Chemical Research in Chinese Universities

Chemical Research in Chinese Universities Vol.40 No.1 February 2024

2024, 40(1): 0-0.

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Recent Advances in Biomass-derived Porous Carbon Materials: Synthesis, Composition and Applications

ZHAI Ziqi, LU Yumiao, LIU Guangyong, DING Wei-Lu, CAO Bobo, HE Hongyan

2024, 40(1): 3-19. doi:10.1007/s40242-024-3259-6

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Porous carbon materials (PCMs) play a pivotal role in diverse applications, such as energy storage, adsorption, catalysis, environmental remediation, and microwave adsorption. The selection of carbon precursors, in particular, is crucial for tailoring porous structures with specific functionalities. Biomass, with its rich carbon feedstock, abundant availability, renewability, and versatile structures, has emerged as a promising precursor for porous carbon material synthesis. This review comprehensively summarizes the recent advances in biomass-derived porous carbon materials (BPCMs) encompassing synthetic strategy, morphology, structural composition, and multiple applications. We first review synthetic approaches aiming at regulating porosity, followed by morphological and composition features of BPCMs, with a special emphasis on elucidating the dimensional clarification and heteroatom doping effects. The discussion then extends to the wide-ranging applications of BPCMs, covering energy-related applications and CO₂ adsorption to environmental remediation. Finally, the review outlines the existing challenges and prospects in the field. In summary, this review systematically describes BPCMs and provides valuable guidance for researchers to select and synthesize BPCMs that meet specific functional requirements.

Recent Advances in Microbial Production of Terpenoids from Biomass-derived Feedstocks

CAO Yujin, XIAN Mo

2024, 40(1): 20-28. doi:10.1007/s40242-024-3242-2

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Terpenoids are a diverse class of natural products widely used as pharmaceuticals, perfumes, flavors, and biofuels. Traditionally, terpenoids are obtained from natural sources, such as plants, but their production is limited by the insufficiency of resources and low yields of extraction. Microbial production of terpenoids has emerged as a promising alternative due to that it is sustainable and easy to scale up. This review aims to summarize recent advances in microbial production of terpenoids from inexpensive biomass-derived feedstocks. Metabolic pathways and key enzymes involved in terpenoid biosynthesis are introduced. Microorganisms that can utilize low-cost lignocellulosic feedstocks for terpenoid production are highlighted. The challenges and prospects faced by microbial terpenoid production are proposed. We believe that continuous progress in the fields of biomass transformation and synthetic biology will ultimately achieve industrial production of microbial terpenoids.

Robust Carbon-Carbon Cleavage in Lignin to Produce Phenol and Cyclohexanone

WANG Lulin, CHENG Xiaomeng, DONG Minghua, LUAN Sen, WU Yuxuan, HAN Buxing, LIU Huizhen

2024, 40(1): 29-35. doi:10.1007/s40242-024-3279-2

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The challenge of breaking 5-5' bonds in lignin, attributed to their high bonding energy, has prompted the development of a new transformation pathway. Biphenyl, an important model compound for lignin, contains these 5-5' bonds, making it crucial to devise a strategy for their cleavage in lignin transformation. This study introduces a novel method for transforming biphenyl, involving selective hydrogenation to cyclohexylbenzene by Ni/SiO₂ catalyst, followed by its oxidation to phenol and cyclohexanone through a radical mechanism. Results demonstrate that the catalysts with small particles have strong catalytic activity, while there is little difference in selectivity. The reason for the high selectivity of cyclohexylbenzene is due to the limited adsorption of cyclohexylbenzene on Ni/SiO_2. This work presents a fresh approach to breaking resilient C-C bonds in lignin.

A Highly Efficient Ni/Al₂O₃-LaO_x Catalyst for the Reductive Amination of Furfural to Furfurylamine: the Promoting Effect of La

YANG Yinze, ZHANG Liyan, ZHOU Leilei, CHENG Haiyang, ZHAO Fengyu

2024, 40(1): 36-46. doi:10.1007/s40242-023-3216-9

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The reductive amination of furfural to furfurylamine is an important and still challenging topic in the field of biomass conversion. In this work, we prepared a series of Ni/Al₂O₃-LaO_x catalysts by co-precipitation method, the role of La played in promoting the catalytic performances of reductive amination furfural was discussed based on the changes in the electronic state of Ni species, acidity, and Ni particle size. The catalytic activity and the selectivity of furfurylamine are highly dependent on the surface properties and the structure of the catalyst. The addition of La promoted the amount of strong acidic sites and the H₂dissociation and spillover on the surface, thus inducing the improvement of the catalytic activity and furfurylamine selectivity. The Ni/Al₂O₃-0.5LaO_xcatalyst with suitable acid sites gave a high yield of furfurylamine (94.9%) under mild reaction conditions. Moreover, the catalyst could be recycled five times without significant loss in activity. The Ni/Al₂O₃-LaO_x catalyst is of great promise in the production of amines via reductive amination reaction.

Engineering the Interface Between Au Nanoparticles and CoO-Ov to Enhance the Catalytic Performance of 5-Hydroxymethylfurfural (HMF) to 2,5-Dimethylfuran (DMF)

XIANG Shuang, GUO Yong, LIU Xiaohui, WANG Yanqin

2024, 40(1): 47-54. doi:10.1007/s40242-023-3235-6

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The interface between Au and support has attracted extensive interest because of its unique catalytic ability for hydrogen activation in catalytic hydrogenation/hydrogenolysis reactions. Herein, we create the Au-CoO-O_V interface in the 1.0%Au/Co₃O₄-Rod-250 catalyst, which could dissociate H₂ via the heterolytic way to yield rich hydride species and achieve excellent catalytic performance in the hydrogenolysis of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF). The XRD and HRTEM analyses show that Au nanoparticles are uniformly dispersed on CoO-O_V surface and in situ DRIFTS spectra show the enhancement of heterolytic dissociation of hydrogen (signals of Au-D and O-D vibration) compared with bare CoO (Co₃O₄-Rod-250). This work provides insights for fabricating highly active Au-support catalysts for catalytic hydrogenation/hydrogenolysis reactions.

Predication of Selective Ring-opening Hydrogenolysis for Furfuryl Alcohol to Produce Pentanediol over Dual-atom Catalysts

WANG Tingting, WANG Jia, XI Yongjie, HU Bin, LI Fuwei

2024, 40(1): 55-63. doi:10.1007/s40242-024-3243-1

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Selective activation of C-O bond is of fundamental importance in the precise conversion of oxygenates into value-added compounds in an atom-economic and sustainable manner, and meanwhile, the structurally well-defined dual-atoms catalysts (DACs) have been scarcely investigated in this field. In this study, a series of transition metal DACs anchored on nitrogen-doped graphene (TM₂/NC, TM=Pt, Ir, Rh, Pd, Ru, Co, Ni and Cu) was constructed to make a comprehensive investigation of their selectivity in the hydrogenative transformation of furfuryl alcohol (FAL), an important biomass platform molecule, to 1,2-pentanediol (1,2-PeD) via selective cleavage of furanic C5-O bond, by density functional theory (DFT) calculations and microkinetic modeling. We found that Ir₂/NC demonstrated a high selectivity for the cleavage of furanic C5-O bond to produce 1,2-PeD, while the production of THFAL or 1,5-pentanediol (1,5-PeD) on other TM₂/NC catalysts are more favorable. Furthermore, we found that the selective C-O bond cleavage of FAL furan ring is affected by the orbital overlap between the d-orbitals of the anchored metal atoms and the p-orbitals of the adsorbed C atom in FAL, suggesting that the selectivity of the C-O bond cleavage is inextricably related with the electronic property of the anchored metals.

Fatigue-resistant Hydrogels

LI Luofei, LEI Hai, CAO Yi

2024, 40(1): 64-77. doi:10.1007/s40242-023-3250-7

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Hydrogels have been extensively studied for applications in various fields, such as tissue engineering and soft robotics, as determined by their mechanical properties. The mechanical design of hydrogels typically focuses on the modulus, toughness, and deformability. These characteristics play important roles and make great achievements for hydrogel use. In recent years, a growing body of research has concentrated on the fatigue property of hydrogels, which determines their resistance to crack propagation in the networks during cyclic mechanical loads for applications. However, knowledge of hydrogel fatigue behavior remains notably deficient. Here, we present a brief overview of the fatigue behavior of hydrogels, encompassing the general experimental methods to measure the fatigue property and fundamental theoretical calculation models. Then, we highlight multiple strategies to enhance the fatigue resistance of hydrogels. Finally, we present our perspectives on fatigue-resistant hydrogels, outstanding challenges and potential directions for future research.

Zeolite-confined Fe-site Catalysts for the Hydrogenation of CO₂ to Produce High-value Chemicals

HAN Xiaoyang, XIA Huicong, TU Weifeng, WEI Yifan, XUE Dongping, LI Minhan, YAN Wenfu, ZHANG Jia-Nan, HAN Yi-Fan

2024, 40(1): 78-95. doi:10.1007/s40242-023-3269-9

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Zeolite-confined Fe-site catalysts (ZFCs) have emerged as superior materials for sustainably producing high-value chemicals through CO₂ hydrogenation, owing to their adaptable framework, customizable composition, and thermal robustness. They excel in activating, adsorbing, and converting CO₂ with remarkable efficiency and consistency in performance. This has sparked a surge in research interest in recent years. The review delves into the latest advancements in CO₂ catalytic hydrogenation to olefins, alcohols, aromatics, and other liquid hydrocarbons, examining the synthesis, modification tactics, and the correlation between structure and performance across various ZFCs. Additionally, it underscores the pivotal factors affecting performance and sheds light on the mechanisms behind selectivity control in the CO₂ hydrogenation process facilitated by ZFCs. To conclude, it presents pressing challenges and strategic recommendations to inspire the development of high-performance, durable ZFCs for CO₂ hydrogenation applications.

Discovery of Novel Anthranilic Diamide Derivatives Bearing Sulfoximine Group as Potent Insecticide Candidates

ZHANG Hongyuan, PENG Jinmin, ZHONG Yuanhan, CHEN Yue, WANG Qing, Haditullah HADIATULLAH, XIE Weibin, XIONG Lixia, YUCHI Zhiguang, LIU Jingbo, LI Yuxin

2024, 40(1): 96-108. doi:10.1007/s40242-023-3218-7

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The fall armyworm, Spodoptera frugiperda (S. frugiperda), represents the most resistant insect species and poses serious threat to grain yield. Chlorantraniliprole (CHL), which targets the ryanodine receptors (RyRs) in insects, has demonstrated the efficacy in controlling S. frugiperda. Nevertheless, this has led to emerging resistance in several countries. To counter this resistance, a viable approach involves the development of novel compounds that bind against RyRs via distinct binding sites or modes. In this study, a series of 22 novel anthranilic diamide derivatives was designed and synthesized, and their insecticidal activities were evaluated. Most of these derivatives showed moderate to good insecticidal activity against S. frugiperda and Mythimna separata. Time-lapse fluorescence measurements of endoplasmic reticulum luminal calcium revealed that most derivatives elicited cellular responses similar as CHL when assessed on HEK293 cells expressing S. frugiperda ryanodine receptors (SfRyRs). The mode of action of compound 13a was studied and verified on the isolated neurons by calcium imaging technique. Finally, molecular docking analysis was employed to predict the binding mechanism of compound 13a against SfRyRs. Overall, these novel diamide derivatives hold promise as a valuable resource for guiding the future design of insecticidal compounds targeting RyRs.

Electrocatalytic Performance of Carbon Layer and Spherical Carbon/Carbon Cloth Composites Towards Hydrogen Evolution from the Direct Electrolysis of Bunsen Reaction Product

ZHANG Wanjia, GUO Tingyu, LIU Yanhua, ZHANG Xuewei, ZOU Bo, ZHAO Chun, SUO Hui, WANG Hui, ZHAO Xu

2024, 40(1): 109-118. doi:10.1007/s40242-023-3223-x

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A composite material comprising a carbon layer and spherical carbon/carbon cloth (C-SC/CC) was fabricated using a hydrothermal-pyrolysis method, employing carbon cloth as the substrate and glucose as the carbon source. The C-SC/CC electrode was evaluated as an electrocatalytic electrode for hydrogen production by electrolysis of Bunsen reaction products. The electrode prepared with 4 g of glucose and annealed at 800℃ showed excellent electrocatalytic activity. It requires only a potential of 185 mV (vs. SCE) to achieve a current density of 10 mA/cm². Furthermore, the electrode demonstrated good stability with a 6% loss in current density after 1000 cycles of scanning from 0.2 V to 1.2 V. These results indicate the potential of the SC/CC electrode as an efficient and durable electrocatalyst for the electrolysis of H₂SO₄ and HI.

Two Indium(III)-based Fluorescent Metal-Organic Frameworks for Highly Sensing Fe³⁺, 2,4-DNP, and TNP

WANG Dan, LI Wen, LI Guanghua, HUA Jia, LIU Yunling

2024, 40(1): 119-126. doi:10.1007/s40242-023-3228-5

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Two novel metal-organic frameworks (MOFs), JLU-MOF130 ([In(NH₂-BDC)(Imi)(1H-Imi)]·DMF·H₂O, NH₂-H₂BDC=2-aminoben-zene-1,4-dicarboxylic acid, 1H-Imi=1H-imidazole, DMF=N,N-dimethylformamide) and JLU-MOF131 ([In(1,4-NDC)(Imi) (1H-Imi)]·DMF_0.5, 1,4-H₂NDC=1,4-naphthalene-dicarboxylic acid), were synthesized. JLU-MOF130 features a three-dimensional (3D) architecture with a neb topology. JLU-MOF131 is characterized by a two-dimensional (2D) structure with an sql topology. JLU-MOF130 has excellent fluorescence detection performance towards Fe³⁺, 2,4-dinitrophenol (2,4-DNP), and 2,4,6-trinitrophenol (TNP), but the fluorescence detection performance of JLU-MOF131 is further improved by converting NH₂-H₂BDC to more conjugated 1,4-H₂NDC. The Stern-Volmer (SV) quenching constant (K_SV) values of JLU-MOF130 sensing 2,4-DNP, TNP, and Fe³⁺ are 5.24×10⁴, 4.44×10⁴, and 4.73×10³ L/mol, respectively. The corresponding limit of detection (LOD) values are 1.17, 1.36, and 14.59 µmol/L. The K_SV values for JLU-MOF131 are 1.26×10⁵, 9.02×10⁴, and 8.48×10³ L/mol, and the corresponding LOD values are 0.35, 0.42, and 3.60 µmol/L, respectively. Interestingly, the emission wavelengths of the two MOFs obviously shift as the fluorescence emission intensities decrease upon the addition of 2,4-DNP and TNP, which can be applied in selective detection.

Rapid Degrading Carbamazepine in a Novel Advanced Oxidation Process of Bisulfite Activated by Lithium Cobaltate Recovered from Spent Lithium-ion Battery

YAN Jiali, YANG Kaiying, WANG Xi, ZHAI Jinli, ZHU Wenjie, YANG Daoli, LUO Yongming, GAO Xiaoya

2024, 40(1): 127-135. doi:10.1007/s40242-024-3237-z

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Maximizing the sustainable recycling of spent lithium-ion batteries (LIBs) shows economic and environmental significance. This study recovered lithium cobaltate (LiCoO₂, LCO) from spent LIBs cathode powder. The recovered LCO was then combined with NaHSO₃ to remove refractory organic pollutants of carbamazepine (CBZ) in water. The degradation of CBZ reached 80.0% within 60 min, by ¹O₂, SO₄^-·, ^·OH and O₂^-· generated in the LCO/NaHSO₃ reaction. The electron transfer between Co (III) and Co (II) was beneficial to the generation of free radicals. The LCO/NaHSO₃ degraded CBZ effectively in both secondary outlet water and tap water. However, high concentrations of inorganic ions (Cl^‒, HCO₃^-, HPO₄^2-, SO₄^2-, NO₃^-) and natural organic matter (humic acid, HA) could inhibit the degradation of CBZ. After three cycles, the stability of the LCO/NaHSO₃ system was demonstrated by the maintained high efficiency in the degradation of CBZ. The obtained data indicate that the LCO/NaHSO₃ system holds great application potential in the field of advanced oxidation degradation of pollutants.

A Bird's Eye View of Quantitative Proteome of Tumor Tissues from Lung Cancer Patients by a High Precision Mass Spectrometry Method

DU Xiaohui, LI Encheng, WANG Qi, YOU Xin

2024, 40(1): 136-144. doi:10.1007/s40242-024-3246-y

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Lung cancer produces a high incidence of malignant tumors. There have been many studies on lung cancer using mass spectrometry (MS) technologies. However, most studies have focused on humoral samples. In this work, 26 pairs of tissue samples (tumor vs. para-tumor) from patients with lung cancer were analyzed using liquid chromatography-tandem MS (LC-MS/MS) with data-independent acquisition mode. In total, 3152 proteins were quantified from tissue samples with high confidence, including 189 up-regulated and 522 down-regulated proteins (tumor vs. para-tumor). In addition, 79 and 690 proteins were identified only in para-cancerous samples and cancerous samples, respectively. The results from bio-informatics tools indicated that altered proteins like PEBP1, HRG and LYZ could be ideal reservoirs for screening the potential biomarkers for lung cancer. It is believed these tissue-specific proteomics results will assist in the studies of lung cancer.

Strategy for Detecting Systemic Treatment Sensitivity of Primary Liver Cancer Based on a Novel Infrared-emissive Organic Nanoparticle

WU Jun, LI Yongzhi, QIN Hanjiao, GAO Ying, YANG Bing, SHENG Jiyao, ZHANG Xuewen

2024, 40(1): 145-152. doi:10.1007/s40242-023-3248-1

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In this study, we synthesized an organic material with near-infrared emission capabilities:4-(2-(4-(9-(4-(diphenylamino) phenyl) naphtho[2,3-c] [1,2,5] thiadiazol-4-yl) phenyl)-1H-phenol-1-ylidene) malononitrile (TPA). Furthermore, TPA-PEG2000 fluorescent nanoparticles were prepared via coating the shells with PEG2000. TPA-PEG2000 exhibited strong near-infrared emission near 700 nm, with a photoluminescence quantum yield of 15.09%, indicating a high emission efficiency. Molecular biology experiments have confirmed its low toxicity and excellent biocompatibility. Increased cholesterol and phospholipid levels in liver cancer cell membranes with low sensitivity or high drug resistance lead to increased rigidity, reduced membrane fluidity, reduced endocytic efficiency, and reduced uptake. Therefore, the uptake of TPA-PEG2000 nanoparticles into cells and the near-infrared fluorescence intensity can be used to evaluate the sensitivity of systemic liver cancer treatment in a simple and efficient manner.

Open-vessel Synthesis of Poly-N-methoxyethylglycine

LIU Guojian, MA Ke, CHEN Qi, ZHANG Donghui, LIU Runhui

2024, 40(1): 153-158. doi:10.1007/s40242-024-3260-0

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Polypeptoids are widely used in biological applications owing to their diverse functions and proteolytic stability. One type of polypeptoids, poly-N-methoxyethylglycine (P-Nmeg), has been found to possess remarkable hydrophilicity and notable properties in terms of protein, cell, and bacterial antifouling. However, the currently known synthesis methods of P-Nmeg include solid-phase synthesis, which is time-consuming and difficult to scale up, and N-substituted N-carboxyanhydride (NNCA) ring-opening polymerization, whose monomers were difficult to store. In this study, we used the chemical stable Nmeg N-phenoxycarbonyl (NPC) as the monomer, which was obtained without the use of highly toxic reactants, such as phosgene or phosphorus halide, to synthesize P-Nmeg under open-vessel conditions. By adding BnNH₂ as an initiator at 80℃, we can obtain controllable short chain length P-Nmeg with narrow dispersity.

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