin-Induced Invertase Unfolding: Enzyme Kinetics and Activity Regulation.

The effects of metformin on invertase activity and its inhibition on sucrose digestion were studied. The rapid unfolding kinetics of invertases, followed a two-state model with an inactive intermediate formation. The dynamic interaction between metformin and invertase caused the secondary structure of the enzyme to become less β-sheet, more α-helix, and random coiling oriented, which weakened the binding force between enzyme and its substrate. Metformin acted as a chaotrope and disrupted the hydrogen bonds of water, which facilitated the unfolding of invertase. However, some sugar alcohols, which promoted the H-bond formation of water, could repair the secondary structure of metformin-denatured invertase and therefore regulate the enzyme activity. This research enriches our understanding of the mechanism of enzyme unfolding induced by guanidine compounds. Moreover, because metformin and sugar substitutes are of concern to diabetes, this research also provides useful information for understanding the activity of the digestive enzyme that coexists with metformin and sugar alcohols.

Modification of biodegradable thermoplastic cassava starch/kapok fiber incorporated by tartaric acid and processed by compression molding technique

Thermoplastic starch has been attracted due to its availability, biodegradability, and processability. However, its poor tensile properties, high hydrophilicity and lack of antibacterial activity are still the major concerns for many applications. In current study, several thermoplastic cassava starch samples (THPCS), reinforced with kapok (KP) fibers and modified by varying levels of tartaric acid (TA), a natural organic acid, were prepared to enhance their limitations. All samples were mixed and shaped using an internal mixer and a compression molding machine, respectively. The modified THPCS samples were characterized using analytical techniques such as FTIR, SEM and TGA. Morphology, water uptake, mechanical properties, biodegradability, and antimicrobial performance of various samples were also evaluated. IR peak positions of O–H stretching as well as O–H bending were clearly observed for shifting to lower wavenumbers with the addition of KP fibers or KP fibers/TA, indicating of new H-bond formation. In addition, the use of KP fibers caused the enhancement of mechanical strength and thermal properties including the reduction of water uptake. Moreover, THPCS/KP fiber sample modified by TA presented surface smoothness, good biodegradability, and antibacterial performance against both Staphylococcus aureus and Escherichia coli.

New insights into the role of nitrogen doping in microporous carbon on the capacitive charge storage mechanism: From ab initio to machine learning accelerated molecular dynamics

Fundamental understandings of the relationship between ion-electrode interaction and structural feature in porous carbon electrodes at a molecular level provides guidelines for the design of high-performance electric double layer supercapacitors. It is certified by experiments that porous carbon structures doped with nitrogen show enhanced capacitive performance. However, in the theoretical simulations, the fundamental charge storage mechanism is still elusive. In particular, the recent experimental result shows that the generally ignored nitrolic nitrogen (N5) in porous carbon exhibits a positive effect on capacitance, while graphitic nitrogen (N3) does the opposite, which is against with the simulation results based the 2D-modeled porous graphene structure. Here, we perform ab initio molecular dynamics simulations on the N3 and N5-doped carbon/electrolyte interfaces, including both 2D planar and 3D microporous carbon electrodes. Our calculation indicates that N3 in the 3D pore hinders the electrolyte transport, while N5-doped micropore still serves as an electrolyte transport channel through the formation of H-bond. The charge storage mechanism is further elucidated by the analysis of the well equilibrated interfaces obtained from the machine learning force field accelerated molecular dynamics. Our work provides a new insight into the effect of nitrogen doping in 3D porous carbon, which is exactly opposite to the 2D planar graphene. Therefore, we emphasize that differences in the electrochemical conditions of 2D planar and 3D microporous carbon electrodes should be fully considered when analyzing the effects of surface chemistry on charge storage mechanisms.