#### Table of Content

25 January 2023, Volume 2023 Issue 1
Atomic Economic Reactions
 Recent advances in regioselective hydrodifluoroalkylation of alkenes Ying ZHANG, Ling LIAO, Xiaosi HU, Jian ZHOU, Jinsheng YU 2023, 2023 (1):  1-11.  doi: 10.3969/j.issn.1000-5641.2023.01.001 Abstract ( 38 )   HTML ( 4 )   PDF (1845KB) ( 12 )   The regioselective hydrodifluoroalkylation of alkenes has been identified as a straightforward and highly atom-economical approach for synthesizing value-added difluoroalkylated molecules that have important applications in the pharmaceutical and agrochemical industries, as well as in the field of materials science. This is because olefins are structurally diverse raw materials that are inexpensive and easily obtainable from a wide range of sources. Recent years have witnessed significant progress in this field with the rapid development of visible-light catalysis and novel difluoroalkylating reagents. This article review summarizes the latest advances in the regioselective anti-Markovnikov and Markovnikov hydrodifluoroalkylation of various olefins, which provides an inspirational locale for researchers to engage. Herein, we supplement ideas for designing and developing new reactions, difluoroalkyl reagents, and catalytic strategies.
 Aminocarbonylation of propylene (ethylene) epoxide over Co2(CO)8 catalyst modified by bidental O-containing ligand for synthesis of β-hydroxy amides Lin GUO, Guanghui SHI, Xiaochao CHEN, Ye LIU 2023, 2023 (1):  12-20.  doi: 10.3969/j.issn.1000-5641.2023.01.002 Abstract ( 30 )   HTML ( 4 )   PDF (761KB) ( 8 )   This work reports a one-step protocol for the synthesis of β-hydroxyamides via amino-carbonylation of epoxides using aromatic amines as the ammonia source instead of silylamine. The reaction was catalyzed by Co2(CO)8 modified with bidentate O-containing ligand L2, which was prepared by the oxidation of Xantphos [9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene] by H2O2 as a diphosphine-dioxide. Under mild conditions (60 °C, CO 3.0 MPa, 6 h), L2-modified Co2(CO)8 efficiently catalyzed the amino-carbonylation of propylene oxide with aniline to generate 3-hydroxy-N-phenylbutanamide with the yield of 64%. The developed catalytic system exhibited fair stability and general substrate scope.
 Natural products: A bridge between new targets and novel pesticide discovery Zhengqi FANG, Shuanhu GAO, Haibing HE 2023, 2023 (1):  21-30.  doi: 10.3969/j.issn.1000-5641.2023.01.003 Abstract ( 43 )   HTML ( 4 )   PDF (3235KB) ( 20 )   Pesticides are important tools to control crop diseases and pest hazards, guaranteeing the crop harvest. Natural products and their derivatives are major sources of novel pesticides and play indispensable roles in various fields, such as insecticide, fungicide, plant growth regulation, immune regulation and so on. In recent years, numerous fields of biotechnology have made great progress, like genomics, proteomics and structural biology. And thus, the identification of pesticide targets based on natural products and the creation of novel pesticide molecules based on target structures developed rapidly. The concept, rational design, received more attention in pesticide creation. In this article, the discovery of active natural products based on existed targets or novel targets verifying by natural products were demonstrated by several cases, and the subsequent progress in the development of new pesticides were also discussed. The cases explained the important role of natural products in bridging new targets and novel pesticides.
 Catalytic asymmetric synthesis of chiral heterocyclic compounds with CO2 as the C1 synthon Zhipeng ZHAO, Ying SUN, Xiaotong GAO, Feng ZHOU 2023, 2023 (1):  31-40.  doi: 10.3969/j.issn.1000-5641.2023.01.004 Abstract ( 34 )   HTML ( 3 )   PDF (1463KB) ( 21 )   As the main component of greenhouse gases, CO2 represents an inexpensive and readily available renewable C1 synthon. In the past few decades, great efforts have been made toward the development of chemical processes that use CO2 as a promising fossil fuel alternative for C1 feedstocks for the production of industrially attractive chemicals. This could provide access to materials of commercial interest from an abundant, nontoxic, renewable, and low-cost carbon source, thus offering interesting opportunities for the chemical industry, organic synthesis, and so on. Considering the importance of chiral heterocycles in organic synthesis and drug development, the development of highly stereoselective and efficient catalytic asymmetric reactions using CO2 as a C1 synthon for these chiral heterocycles has received considerable attention. Successful examples for chiral lactones, carbonates, and carbamates have already been demonstrated. In this paper, we summarize the recent advances in this field.
Functional Materials
 Green synthesis of structural colored fabrics by spraying aqueous colloidal solutions Luyao LIU, Yuying HE, Qianqian FU, Jianping GE 2023, 2023 (1):  41-49.  doi: 10.3969/j.issn.1000-5641.2023.01.005 Abstract ( 34 )   HTML ( 3 )   PDF (3866KB) ( 13 )   This study developed a one-step spraying method using an aqueous solution of SiO2 particles to prepare SiO2/PET fabrics with saturated and uniform structural colors. The color brightness and uniformity were significantly improved by optimizing the treatment temperature, pH of the colloidal solution, and by introducing a small amount of ethanol. This method would promote the applications of structural colored fabrics because using water would reduce both environmental pollution and production cost.
 Recent progress in the construction and application of self-assembled glycomaterials Weitao DOU, Lin XU, Haibo YANG 2023, 2023 (1):  50-59.  doi: 10.3969/j.issn.1000-5641.2023.01.006 Abstract ( 35 )   HTML ( 2 )   PDF (2847KB) ( 18 )   As essential signaling molecules in biological systems, carbohydrates are involved in several vital physiological and pathological processes via specific recognition by receptors. Hence, nanomaterials comprising carbohydrates are crucial for deciphering and regulating biological processes. A non-covalent assembly process can conveniently yield carbohydrate-based nanomaterials owing to the unique merits of simplicity and controllability of the process. This review summarizes the construction and application of glyco-based functional materials through host-guest interactions and coordination-driven self-assembly processes. Additionally, their potential challenges and future directions are highlighted with the aim of improving understanding on carbohydrate-related physiological and pathological processes.
 Synthesis, physicochemical properties, and applications of sulphate ionic liquids Man WANG, Lulu DANG, Huixia YUAN, Jing ZHOU, Dawei ZHANG, Guohua GAO 2023, 2023 (1):  60-72.  doi: 10.3969/j.issn.1000-5641.2023.01.007 Abstract ( 31 )   HTML ( 1 )   PDF (1032KB) ( 15 )   Sulfate ionic liquids, a new type of ionic liquid, are formed by the combination of sulfate anions and organic cations. Sulfate ionic liquids are important because of their unique characteristics, such as a lack of halogen ions, extremely low vapor pressure, high thermal stability, a high viscosity index, low isothermal compressibility, selective solubility, and good biocompatibility. In this paper, the recent progress in sulfate ionic liquids is reviewed, with focus on one-step and two-step synthetic methods. The physicochemical parameters, such as the density, viscosity, refractive index, surface tension, isothermal compression coefficient, and sound conduction, are summarized, and the effects of the physicochemical properties of sulfate ionic liquids, such as the length of the alkyl chains with anionic and cationic groups, are discussed. The sulfate ionic liquids discussed in this review could be used in various fields as new environmentally friendly solvents, extractants, catalysts, lubricating materials, gas absorption materials, and to separate or dope composite materials.
 N-alkylation modification of metal-organic frameworks to afford responsive fluorescence Xiaoyan LIU, Enqing GAO 2023, 2023 (1):  73-81.  doi: 10.3969/j.issn.1000-5641.2023.01.008 Abstract ( 22 )   HTML ( 1 )   PDF (2623KB) ( 8 )   In this study, the electron-deficient pyridinium group and the naphthalene fluorophore were simultaneously introduced to a bipyridyl-containing Zr(Ⅳ) metal-organic framework (MOF) by the N-alkylation post-synthetic modification. The obtained ionic MOF, Zr-bpy-MNap, is nonluminous in the pristine state but shows selective fluorescence turn-on responses to some solvents and ammonia. Test papers were prepared using the MOF for the identification of solvents and detection of ammonia in air. The fluorescence turn-on response is considered to be due to complex host-guest interactions and solvation effects. The MOF is non-fluorescent due to the quenching effects of the host-guest communications between the bromide ion and the framework. On exposure to some solvents or ammonia, the quenching mechanisms are weakened or destroyed by the solvation of bromide or host-guest interactions between ammonia and the framework, resulting in fluorescence turn-on responses. The fluorescence originates from the charge-transfer transition between the naphthyl group and the electron-deficient framework.
 Review of zeolite-confined subnanometric cluster catalysts Yue MA, Hao XU, Yueming LIU, Kun ZHANG, Peng WU, Mingyuan HE 2023, 2023 (1):  82-94.  doi: 10.3969/j.issn.1000-5641.2022.00.009 Abstract ( 48 )   HTML ( 5 )   PDF (5085KB) ( 35 )   The design of efficient and stable supported metal catalysts to prevent metal species from sintering into large nanoparticles under harsh preparation and reaction conditions is key for various important processes, including the conversion of C1 resources and dehydrogenation of low carbon alkanes to C2 and C3 olefins. Zeolites with uniform subnano micropores and various three-dimensional crystalline structures have been proven as ideal supports for preparing highly efficient and stable metal catalysts via encapsulating subnanometric metal clusters within their pores, cages, and channels. Interactions between metal clusters and the zeolite skeleton can regulate their geometric and electronic structure. The development of zeolite-confined subnanometric cluster catalysts aims to take advantage of this joint confinement effect and induce synergy between guest metal species and active sites in host zeolite frameworks. This can further improve the catalytic activity of resultant composite catalysts, for applications in multiple catalytic reaction processes . In this review, typical preparation methods of zeolite-confined subnanometric clusters and their catalytic applications in selective hydrogenation of CO2 and alkynes, hydrogen generation by formic acid decomposition and ammonia borane hydrolysis, and propane dehydrogenation to propene are discussed.
Catalytic Reaction Technologies
 Study of an Na2WO4/Mn7SiO12-SiO2 oxygen-carrier catalyst for chemical looping-oxidative coupling of methane Ya GAO, Weidong SUN, Guofeng ZHAO, Ye LIU, Yong LU 2023, 2023 (1):  95-103.  doi: 10.3969/j.issn.1000-5641.2023.01.010 Abstract ( 26 )   HTML ( 1 )   PDF (1059KB) ( 15 )   A promising chemical looping-oxidative coupling of methane (CL-OCM) oxygen-carrier catalyst, Na2WO4/Mn7SiO12-SiO2, was obtained by adding extra Mn2O3 to Mn2O3-Na2WO4/SiO2 and in-situ activating in the reaction stream. After experiencing an induction period, the oxygen-carrier phase transformed from Mn2O3 to Mn7SiO12 in association with an improvement in C2-C3 selectivity but decreased CH4 conversion. The Na2WO4/Mn7SiO12-SiO2 oxygen-carrier catalysts could also be obtained by directly calcining the Na2WO4/Mn2O3-SiO2 precursor at 800 ℃ in air. At 750 ℃ and a CH4 residence time of 12 s, the catalyst achieved 12% (or 7%) CH4 conversion and 81.5% (or 90.0%) C2-C3 selectivity using a mCat/mCH4 weight ratio of 27 (or 13.5). Notably, only C3H6 was detected as C3 products, whose selectivity was about 5%. The CL-OCM reaction proceeded selectively through the redox cycle mode of Mn7SiO12 $\leftrightarrow$ [MnSiO3 + MnWO4]. The lattice-oxygen mobility in Mn7SiO12 was much weaker than that in Mn2O3, which improved C2-C3 selectivity but decreased CH4 conversion. Our findings provide guidance for the exploration of more advanced catalytic oxygen-carrier catalysts toward efficient CL-OCM process.
 Progress in synthesis of methyl glyoxylate by selective oxidation of methyl glycolate with molecular oxygen Hao WANG, Guofeng ZHAO, Yong LU 2023, 2023 (1):  104-113.  doi: 10.3969/j.issn.1000-5641.2023.01.011 Abstract ( 34 )   HTML ( 2 )   PDF (834KB) ( 26 )   Methyl glyoxylate is widely used in organic synthesis and chemical production. The application of traditional preparation methods is limited by high cost, low efficiency, and significant environmental pollution. During the coal to ethylene glycol process, methyl glycolate is produced as an intermediate product of the hydrogenation of dimethyl oxalate (DMO) to ethylene glycol. Methyl glycolate can be selectively obtained from DMO via hydrogenation, and therefore, has the potential to serve as raw material for methyl glyoxylate. However, only few studies have considered this process. Herein , the applications, traditional preparation methods, and state-of-the-art research progress of methyl glycolate oxidation are reviewed. Recent research on selective oxidation of related alcohols (such as ethanol) to aldehydes and ketones is also summarized.
 Progress in supported Pt-based catalysts for the liquid-phase selective hydrogenation of cinnamaldehyde Mengnan LI, Huiyue XIN, Peng WU, Xiaohong LI 2023, 2023 (1):  114-128.  doi: 10.3969/j.issn.1000-5641.2023.01.012 Abstract ( 28 )   HTML ( 1 )   PDF (3712KB) ( 11 )   The selective hydrogenation of cinnamaldehyde is an important model reaction for investigating the relationship between catalyst structures and regioselectivity. In recent years, researchers have designed and synthesized a series of better-performing, supported Pt-based catalysts for the selective hydrogenation of cinnamaldehyde, based on electronic, synergistic, and geometric effects to improve the selectivity. In this mini-review, we aim to summarize the recent progress in different supported Pt-based catalysts for the selective hydrogenation of cinnamaldehyde and discuss the performance of these supported catalysts to provide ideas for the design of novel better-performing Pt-based catalysts.
CO2 Utilization
 Electrodeposition performance of a copper-based catalyst for the electroreduction of CO2 Meng’en CHU, Chunjun CHEN, Haihong WU, Mingyuan HE, Buxing HAN 2023, 2023 (1):  129-139.  doi: 10.3969/j.issn.1000-5641.2023.01.013 Abstract ( 42 )   HTML ( 3 )   PDF (4857KB) ( 16 )   To improve the catalytic performance of copper-based catalysts in the electroreduction of CO2, nitrotriacetic acid (NTA) was used as an additive to prepare copper-based catalysts having a three-dimensional structure by applying electrodeposition. The prepared catalysts exhibited excellent selectivity and activity for the electroreduction of CO2 to multi-carbon (C2+) products. At –1.26 V vs. RHE, the faradaic efficiency of C2H4 and C2+ products over the Cu-0.5/CP electrode reached 44.0% and 61.6%, respectively, and the total current density reached 12.3 mA·cm–2. In addition, Pd- and Zn-based catalysts were prepared by employing electrodeposition; the results showed that their selectivity for CO was significantly improved, proving that NTA has a certain universality in the preparation of electrocatalysts by using electrodeposition.
 Electrocatalytic coupling of CO2 with organic compounds to value-added chemicals Huan WANG, Jiaxing LU 2023, 2023 (1):  140-148.  doi: 10.3969/j.issn.1000-5641.2023.01.014 Abstract ( 24 )   HTML ( 1 )   PDF (877KB) ( 22 )   The efficient fixation and utilization of CO2 under mild conditions is one of the key components of green carbon science. The electrocatalytic coupling of CO2 and organic compounds can produce value-added chemicals, which is beneficial to sustainable development. In this review, we summarize the current methods of synthesizing carboxylic acids, organic carbonates, carbamates, and other chemicals via electrocatalytic CO2 coupling with organic compounds. We also present the latest research progress and opportunities in this field, such as asymmetric electrocarboxylation to construct chiral molecules, electrochemical ring-opening carboxylation, electrochemical N-methylation, electrocarboxylation with non-sacrificial anodes, and paired electrosynthesis.
 Application of Cu-based catalysts in the electroreduction of carbon dioxide Jing TANG, Zining ZHANG, Xiang ZHENG 2023, 2023 (1):  149-159.  doi: 10.3969/j.issn.1000-5641.2023.01.015 Abstract ( 46 )   HTML ( 2 )   PDF (1081KB) ( 14 )   To achieve the national strategy of carbon neutralization, the electroreduction of carbon dioxide into usable reagents via renewable energy has caused widespread concern in the scientific community. Cu-based electrocatalysts can reduce carbon dioxide to high value-added multi carbon products, but the catalytic mechanism still needs to be studied to improve its selectivity and efficiency. Depending on the state of the Cu, Cu-based catalysts can be divided into Cu alloy/composite catalysts, single-atom, oriented crystalline, and oxidized Cu-based catalysts. This paper introduced the common preparation methods, structural characteristics, effect of electro catalytic reduction of carbon dioxide, and possible catalytic mechanism of the four types of Cu-based catalysts mentioned above.
Biomass Conversion and Chemical Recource Recycle
 Comprehensive review on green synthesis of bio-based 2,5-furandicarboxylic acid Lei ZHAO, Zelin LI, Bolong LI, Shuchang BIAN, Jianhua WANG, Hailan ZHANG, Chen ZHAO 2023, 2023 (1):  160-169.  doi: 10.3969/j.issn.1000-5641.2023.01.016 Abstract ( 49 )   HTML ( 4 )   PDF (1090KB) ( 22 )   Bio-based 2,5-furandicarboxylic acid (FDCA) is expected to partially replace petroleum-based terephthalic acid (PTA) for the synthesis of high-performance polymer materials. This review article summarizes the latest achievements on the various synthesis routes of FDCA from 5-hydroxymethylfurfural (HMF), furoic acid, furan, diglycolic acid, hexaric acid, 2,5-dimethylfuran, and 2-methylfuran. In particular, the direct oxidation, heterogeneous thermal catalytic oxidation, photoelectric catalytic oxidation of HMF and furoic acid carboxylation, disproportionation, carbonylation, and other routes to synthesize FDCA are reviewed in detail. Based on the comparative analysis of the advantages and disadvantages of each route, the HMF route and the furoic acid route are considered the most promising candidates for the large-scale production of FDCA. Further exploration and future research should be carried out to improve the catalytic production and separation efficiency of FDCA, simplify the reaction process, and reduce production wastes.
 Research progress on pollution and degradation of plastic waste Kaizhen MIAO, Jiaolong MENG, Xuefeng JIANG 2023, 2023 (1):  170-176.  doi: 10.3969/j.issn.1000-5641.2023.01.017 Abstract ( 37 )   HTML ( 3 )   PDF (1177KB) ( 13 )   Plastics are widely used in daily life owing to their light weight, portability, and affordability. However, post-consumer-waste plastics do not degrade easily in the natural environment, making plastic pollution a new global environmental issue. Thus, exploration in the field of plastic degradation has increased in recent years. To promote the treatment of plastic waste and provide a scientific reference for environmental protection and sustainable development, this study describes the current state of plastic pollution. It also systematically summarizes various research fields of plastic degradation and presents the development prospect of photocatalysis and bio-based plastics in the future.
Green Chemical Analysis
 Biomedical applications of synthetic nucleic acid engineering Mengyao CAO, Li LI, Hao PEI 2023, 2023 (1):  177-185.  doi: 10.3969/j.issn.1000-5641.2023.01.018 Abstract ( 33 )   HTML ( 4 )   PDF (1728KB) ( 10 )   The simple rule of base-pairing of nucleic acids enables nucleic acid structures to be designed via powerful energy-based prediction tools. Thus, nucleic acid structures have attracted considerable attention owing to their ability to fold into a variety of synthetic structures. However, the lack of chemical diversity of nucleic acid bases makes nucleic acid structures less functionally diverse than proteins, thereby limiting their practical applications. This review focuses on the underlying technology of nucleic acid molecular engineering, especially on the studies of nucleic acid structures and their molecular interactions. As nucleic acid structures are fully spatially addressable, a diversity of particles could be linked to designated positions on the surface of nucleic acid structures. Additionally, the intermolecular reaction kinetics of nucleic acids could be continuously fine-tuned by rational design of nucleic acid sequences. This review also summarizes the development of synthetic molecular networks, dynamic molecular machines, and nucleic acid-based biomaterials, as well as the application of these as green biomedical devices in biomolecular recognition, cell surface engineering, and biocatalysis.
 Preparation and photothermal studies on a cucurbit[8]uril-based near-infrared organic supramolecular photothermal agent Wenyan CAI, Yue PAN, Qiwei ZHANG, Yang TIAN 2023, 2023 (1):  186-193.  doi: 10.3969/j.issn.1000-5641.2023.01.019 Abstract ( 35 )   HTML ( 4 )   PDF (2397KB) ( 16 )   Photothermal therapy has attracted attention as a novel cancer treatment with high specificity, minimal invasiveness, and low toxicity. In this study, a facile, effective, and green method was developed to prepare a novel supramolecular photothermal material. Grinding a commercial dye, dibenzotetrathiafulvalene (DBTTF, with absorption <400 nm) with cucurbit[8]uril (CB[8]) in air with a small amount of water leads to the oxidation of DBTTF to radical cations. Furthermore, DBTTF dimerizes, assembles into the cavity of CB[8], and forms a ternary supramolecular complex with strong absorption in the visible and near-infrared regions, where the longest absorption wavelength exceeds 1000 nm. The photothermal conversion efficiency of the supramolecular system is 18.7%. The system exhibits good photothermal stability and biocompatibility, and has been successfully applied in the photothermal ablation of live tumor cells. This supramolecular material has potential applications in photothermal therapy and other photothermal conversion fields.