Sulfoxide Product Research Articles

Microplastics and copper impacts on feeding, oxidative stress, antioxidant enzyme activity, and dimethylated sulfur compounds production in Manila clam Ruditapes philippinarum

Microplastics (MPs) are widespread ocean pollutants and many studies have explored their effects. However, research on MPs combined impact with copper (Cu) on dimethylated sulfur compound production is limited. Dimethyl sulfide (DMS) is an important biogenic sulfur compound related to global temperatures. This study examined the ecotoxicological effects of polyamide 6 MPs and Cu on dimethylsulfoniopropionate (DMSP), DMS, and dimethyl sulfoxide (DMSO) production in Manila clams (Ruditapes philippinarum). Our findings showed that MPs and Cu increased oxidative stress, indicated by higher superoxide anion radical production and malondialdehyde levels while decreasing glutathione contents and increasing superoxide dismutase activities. Additionally, MPs and Cu exposure reduced DMS and dissolved DMSO (DMSOd) concentrations due to decreased grazing. These results contribute to a better understanding of the ecotoxicological effects of MPs/Cu on bivalves and their roles in the organic sulfur cycle, suggesting a need for further research on long-term impacts on them.

Unveiling Ru(bpy)3 2+-Encapsulated Zeolite Y as Photocatalyst: Harnessing Photocatalytic Singlet Oxygen Generation for Mustard Gas Simulant Detoxification.

This study explores the encapsulation of Ru(bpy)3 2+ within Zeolite Y (ZY) to improve photocatalytic singlet oxygen generation for the degradation of a mustard gas simulant, namely 2-chloroethyl ethyl sulfide (CEES). Mustard gas simulants are known to disrupt several biological processes; thus, their effective degradation is essential. Zeolite Y, with its hierarchical structure and adjustable Si/Al ratios, is an ideal host for Ru(bpy)3 2+, significantly improving its photocatalytic efficiency and stability. It is demonstrated through XRD and spectroscopic analyses that encapsulated Ru(bpy)3 2+ maintains its structural and photophysical properties, which are essential for generating singlet oxygen. Ru(bpy)3(1.0) loaded ZY(15) (where 1.0 and 15 represent the encapsulated amount of Ru(bpy)3 2+ and Si/Al ratio, respectively) outperforms other investigated photocatalytic systems in the oxidation of CEES, demonstrating high conversion rates and selectivity toward nontoxic sulfoxide products. Immobilization of Ru(bpy)3 2+-encapsulated zeolite Y onto cotton fabric results in effective degradation of CEES. The experimental results, validated by theoretical calculations, indicate an improved oxygen affinity and accessibility in zeolites with higher Si/Al ratios. This study advances the design of photocatalytic materials for environmental and defense applications, providing sustainable solutions for hazardous chemical degradation.

Size-dependent influences of nano- and micro-plastics exposure on feeding, antioxidant systems, and organic sulfur compounds in ciliate Uronema marinum

Protozoa play a pivotal role in the microbial cycle, and ciliated protozoan grazing habits are associated with dimethyl sulfide (DMS) cycle. Many studies have explored the impacts of nanoplastics (NPs) and microplastics (MPs) on ecotoxicological effects of ciliates. However, limited research exists on NPs and MPs influences on the production of organic sulfur compounds. The impact of NPs and MPs on the production of dimethyl sulfoxide (DMSO) and carbonyl sulfide (COS) remains unclear. Therefore, we examined the impacts of three concentrations (1 × 105, 5 × 105, and 1 × 106 items/mL) of polystyrene (PS) NPs (50 nm) and MPs (1 and 5 μm) on the ecotoxicology and DMS/dimethylsulfoniopropionate (DMSP)/DMSO/COS production in the ciliate Uronema marinum. NPs and MPs exposure were found to reduce the abundance, growth rate, volume, and biomass of U. marinum. Additionally, NPs and MPs increased the superoxide anion radical (O2˙─) production rates and malondialdehyde (MDA) contents (24 h), leading to a decline in glutathione (GSH) content and an ascend in superoxide dismutase (SOD) activity to mitigate the effects of reactive oxygen species (ROS). Exposure to PS NPs and MPs decreased the ingestion rates of algae by 7.5–14.4%, resulting in decreases in DMS production by 56.8–85.4%, with no significant impact on DMSO production. The results suggest a distinct pathway for the production of DMSO or COS compared to DMS. These findings help us to understand the NPs and MPs impacts on the marine ecosystem and organic sulfur compound yield, potentially influencing the global climate.

One-pot synthesis of a porphyrin functionalized metal-organic frameworks as a recyclable visible-light-driven photosensitizer for efficient detoxification of a sulfur mustard simulant in air

Herein, we report a facile one-pot in situ self-assembly approach that enables a porphyrin photosensitizer, [5,10,15,20-tetrakis(4-methoxycarbonylphenyl)porphyrin]-Zn(II) (ZnTPP), to be enshrouded by a zeolitic imidazolate framework-8 (ZIF-8) to afford a novel visible-light-driven heterogeneous photosensitizer, ZnTPP@ZIF-8 composite. The ZnTTP photosensitizer was well dispersed and fully confined within the ZIF-8 crystals and the framework intactness and porosity were well maintained. The as-prepared ZnTPP@ZIF-8 composite integrates the advantages of ZIF-8 MOFs and ZnTTP photosensitizer. It not only can effectively produce both singlet oxygen (1O2) and superoxide ion (∙O2−) under visible light irradiation, but also exhibit high surface area and excellent stability. The structure characterization of ZnTPP@ZIF-8 composite was first carried out, and then this material can be used as a heterogeneous photosensitizer for the rapid and highly selective detoxification of a sulfur mustard simulant (2-chloroethyl ethyl sulfide) into the corresponding much less toxic sulfoxide product with a half-life of only 1.5 min under visible light irradiation at room temperature in air atmosphere. This catalyst can be readily recycled and reused at least six times without obvious loss of catalytic activity. This study will provide us a new strategy for the facile, rapid and environmentally friendly preparation of photosensitizer@MOFs composites and the rapid detoxification of sulfur mustard under ambient conditions in the future.

Phosphonate-substituted porphyrins as efficient, cost-effective and reusable photocatalysts.

Recent advances in visible light photocatalysis represent a significant stride towards sustainable catalytic chemistry. However, its successful implementation in fine chemical production remains challenging and requires careful optimization of available photocatalysts. Our work aims to structurally modify bioinspired porphyrin catalysts, addressing issues related to their laborious synthesis and low solubility, with the goal of increasing their efficiency and developing reusable catalytic systems. We have demonstrated the catalytic potential of readily available meso-tetrakis[4-(diethoxyphosphoryl)phenyl]porphyrins (M(TPPP)). Novel metal (Pd(II), Co(II) and In(III)) complexes with this ligand were prepared in good yields. These chromophores were characterized in solution using spectroscopic (NMR, UV-vis, fluorescence) and electrochemical methods. The introduction of phosphonate groups on the phenyl substituents of meso-tetraphenylporphyrins (M(TPP)) improves solubility in polar organic solvents without significantly altering the photophysical properties and photostability of complexes. This structural modification also leads to easier reductions and harder oxidations of the macrocycle for all investigated complexes compared to the corresponding TPP derivatives. The free base porphyrin, zinc(II), palladium(II), and indium(III) complexes were studied as photocatalysts for oxidation of sulfides to sulfoxides using molecular oxygen as a terminal oxidant. Both dialkyl and alkyl aryl sulfides were quantitatively transformed into sulfoxides under blue LED irradiation in the acetonitrile-water mixture (10 : 1 v/v) with a low loading (0.005-0.05 mol%) of porphyrin photocatalysts, where H2(TPPP) and Pd(TPPP) were found to be the most efficient. The reaction mechanism was studied using photoluminescence and EPR spectroscopies. Then, to access reusable catalysts, water-soluble derivatives bearing phosphonic acid groups, H2(TPPP-A) and Pd(TPPP-A), were prepared in high yields. These compounds were characterized using spectroscopic methods. Single-crystal X-ray diffraction analysis of Pd(TPPP-A) reveals that the complex forms a 3D hydrogen-bonded organic framework (HOF) in the solid state. Both H2(TPPP-A) and Pd(TPPP-A) were found to catalyze the photooxidation of sulfides by molecular oxygen in the acetonitrile-water mixture (1 : 1 v/v), while only Pd(TPPP-A) resulted in selective production of sulfoxides. The complex Pd(TPPP-A) was easily recovered through extraction in the aqueous phase and successfully reused in five consecutive cycles of the sulfoxidation reaction.

Rapid Oxidative Detoxification of Mustard Simulant by the Multisite Synergistic Catalytic Action of {PMoVI11MoVO40CuI8} Units.

Under hydrothermal and solvent-thermal conditions, we synthesized two novel polyoxometalate (POM)-based hybrids: [CuI4(Pz)2(H2O)8(PMoVI11MoVO40)]·3.5H2O (1, Pz = pyrazine) and [(C2H8N)5(HPMoVI9MoV3O40)]·DMF·4H2O (2). Single-crystal X-ray diffraction indicates that compound 1 is a three-dimensional structure consisting of Cu (I), {PMo12} anions, Pz, and water, where Cu (I) can be considered as Lewis acid sites. Furthermore, both compounds 1 and 2 possess favorable catalysis activity in catalyzing the conversion of chemical warfare agent simulant 2-chloroethylethyl sulfide (CEES) to nontoxic production of 2-chloroethylethyl sulfoxide (CEESO) under ambient temperature. Significantly, 1 could realize 98% conversion and 100% selectivity of CEES owing to the multisite synergy in the {PMoVI11MoVO40CuI8} units in which the tricoordinated Cu (I) could interact with S and O atoms from CEES and H2O2, respectively. This interaction not only decreases the distance of CEES from peroxomolybdenum species formed by H2O2 but also activates CEES.

Nontoxic chemical crosslinked bacterial cellulose-heparin-gelatin composite hydrogel as antibacterial dressing

A hydrogel dressing based on bacterial cellulose (BC), which is grafted with quaternary ammonium functional and crosslinked with the gelatin-heparin system, is prepared to provide the features mainly concerning softness, high swelling ratio, antibacterial property, and biocompatibility. An innovation of preparation is that the BC is beaten into short-chain scaffolds to improve the efficiency of grafting, which not only simplifies the preparation process but also avoids the biotoxicity caused by the introduction of toxic catalyst such as dimethyl sulfoxide (DMSO) or uncertain toxic side products in long-chain grafting. Scanning electron microscopy (SEM) shows that the QBC/Hep/Gel composite hydrogel possesses a three-dimensional mesh structure with high porosity. The hydrogel shows outstanding water management performance indicated by the swelling ratio of 1476%, water retention ratio of more than 90% at 120 h, and moisture permeability of 3296 g m−2 24 h−1. The antibacterial experiment is implemented with staphylococcus aureus, and the antibacterial effect is represented by an inhibition zone of 3 cm in diameter. In vivo animal experiments suggested that QBC/Hep/Gel could effectively promote epithelial reconstruction, collagen deposition, and angiogenesis in normal wounds, reduce inflammation, and accelerate wound healing. All these results indicate that the proposed QBC/Hep/Gel hydrogel is a potential composite for antibacterial dressing.

Symmetry-dependent photocatalysis of conjugated microporous polymers based on pyrene for oxygenation of sulfides with O2

To date, conjugated microporous polymers (CMPs) have been developed into multifaceted photocatalysts. Here, two CMPs based on pyrene with the linkages of thiazolo[5,4-d]thiazole (TzTz) are prepared for visible light photocatalysis. The dimension of the molecular building block’s symmetry on the property and activity of CMPs is systematically investigated. Py(4)-TzTz-CMP with a pyrene building block of D2h symmetry gives rise to better optoelectronic property than Py(2)-TzTz-CMP with a pyrene building block of C2 symmetry. Therefore, Py(4)-TzTz-CMP photocatalyst is endowed with superior conversions for the green light-promoted oxygenation of sulfides with O2. Intriguingly, mechanistic explorations disclose that both superoxide and singlet oxygen are responsible for the production of the target sulfoxides. This work gives insight into the rational design of highly active CMP photocatalysts for selective chemical transformations.

Kinetic and Product Study of the S‐oxidation vs HAT Chemoselectivity in Reactions Promoted by Nonheme Iron(IV)‐oxo Complex/NHPI Mediator System

AbstractThe chemoselectivity between S‐oxidation and hydrogen atom transfer (HAT) from C−H bonds has been investigated in the oxidations of a series of aryl sulfides, alkyl aromatic compounds and benzylic alcohols promoted by the iron(IV)‐oxo complex [(N4Py)FeIV(O)]2+ (N4Py: N,N‐bis(2‐pyridylmethyl)‐N‐bis(2‐pyridyl)‐methylamine) either alone or in the presence of the N‐hydroxyphthalimide (NHPI) mediator via kinetic and product studies. Kinetic analyses indicate a generally higher reactivity of [(N4Py)FeIV(O)]2+ for S‐oxidation process while HAT is favored in the reactions promoted by phthalimide‐N‐oxyl radical (PINO) deriving from NHPI oxidation. Product analysis in intermolecular competitive oxidations confirms the kinetic results with sulfoxides obtained as major products in the oxidation promoted by [(N4Py)FeIV(O)]2+. Conversely, when NHPI is employed as a mediator, significant differences in terms of chemoselectivity are observed, and HAT‐derived products are obtained in higher yields which translate into an inversion of selectivity in the case of the substrates containing activated C−H bonds like diphenylmethane, triphenylmethane and benzylic alcohols. A similar change of chemoselectivity is also observed in the oxidation of aromatic substrates containing both a sulfur atom and α to OH benzylic C−H bonds, with the sulfoxide product more abundant in the absence of NHPI and carbonyl products prevailing with the [(N4Py)FeIV(O)]2+/NHPI system.

Bioelectrochemical platform with human monooxygenases: FMO1 and CYP3A4 tandem reactions with phorate

It is highly advantageous to devise an in vitro platform that can predict the complexity of an in vivo system. The first step of this process is the identification of a xenobiotic whose monooxygenation is carried out by two sequential enzymatic reactions. Pesticides are a good model for this type of tandem reactions since in specific cases they are initially metabolised by human flavin-containing monooxygenase 1 (hFMO1), followed by cytochrome P450 (CYP). To assess the feasibility of such an in vitro platform, hFMO1 is immobilised on glassy carbon electrodes modified with graphene oxide (GO) and cationic surfactant didecyldimethylammonium bromide (DDAB). UV–vis, contact angle and AFM measurements support the effective decoration of the GO sheets by DDAB which appear as 3 nm thick structures. hFMO1 activity on the bioelectrode versus three pesticides; fenthion, methiocarb and phorate, lead to the expected sulfoxide products with KM values of 29.5 ± 5.1, 38.4 ± 7.5, 29.6 ± 4.1 µM, respectively. Moreover, phorate is subsequently tested in a tandem system with hFMO1 and CYP3A4 resulting in both phorate sulfoxide as well as phoratoxon sulfoxide. The data demonstrate the feasibility of using bioelectrochemical platforms to mimic the complex metabolic reactions of xenobiotics within the human body.

Tannic acid-based hypercrosslinked polymer as heterogeneous catalyst for aerobic oxidation reaction

Hypercrosslinked polymers (HCPs) are a type of porous organic materials with high surface area and maneuverable preparation process. Metal-functionalization is a popular and effective post-synthesis modification strategy to construct catalytically active HCPs. Tannic acid (TA) is a biomolecule containing multiphenol moieties that possess the ability to conduct Friedel–Crafts alkylation reaction and metal-bonding active sites. We utilized TA to prepare the hypercrosslinked polymer (TA-HCP) with 1,2-dichloroethane as the crosslinker. After post-synthesis reaction, the vanadium-functionalized TA-HCP-VO was obtained with well-maintained chemical structure and moderate surface area. TA-HCP-VO exhibits an excellent catalytic performance in thioether oxidation reaction to produce sulfoxide compounds. Various thioether substrates with different substituents are transformed to sulfoxide products with high conversion rates (99%) and selectivities (86–95%) under the catalysis of TA-HCP-VO. Furthermore, heterogeneous TA-HCP-VO retains fine catalytic activity and chemical structure after four cycling reactions, which demonstrates the superiority of heterogeneous porous catalysts. • A biomolecule, tannic acid, is used to prepare hypercrosslinked polymer, TA-HCP. • Phenol moieties in TA-HCP act as reactive sites in post-synthesis modification. • Vanadium is facilely immobilized onto TA-HCP to form catalytic TA-HCP-VO. • TA-HCP-VO shows excellent catalytic performance in thioether oxidation reaction.

Two pseudo-polymorphic porous POM-pillared MOFs for sulfide-sulfoxide transformation: Efficient synergistic effects of POM precursors, metal sites and microstructures

Developing sustainable and powerful heterogeneous catalytic systems to convert sulfides into high-value sulfoxide products has become a particularly appealing field and an arduous challenge. In this work, two porous polyoxometalate-pillared metal-organic frameworks, formulated as H3n[Cu3(pidc)2(H2O)2.5]2[PW12O40]n·xH2O (n = 1.5, x = 6 for 1, n = 1, x = 12 for 2; and H3pidc = 2-(3-pyridinyl)-1H-imidazole-4,5-dicarboxylic acid), were consciously manufacture and employed for heterogeneously catalyzed sulfide-sulfoxide transformation. Structural analysis shows that 1 and 2 exhibit similar porous frameworks with nearly identical two-dimensional metal-organic layers further pillared by tetradentate POM ligands with different coordination modes, which also result in the porosity of 1 being almost twice that of 2. In catalyzing the conversion of methyl phenyl sulfide (MPS) to methyl phenyl sulfoxide (MPSO), 1 can convert nearly 100% of MPS into MPSO within 30 min, while 2 achieved the similar results requires 50 min. The higher activity of 1 may be attributed to its larger channel that can provide more active sites and more efficient mass transfer process. Systematic structure-activity analyses and mechanistic studies revealed dual-reaction pathways driven by POM sites and metal sites assisted by the structural microenvironment.

Chalcogen bond-guided conformational isomerization enables catalytic dynamic kinetic resolution of sulfoxides

Conformational isomerization can be guided by weak interactions such as chalcogen bonding (ChB) interactions. Here we report a catalytic strategy for asymmetric access to chiral sulfoxides by employing conformational isomerization and chalcogen bonding interactions. The reaction involves a sulfoxide bearing two aldehyde moieties as the substrate that, according to structural analysis and DFT calculations, exists as a racemic mixture due to the presence of an intramolecular chalcogen bond. This chalcogen bond formed between aldehyde (oxygen atom) and sulfoxide (sulfur atom), induces a conformational locking effect, thus making the symmetric sulfoxide as a racemate. In the presence of N–heterocyclic carbene (NHC) as catalyst, the aldehyde moiety activated by the chalcogen bond selectively reacts with an alcohol to afford the corresponding chiral sulfoxide products with excellent optical purities. This reaction involves a dynamic kinetic resolution (DKR) process enabled by conformational locking and facile isomerization by chalcogen bonding interactions.

Elucidating Sulfide Activation Mode in Metal-Catalyzed Sulfoxidation Reactivity.

Interest in the catalytic activation of peroxides, together with the requirement of stereoselectivity for the production of enantiopure sulfoxides, has made sulfoxidation the ideal playground for theoretical and experimental physical organic chemists investigating oxidation reactivity. Efforts have been dedicated for elucidating the catalytic pathway regarding these species and for dissecting out the dominant factors influencing the yield and stereochemistry. In this article, Ti(IV) and Hf(IV) aminotriphenolate complexes have been prepared and investigated as catalysts in the presence of peroxides in sulfide oxidation. Experimental results have been combined with theoretical calculations obtaining detailed mechanistic information on oxygen transfer processes. The study revealed that steric issues are mainly responsible for the formation of intermediates in the oxidation pathway. In particular, we could highlight the occurrence of a blended situation where the steric effects of sulfides, ligands, and oxidants influence the formation of different intermediates and reaction pathways.

Selective and efficient catalytic and photocatalytic oxidation of diphenyl sulphide to sulfoxide and sulfone: the role of hydrogen peroxide and TiO2 polymorph.

In this paper, we describe the role of anatase and rutile crystal phases on diphenyl sulphide (Ph2S) catalytic and photocatalytic oxidation. The highly selective and efficient synthesis of diphenyl sulfoxide (Ph2SO) and diphenyl sulfone (Ph2SO2) at titanium dioxide was demonstrated. Ph2S oxidation in the presence of hydrogen peroxide at anatase-TiO2 can take place both as a catalytic and photocatalytic reaction, while at rutile-TiO2 only photocatalytic oxidation is possible. The reaction at anatase leads mainly to Ph2SO2, whereas, in the presence of rutile a complete conversion to Ph2SO is achieved after only 15 min (nearly 100% selectivity). Studies on the mechanistic details revealed a dual role of H2O2. It acts as a substrate in the reaction catalysed only by anatase, but it also plays a key role in alternative photocatalytic oxidation pathways. The presented study shows the applicability of photocatalysis in efficient and selective sulfoxide and sulfone production.

Synthesis of Various α‐Substituted Alkenyl Sulfoxides from Alkynes and β‐Sulfinyl Esters

AbstractMethods to synthesize α‐substituted alkenyl sulfoxides are highly useful as they are widely used to construct diverse molecules of high synthetic importance. We have described a synthetic route for expedient access to the numerous α‐substituted alkenyl sulfoxides from alkynes and β‐sulfinyl esters. This protocol exhibits a vast substrate scope, readily accommodates a wide range of functional groups, and is scalable in a gram‐scale. Besides, we demonstrated a direct synthesis of alkenyl sulfoxides from thiols via the in situ generation of the requisite β‐sulfinyl ester. The ensuing α‐substituted alkenyl sulfoxide product was readily transformed into benzofuran and sulfonyl derivatives. Mechanistic investigations were done to comprehend the reaction mechanism.

Direct C-H Thiolation for Selective Cross-Coupling of Arenes with Thiophenols via Aerobic Visible-Light Catalysis.

An aerobic metal-free, visible-light-induced regioselective thiolation of phenols with thiophenols is reported. The cross-coupling protocol exhibits great functional group tolerance and high regioselectivity. Mechanistic studies reveal that the disulfide radical cation plays a crucial role in the visible-light catalysis of aerobic thiolation. Simply controlling the equivalent ratio of substrates enables the selective formation of sulfide or sulfoxide products with high activity in a one-pot reaction.

Photooxidase Mimicking with Adaptive Coordination Molecular Capsules.

One important feature of enzyme catalysis is the induced-fit conformational change after binding substrates. Herein, we report a biomimetic water-soluble molecular capsule featuring adaptive structural change toward substrate binding, which offers an ideal platform for efficient photocatalysis. The molecular capsule was coordination-assembled from three anthracene-bridged bis-TPT [TPT = 2,4,6-tris(4-pyridyl)-1,3,5-triazine] ligands and six (bpy)Pd(NO3)2 (bpy = 2,2'-bipyridine). Once substrates bind to its hydrophobic cavity, this capsule would undergo quantitative capsule-to-bowl transformation. Visible-light absorption brought about by both the anthracene units and the charge-transfer absorption on the late-formed quintuple π-π stacked host-guest complex efficiently facilitates aerobic photooxidation for the sulfide guests by visible-light irradiation under mild conditions. Desired turnover numbers and product selectivity (sulfoxide over sulfone) have been achieved by the transformable nature of the catalyst and the hydrophilicity of the sulfoxide product. Such a photocatalytic process enabled by an adaptive coordination capsule and substrates as the allosteric effector paves the way for constructing artificial systems to mimic enzyme catalysis.

Singlet Oxygen Generation, Quenching and Reactivity with Metal Thiolates.

Metal thiolate complexes can act as photosensitizers for the generation of singlet oxygen, quenchers of singlet oxygen, and they may undergo chemical reactions with singlet oxygen leading to oxidized thiolate ligands. This review covers all of the chemical reactions of thiolate ligands with singlet oxygen (through early 2021). Since some of these reactions are self-sensitized photooxidations, singlet oxygen generation by metal complexes is also discussed. Mechanistic features such as the effects of protic vs. aprotic conditions are presented and compared with the comparatively well-understood photooxidation of organic sulfides. In general, the total rate of singlet oxygen removal correlates with the nucleophilicity of the thiolate ligand which in turn can be influenced by the metal. Some interesting patterns of reactivity have been noted as a result of this survey: Metal thiolate complexes bearing arylthiolate ligands appear to exclusively produce sulfinate (metal-bound sulfone) products upon reaction with singlet oxygen. In contrast, metal thiolate complexes bearing alkylthiolate ligands may produce sulfinate and/or sulfenate (metal-bound sulfoxide) products. Several mechanistic pathways have been proposed for these reactions, but the exact nature of any intermediates remains unknown at this time.

Biomimetic donor-acceptor motifs in carbon nitrides: Enhancing red-light photocatalytic selective oxidation by rational surface engineering

Oxidation, especially selective oxidation by a heterogeneous catalyst with molecular oxygen, is a core technology for the conversion of petrochemical feedstock to commodity chemicals and pharmaceuticals. Existing catalytic approaches for efficient aerobic oxidation normally rely on the engagement of organometallic centers or transition-metal nanoparticles. In light of the necessity to develop sustainable production methodologies, multiple approaches for the metal-free polymeric carbon nitride (PCN) photocatalytic selective oxidation have been evaluated. However, the insufficient visible light optical absorption, poor charge-carriers separation and the weak driving force towards oxidation reaction impart a serious restriction on the efficiency and selectivity of the organic photosynthesis, especially under extended wavelength solar light irradiation. Here, we report a surface engineering photochemical modification method to fabricate a donor-acceptor (D-A) functional carbon nitride photocatalyst (ECN) under ambient conditions. The well-developed d-A structure, preserved high crystallinity and enlarged π-conjugation framework of the hybrid semiconductor-molecule ECN samples favor the improvement of the optical absorption, as well as the enhanced separation and migration of the photo-generated charge carriers. As a result, the obtained ECN photocatalysts exhibited remarkable enhancement in the photocatalytic aerobic oxidation of alcohols, even under an extended light wavelength of 620 nm red-light irradiation. The photocatalytic aerobic sulfides and sp3 C–H oxidation reactions were also considerably accelerated over ECN and may serve as a direct approach for the construction of value-added sulfoxide and ketone products.