Bond Formation Research Articles

Self-promoted Controlled Ring-opening Polymerization via Side Chain-mediated Proton Transfer for the Synthesis of Tertiary Amine-pendant Polypeptoids.

Proton transfer is essential in virtually all biochemical processes, with enzymes facilitating this transfer by optimizing the proximity and orientation of reactants through site-specific hydrogen bonds. Proton transfer is also crucial in the rate-determining step for the ring-opening polymerization of N-carboxyanhydrides (NCAs), widely used to prepare various peptidomimetic materials. This study utilizes side chain-assisted strategy to accelerate the rate of chain propagation by using NCAs with tertiary amine pendants. This moiety enables hydrogen bond formation between the incoming NCA and the polymer amino growing end. The tertiary amine side chain of the NCA forms a proton shuttle, via a less constrained transition state, to facilitate the proton transfer process. Moreover, the tertiary amine side chains enable the precipitation of NCA monomers through in situ protonation during the monomer synthesis. This greatly facilitates the synthesis of these unreported monomers, allowing the direct controlled synthesis of tertiary amine-pendant polypeptoids. This side chain-promoted polymerization has rarely been reported. Additionally, the tertiary amine side chains, as widely used functional groups, endow the polymers with unique properties including pH- and thermo-responsiveness, tunable pKas, and siRNA transfection capability. The self-promoted synthesis, facile monomer preparation, and attractive properties make tertiary amine-pendant polypeptoids promising materials for various applications.

Benzylic C-H Radical Sulfation by Persulfates.

Sulfation is a highly valuable pathological and physiological process, yet it is often underappreciated considering the rather difficult accessibility of organosulfates. O-sulfonation (O-SO3), a conventional and still common way to make organosulfates, restricts its applicability to hydroxyl compounds and therein lies a major challenge of library construction. Here, we describe a benzylic C-H radical sulfation with persulfates via C-O bond formation. This strategy leverages modular control over the reactivity of persulfates and the stability of sulfate radicals by coutercations. K+/NH4+ stabilized sulfate radicals act as the oxidant to generate carbon-centered radicals from substrates, and activation of persulfates by NBu4+ provides O-O resource pool to facilitate C-OSO3- bond formation via a bimolecular homolytic substitution (SH2) process.

A Covalent Triazine Framework for Photocatalytic Anti-Markovnikov Hydrofunctionalizations.

Porous materials-based heterogeneous photocatalysts, performing selective organic transformations, are increasing the applicability of photocatalytic reactions due to their ability to merge traditional photocatalysis with structured pores densely decorated with catalytic moiety for efficient mass and charge transfer, as well as added recyclability. We herein disclose a porous crystalline covalent triazine framework (CTF)-based heterogeneous photocatalyst that exhibits excellent photoredox properties for different hydrofunctionalization reactions such as hydrocarboxylations, hydroamination and hydroazidations. The high oxidizing property of this CTF enables the activation of styrenes, followed by regioselective C-N and C-O bond formation at ambient conditions. A change in the physicochemical and optoelectronic properties of the CTF, upon protonation during catalysis, lies at the basis of its photocatalytic properties. This allows us to obtain hydrocarboxylations, hydroamination, and hydroazidations from a myriad of electron-donating and -withdrawing aromatic and aliphatic substrates. This catalytic approach is further extended to late-stage functionalization of bio-active molecules. Finally, detailed characterizations of the CTF and further mechanistic investigations provides mechanistic insights in these reactions.

Inducing disulfidptosis in tumors:potential pathways and significance.

Regulated cell death (RCD) is crucial for the elimination of abnormal cells. In recent years, strategies aimed at inducing RCD, particularly apoptosis, have become increasingly important in cancer therapy. However, the ability of tumor cells to evade apoptosis has led to treatment resistance and relapse, prompting extensive research into alternative death processes in cancer cells. A recent study identified a novel form of RCD known as disulfidptosis, which is linked to disulfide stress. Cancer cells import cystine from the extracellular environment via solute carrier family 7 member 11 (SLC7A11) and convert it to cysteine using nicotinamide adenine dinucleotide phosphate (NADPH). When NADPH is deficient or its utilization is impaired, cystine accumulates, leading to the formation of disulfide bonds in the actin cytoskeleton, triggering disulfidptosis. Disulfidptosis reveals a metabolic vulnerability in tumors, offering new insights into cancer therapy strategies. This review provides a detailed overview of the mechanisms underlying disulfidptosis, the current research progress, and limitations. It also highlights innovative strategies for inducing disulfidptosis and explores the potential of combining these approaches with traditional cancer therapies, particularly immunotherapy, to expedite clinical translation.

Comparative Bindings of Glycosaminoglycans with CXCL8 Monomer and Dimer: Insights from Conformational Dynamics and Kinetics of Hydrogen Bonds.

GAGs bind to both the monomeric and dimeric forms of CXCL8, helping to form a concentration gradient of the chemokine that facilitates the recruitment of neutrophils to an injury site and supports other biological functions. In this study, atomistic molecular dynamics simulations were conducted to investigate the binding behavior of two hexameric GAGs sulfated at two different positions, chondroitin sulfate (CS) and heparan sulfate (HS), with the monomer (SIL8) and dimer (DIL8) forms of the CXCL8 protein. The results support that the conformational diversity of CS and HS appeared to be more when binding with monomer SIL8 than dimer DIL8. CS gained more configurational entropy from glycosidic linkage flexibility when bound to SIL8 than DIL8, with a higher energy barrier, whereas HS exhibited a lower energy barrier for configurational entropy when bound to SIL8 and DIL8. The monomer SIL8 exhibited more favorable and preferential binding with GAGs compared to DIL8. Formation of hydrogen bonds with the basic amino acids of SIL8 and GAG was more rigid and required higher activation energy to break than the other identified hydrogen bondings. Water molecules involved in hydrogen bonding with GAGs, excluding those with basic amino acids of DIL8, showed longer lifetimes and slower relaxation compared to SIL8. This suggests that water-mediated interactions also favor binding of DIL8 with GAGs. Despite having more basic amino acids, DIL8 did not display stronger binding than SIL8, indicating the significant role of basic residues in stabilizing the GAG-protein interactions in the monomers. The reason could be that the greater number of nonbasic amino acids in dimeric CXCL8 stabilizes the complex by forming water-mediated hydrogen bonds, reducing the conformational preferences for binding with GAGs. In contrast, the monomeric form of CXCL8 exhibits a higher conformational preference for protein-GAG interactions.

One‐Pot Reactions of Ynones with Isothiocyanates for Accessing 2‐Aminothiophenone and Indole‐Fused/Indole‐Substituted Thiophenone Derivatives

AbstractA copper or silver‐catalyzed cascade addition/5‐exo‐dig cyclization/isomerization reaction of isothiocyanate with ynone has been developed. This strategy enables the synthesis of a variety of (Z)‐2‐ylidene‐5‐aminothiophen‐3‐one derivatives with diverse substitutions in a single vessel. The method is featured with pot‐economy as well as regio‐ and Z‐selectivity. Several biologically active molecules could be modified using this strategy. Moreover, the relevant indole‐fused and indole‐substituted thiophenone derivatives were also assembled in one pot by merging this strategy with other bond formation methods. Based on the experiments and the related reports, a cascade pathway triggered by the addition of ynone‐derived radical towards the C(sp)‐atom of isothiocyanate was proposed to elucidate the probable process of the transformation.

Photocatalytic C(sp3)-P and C(sp2)-P Bond Formation via a Phosphorus Radical Cation.

A straightforward method for the phosphorylation of electron-deficient alkenes and aryl alkynes has been developed, leading to C(sp3)-P and C(sp2)-P bond formation. This process involves the generation of phosphorus radical cation intermediates through the photocatalyzed oxidation of ethyl diarylphosphinites. The coupling with electron-deficient alkenes encompasses a variety of heteroaromatics, including pyridine, (benzo)thiazole, and benzoxazole, as well as α,β-unsaturated esters and amides. Impressively, the coupling of radical cations with aryl alkynes demonstrated remarkable regioselectivity, thereby facilitating the synthesis of rare α-aryl vinyl phosphine oxides.

A Voltage-Controlled Strategy for Modular Shono-Type Amination.

Shono-type oxidation to generate functionalized heterocycles is a powerful method for late-stage diversification of relevant pharmacophores; however, development beyond oxygen-based nucleophiles remains underdeveloped. The limited scope can often be ascribed to constant current electrolysis resulting in potential drifts that oxidize a desired nucleophilic partner. Herein, we report a voltage-controlled strategy to selectively oxidize a broad scope of substrates, enabling modular C-N bond formation from protected amine nucleophiles. We implement an electroanalytically guided workflow using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) to identify oxidation potentials across a range of heterocyclic substrates. Controlled potential electrolysis (CPE) selectively generates α-functionalized C-N products in moderate to good yields using carbamate-, sulfonamide-, and benzamide-derived nucleophiles. The importance of voltage control is further exemplified through a systematic study comparing our developed CPE method to constant current electrolysis (CCE) protocols. Voltage-guided CCE and traditionally optimized CCE reveal the importance of maintaining voltage control for high yields and selectivity over a broad scope; a case study with a morpholine-derived substrate illustrates the negative impact of potential drifting under CCE. Sulfonamide drugs, which have significant oxidation potential overlap with model substrates, are rendered competent nucleophiles under CPE. Lastly, sequential voltage-controlled C-N and C-O functionalization of a model substrate generates difunctionalized pyrrolidines further broadening the utility of this reaction.

Formal Transformation of Benzylic Carboxylic Acids to Phenols.

Phenols play a crucial role as core structural motifs in natural products and also serve as fundamental building blocks in synthetic chemistry. Apart from the known protocols for the conversion of aryl precursors to phenols (i.e., decarboxylative oxygenation), we report here the efficient synthesis of phenols from the stable and readily available benzylic carboxylic acids under mild reaction conditions. The photocatalytic conversion of carboxylic acids to peroxides is a crucial step in this strategy, allowing the subsequent C-O bond formation via Hock rearrangement.

A Covalent Triazine Framework for Photocatalytic Anti‐Markovnikov Hydrofunctionalizations

Porous materials‐based heterogeneous photocatalysts, performing selective organic transformations, are increasing the applicability of photocatalytic reactions due to their ability to merge traditional photocatalysis with structured pores densely decorated with catalytic moiety for efficient mass and charge transfer, as well as added recyclability. We herein disclose a porous crystalline covalent triazine framework (CTF)‐based heterogeneous photocatalyst that exhibits excellent photoredox properties for different hydrofunctionalization reactions such as hydrocarboxylations, hydroamination and hydroazidations. The high oxidizing property of this CTF enables the activation of styrenes, followed by regioselective C‐N and C‐O bond formation at ambient conditions. A change in the physicochemical and optoelectronic properties of the CTF, upon protonation during catalysis, lies at the basis of its photocatalytic properties. This allows us to obtain hydrocarboxylations, hydroamination, and hydroazidations from a myriad of electron‐donating and ‐withdrawing aromatic and aliphatic substrates. This catalytic approach is further extended to late‐stage functionalization of bio‐active molecules. Finally, detailed characterizations of the CTF and further mechanistic investigations provides mechanistic insights in these reactions.

A Facile Strategy for PEGylated Nanoprodrug of Bortezomib with Improved Stability, Enhanced Biocompatibility, pH-Controlled Disassembly, and Release.

The therapeutic efficacy of bortezomib (BTZ) is often limited due to low solubility, poor stability in vivo and nonspecific toxicity. Herein, a kind of catechol-functionalized polyethylene glycol (mPEG-CA) is first synthesized and then mPEG-CA is readily used to conjugate with BTZ by the formation of dynamic boronate bonds to obtain PEGlyated BTZ prodrug (mPEG-CA-BTZ) with the ability of pH-controlled disassembly and drug release. The structure and morphology, physicochemical characteristics, drug loading, and release as well as in vitro cytotoxicity of mPEG-CA-BTZ nanoparticles are investigated in detail. The results demonstrated that mPEG-CA-BTZ can not only self-assemble into nanostructures with uniform size and stable dispersion in physiological pH condition (pH 7.4) but also respond to the tumor acid microenvironment and achieve pH-controlled BTZ release by acid-triggered cleavage of boronate bonds, decomposition of mPEG-CA-BTZ and thus disassembly of mPEG-CA-BTZ nanoparticles. mPEG-CA-BTZ nanoparticles are expected to have great potential as a promising nanoplatform for pharmaceutical formulations of BTZ to increase therapeutic efficacy and decrease side effects of BTZ. Considering the easily available and biocompatible excipients and simple preparation process, the strategy designed herein provides a facile and promising approach to synergistically integrate the function of PEGylation and pH-sensitiveness into boronic acid-containing small molecule pharmaceutical agents.

Theoretical investigation on Friedel−Crafts reaction followed by rear-rangement/aromatization or ring-opening delivering benzoheterocycle and polycyclic alcohol, biaryl carboxylic acid

Our DFT calculations provide the first theoretical investigation on CF3SO3H-promoted [1,5]Friedel−Crafts of 2-aryoxy-1,3-indandione and base-facilitated [1,6]Friedel−Crafts of 1,3-dicarbonyl. An intramolecular [1,5]Friedel−Crafts addition took place by activating carbonyl through H bridge with CF3SO3H. The resulting tertiary alcohol underwent dehydration producing reactive carbocation, which instigated a cascade of carbox-yl group formation, ring-opening via C−C bond dissociation and C=C bond formation realizing aromatization. The product 3-aryl-2-benzo was yielded with recovered CF3SO3H. The electron-rich phenoxy group was deprotonated by HO- forming water. The initial nucleophilic addition to spatial-adjacent carbonyl afforded dieneone. It isomerized to the first product polycyclic alcohol. Then carboxylation occurred via hydroxyl shift followed by ring-opening aromatization to the second product biaryl carboxylic acid. The positive solvation effect is suggested by decreased absolute and activation energies in solution compared with in gas. These results are supported by Multiwfn analysis on FMO composition of specific TSs, and MBO value of vital bonding, breaking.

Electrochemical conversion of CO2 via C−X bond formation: recent progress and perspective

With the depletion of traditional energy sources and growing environmental concerns, it is becoming increasingly urgent to develop green, low-emission renewable energy technologies to replace fossil fuel-driven methods that emit carbon dioxide (CO2). Currently, the electrochemical production of high-value-added chemicals and fuels from CO2 has aroused great interest from scientists. However, to make full use of CO2 for the preparation of chemicals, it is necessary to expand the range of electrosynthesis methods, in particular by expanding reaction pathways through the reaction of CO2 with different substrates. In general, CO2 can form new covalent bonds with substrate molecules through the formation of C−X bonds, including C−H, C−C, C−N, C−O, and C−S bonds, which would expand the range of possible products by diversifying the reaction pathway. In this review, we focus on the research progress in electrochemical conversion of CO2 through C−X bond formation. We start by examining fundamentals of the reactions and summarizing the reaction modes. Next, we discuss the electrosynthesis of C−X bonds (C−H, C−C, C−N, C−O, C−S) using CO2 and different substrate molecules. Finally, (i) strategies for the design and activity optimization of catalyst materials and (ii) the future development of forming five types of bonds from CO2 and small molecules are discussed, along with an outlook on their future research prospects.

Polymerizable fatty acid surfactant: Encapsulation of organic pigments for excellent colloidal stability in aqueous solution and water-repellent property

Organic pigments are indispensable in various applications due to their vibrant colors and durability, yet their low polarity often hinders their dispersion in an aqueous solution, leading to large aggregation and sedimentation. To address these limitations, dispersants and encapsulation techniques have been explored. In this study, nanoscale encapsulated pigments were synthesized using a novel polymerizable surfactant, sodium 11-methacrylamidoundecanoic acid (NaMAAUA), along with hydrophobic monomer of styrene or butyl methacrylate. NaMAAUA contains a pendant group of amphiphilic fatty acid, and acts as a dispersant and emulsifier, forming a copolymer shell around the pigments. The apolar tail in NaMAAUA provides hydrophobic interaction with pigments, and the polar carboxyl headgroup exposes in the water phase and enables the formation of strong hydrogen bonds with cellulose. Therefore, the resulting encapsulated pigment exhibits excellent dispersion stability, water-repellent property, washing fastness and UV resistance when applied to paper and cotton fabric, expanding the practical utility of organic pigments in an environmentally conscious manner. Characterization via various analytical techniques validates the efficacy of this approach, paving the way for enhanced pigment applications.

Construction of supramolecular assembly frameworks based on salamo-type polynuclear Cu(II) polymer and dimer utilizing secondary bonds

Using the advantages of the salamo structure, we successfully constructed a coordination polymer [Cu2(L)]n(ClO4)n (CP) and a coordination dimer [Cu4(L)2(EtOH)2](NO3)2 (CD). The CP has primary building unit [Cu2(L)], which contains a fully deprotonated part (L)3− and two Cu(II) ions. These units are infinitely connected by Cu-O coordination bonds to form a 1-D chain-like secondary building unit [Cu2(L)]n. The CD has primary building unit [Cu2(L)(EtOH)], which contains a fully deprotonated part (L)3−, two Cu(II) ions, and a coordinated ethanol molecule. Two primary building units are connected by Cu-O coordination bonds to form a dimer, which serves as the secondary building unit [Cu4(L)2(EtOH)2]. Both the CP and CD are stabilized through the formation of Cu-O coordination bonds and π···π interactions. Additionally, secondary bonds are used to form supramolecular assembly frameworks (SAFs). Reaction sites and secondary bonds were further analyzed and discussed through theoretical calculations including molecular orbitals (MO), molecular electrostatic potentials (MEPs), Hirshfeld surfaces (HS), Interaction Region Indicators (IRI), Localized Orbital Locator (LOL), and Electron Localization Function (ELF).

Advanced glycation end-product crosslinking activates a type VI secretion system phospholipase effector protein

Advanced glycation end-products (AGE) are a pervasive form of protein damage implicated in the pathogenesis of neurodegenerative disease, atherosclerosis and diabetes mellitus. Glycation is typically mediated by reactive dicarbonyl compounds that accumulate in all cells as toxic byproducts of glucose metabolism. Here, we show that AGE crosslinking is harnessed to activate an antibacterial phospholipase effector protein deployed by the type VI secretion system of Enterobacter cloacae. Endogenous methylglyoxal reacts with a specific arginine-lysine pair to tether the N- and C-terminal α-helices of the phospholipase domain. Substitutions at these positions abrogate both crosslinking and toxic phospholipase activity, but in vitro enzyme function can be restored with an engineered disulfide that covalently links the N- and C-termini. Thus, AGE crosslinking serves as a bona fide post-translation modification to stabilize phospholipase structure. Given the ubiquity of methylglyoxal in prokaryotic and eukaryotic cells, these findings suggest that glycation may be exploited more generally to stabilize other proteins. This alternative strategy to fortify tertiary structure could be particularly advantageous in the cytoplasm, where redox potentials preclude disulfide bond formation.

Cellulose Nanocrystal-in-Solvent Processing for Efficient One-Pot Upcycling of Commercial Polymeric PFAS.

Upcoming regulations aim to ban per- and polyfluoroalkyl substances (PFAS), including commercial polymeric PFAS, or fluoropolymers, such as poly(tetrafluoroethylene) (PTFE) and poly(vinylidene fluoride) (PVDF), due to their environmental and toxicological impacts. However, fluoropolymers also provide crucial properties for clean energy transitions, and their regulation may hinder further technological advancements. Therefore, a facile one-pot recycling-upcycling strategy for fluoropolymers using inexpensive biomass, such as cellulose nanocrystals (CNCs), as absorbents and cocomponents for fluoro-functionalized composites could align with global sustainability goals and technological demands. Herein, we present a closed-loop CNC-in-solvent (CiS) processing system, which involves stirring fluoropolymers and CNCs in only low-polarity solvents like toluene (CiS-T). Our study reveals that CiS-T is a two-step process where the CNC-solvent interaction exposes CNCs' reducing end aldehyde protons due to solvent polarity and promotes H-F bond formation. The solvent used was recollected and reused. Additionally, we demonstrate the practical application of PTFE- and PVDF-CNC hybrids, byproducts of the CiS-T process, as performance-enhancing agents in green-energy-harvesting devices such as triboelectric nanogenerators. Our findings not only offer a sustainable method to overcome challenges from regulations against commercial fluoropolymers but also offer insights into developing an efficient, solvent-mediated CNC functionalization process that addresses forthcoming challenges in key industries.

Xylooligosaccharide interferes with the cell cycle and reduces the antibiotic tolerance of avian pathogenic Escherichia coli by associating with its potential antimetabolic actions

This study aimed to probe if xylooligosaccharide (XOS) could act as an antimetabolite to impact the cell cycle and antibiotic tolerance of avian pathogenic Escherichia coli (APEC). We firstly measured the bacteriostasis of XOS against APEC O78 and its effect on the growth of APEC O78 growing on different medium. Afterwards, the effects of XOS on xylose operon activation along with the cell cycle and antibiotic tolerance of APEC O78 were analyzed. The results showed that XOS caused no inhibitory circle against APEC O78 and did not affect (P > 0.05) the growth of APEC O78 growing on LB medium. Besides, APEC O78 was unable to grow on M9 medium (carbon-free) added with XOS. However, XOS exerted a similar role as xylose in increasing (P < 0.05) the expression of certain xylose operon genes including xylose isomerase (XylA)-encoding gene (xylA) and xylose-binding periplasmic protein (XylF)-encoding gene (xylF) in APEC O78. The molecular docking simulation revealed that the major monomer components (xylobiose, xylotriose and xylotetraose) of XOS had stable binding potentials to both XylA and XylF proteins of E. coli, as supported by the low binding free energy and the formation of considerable hydrogen bonds between them. The subsequent analysis showed that XOS altered certain cell cycle-related genes expression, especially elevated (P < 0.05) nrdB expression and decreased ihfB expression to a degree. Moreover, XOS played a similar role as 2-deoxy-glucose (a glucose analogue serving as a typical antimetabolite) in lowering (P < 0.05) the number of ampicillin-tolerant APEC O78. Collectively, XOS had no direct bacteriostasis against APEC and could not be metabolized/utilized by APEC O78. However, it might become an analogue of xylose and then activate xylose transport- and metabolism-related proteins in APEC O78, thus functioning as a potential antimetabolite and exerting anti-metabolic actions. This could at least partially interpret the observed roles of XOS in interfering with the cell cycle and diminishing the antibiotic tolerance of APEC O78. The above findings expand the knowledges about the functions of XOS and provide a basis for exploring novel strategies to reduce the antibiotic tolerance of APEC.

Fast Collective Hydrogen-Bond Dynamics in HexafluoroisopropanolRelated to its Chemical Activity.

Using fluorinated mono-alcohols, in particular hexafluoro-isopropanol (HFIP), as a solvent can enhance chemical reaction rates in a spectacular manner. Previous work has shown evidence that this enhancement is related to the hydrogen-bond structure of these liquids. Here, we investigate the hydrogen-bond dynamics of HFIP and compare it to thatof its non-fluorinated analog, isopropanol. Ultrafast infrared spectroscopy show that the dynamics of individual hydrogen-bonds is about twice as slow in HFIP as in isopropanol. Surprisingly, from dielectric spectroscopy we find the opposite behavior for the dynamics of hydrogen-bonded clusters: collective rearrangements are3 times faster in HFIP than in isopropanol. This difference indicates that the hydrogen-bonded clusters in HFIP are smaller than in isopropanol. The differences in cluster size can be traced to changes in the hydrogen-bond donor and acceptor strengths upon fluorination. The smaller cluster size canboostreaction rates in HFIP by increasing the concentration of reactive, terminal OH-groups of the clusters, whereas the fast collective dynamics can increase the rate of formation of hydrogen bonds with the reactants. The longer lifetime of the individual hydrogen bonds in HFIP can enhance the stability of the hydrogen-bonded clusters, and so increase the probability of reactant-solvent hydrogen bonding.

Unraveling abiotic organic synthesis pathways in the mafic crust of mid-ocean ridges

The aqueous alteration of the oceanic lithosphere provides significant energy that impacts the synthesis and diversity of organic compounds, which are crucial for the deep carbon cycle and may have provided the first building blocks for life. Although abiotic organic synthesis has been documented in mantle-derived rocks, the formation mechanisms and complexity of organic compounds in crustal rocks remain largely unknown. Here, we show the specific association of aliphatic carbonaceous matter with Fe oxyhydroxides in mafic crustal rocks of the Southwest Indian Ridge (SWIR). We determine potential Fe-based pathways for abiotic organic synthesis from CO2 and H2 using multimodal and molecular nano-geochemical tools. Quantum mechanical modeling is further employed to constrain the catalytical activity of Fe oxyhydroxides, revealing that the catalytic cycle of hydrogen may play a key role in carbon-carbon bond formation. This approach offers the possibility of interpreting physicochemical organic formation and condensation mechanisms at an atomic scale. The findings expand our knowledge of the existence of abiotic organic carbon in the oceanic crustal rocks and emphasize the mafic oceanic crust of the SWIR as a potential site for low-temperature abiotic organic synthesis.