Table of Content

01 December 2023, Volume 39 Issue 6

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Contents

Chemical Research in Chinese Universities Vol.39 No.6 December 2023

2023, 39(6):  0-0. 

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Volume Contents of Chemical Research in Chinese Universities to Vol.39(2023)

2023, 39(6):  1-8. 

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Review

Cyclodextrin Based Host-Guest Inclusion Complex, an Approach to Enhancing the Physicochemical and Biopharmaceutical Application of Poorly Water-soluble Drugs

Muhammad INAM, Moshirian-Farahi SAREH SADAT, and Wenjie CHEN

2023, 39(6):  857-861.  doi:10.1007/s40242-023-3204-0

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Host-guest inclusion complexes have been extensively studied for drug delivery applications. The host molecule, typically cyclodextrin, creates a cavity, in which the guest molecule, such as a drug, can be encapsulated. This encapsulation can protect the drug from degradation, improve its solubility and stability, and enhance its bioavailability. Moreover, host-guest inclusion complexes can facilitate targeted drug delivery by selectively releasing drugs at the site of action. Various techniques, such as covalent bonding, non-covalent interactions, and self-assembly have been used to form these complexes. Host-guest inclusion complexes have shown great potential for improving the efficacy and safety of drug delivery systems. This mini review summarizes the application and recent progress of the cyclodextrin-based host-guest inclusion complex, highlighting the enhanced physicochemical and biopharmaceutical application of pharmaceutical drugs via formulation of its inclusion complex.



Comment

Ultrathin Nanofilms Prepared by Interfacial Polymerization

LI Linji, SHI Yongli, and ZHANG Kai

2023, 39(6):  862-863.  doi:10.1007/s40242-023-3116-z

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Recently, Livingston and his colleagues published two articles in Nature and Science, respectively, to tackle the challenges of accurate molecular sieving and crude oil separation in the field of membrane separation by preparing ultrathin nanofilms through interfacial polymerization. One is that the nanofilms with ordered sub-nanopores achieve accurate molecular sieving at ångström precision, and the other is that the permeability of hydrophobic polyamide nanofilms to hydrophobic liquid is significantly enhanced by an order of magnitude. The thoughtful design and excellent performance provide a feasible strategy for the development of membrane separation, and show great potential in industrial applications (drug separation and crude oil fractionation).



Articles

Dipyridyl Azo Compound 4,4'-Azopyridine as a Potential Coating Material for Toilet Sanitizer

WANG Qiwei, JIANG Lu, LAM Pik-Ling, CHUI Chung-Hin, and WONG Wai-Yeung

2023, 39(6):  864-869.  doi:10.1007/s40242-023-3109-y

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Good toilet hygiene can reduce the risk of pathogenic transmission. During flushing, pathogenic bacteria can be spread by the water droplets, especially in the toilet seat. Escherichia coli (E. coli) is one of the frequently occurring Gram-negative bacterial pathogens found in the toilet seats. In this study, we investigated the potential anti-E. coli activity of some azobenzene compounds. Among them, compound 2, with the heterocyclic nitrogen in both phenyl rings, showed the strongest antibacterial effect on E. coli, with the minimum inhibitory concentration of 80 μg/mL and the minimum bactericidal concentration of 320 μg/mL. Compound 2 displayed a comparative zone of clearance [(14.50±2.29) mm] to that of ampicillin [(13.17±1.76) mm]. The reactive oxygen species (ROS) assay suggested that compound 2 might induce the loss of bacteria via the oxidative stress by eliciting the generation of intracellular ROS. We further examined the potential cytotoxicity of compound 2 to the human skin HaCaT cells. Compound 2-treated skin cells showed a good maintenance of cellular morphology and a clear definition of cell nuclei, with a satisfactory cell viability (ca. 90%) at 80 μg/mL. Overall, compound 2 would be a possible antibacterial coating agent for the surface sanitizer of the toilet seats to inhibit the growth of E. coli.



Zeolite-encaged Ultrasmall Pt-Zn Species with Trace Amount of Pt for Efficient Propane Dehydrogenation

QU Ziqiang, ZHANG Tianjun, YIN Xichen, ZHANG Junyi, XIONG Xiaoyun, and SUN Qiming

2023, 39(6):  870-876.  doi:10.1007/s40242-023-3063-8

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Propane dehydrogenation (PDH) has become a globe- welcoming technology to meet the massive demand for propylene, but the most commonly used Pt-based catalysts suffer from quick sintering, poor selectivity for propylene, and unsatisfied Pt utilization. Herein, a series of Silicalite-1 (S-1) zeolite- encaged ultrasmall Pt-Zn clusters with a trace amount of Pt [40— 180 ppm (parts per million)] were developed by using a one-pot ligand-protected direct H₂ reduction method. Interestingly, the extremely low amount of Pt can significantly promote the activity of zeolite-encaged Zn catalysts in PDH reactions. Thanks to the high Pt dispersion, the synergy between Pt and Zn species, and the confinement effect of zeolites, the optimized PtZn@S-1 catalyst with 180 ppm Pt and 1.88% (mass fraction) Zn, exhibited an extraordinarily high propane conversion (33.9%) and propylene selectivity (99.5%) at 550 ℃ with a weight hourly space velocity (WHSV) of 8 h^-1, affording an extremely high propylene formation rate of 340.7 mol_C3H6·g_Pt^-1·h^-1. This work provides a reference for the preparation of zeolite-encaged metal catalysts with high activity and noble metal utilization in PDH reactions.



Bioassay of Carcinoembryonic Antigens by Organic Field-effect Transistors Based on D-A Type Conjugated Polymer

LYU Xiaomeng, DUAN Yuchen, CHEN Yulan, and CHENG Shanshan

2023, 39(6):  877-883.  doi:10.1007/s40242-023-3115-0

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Biosensors based on organic field-effect transistors (OFETs) are one of the most promising electronic devices for emerging bioanalytical applications. The selection of organic semiconductors (OSCs) is essential to improve the sensitivity and reliability of this kind of biosensors. Given the good field effect performance and tunable structures of D-A type conjugated polymers, here, we design two D-A type copolymers [P(BDT- co-DPP2T-ThC2) and P(BDT-co-DPP2T-Th)], which are applied as the OSC layers. With carcinoembryonic antigen antibody (anti-CEA) adsorbed onto the OSC layers as the recognition sites, OFETs based biosensors for CEA detection are developed. The experimental findings support that the attachment of ester side groups onto the polymer backbone[as for P(BDT-co-DPP2T-ThC2)] is favorable for improved solubility and filming properties of the polymer. The introduction of ester side groups affects molecular stacking and enhances intermolecular forces. The resultant devices show high charge mobility and antibody adsorption ability, both of which are critical for sensitive and facile detection of CEA biomarkers. The reliable determination of CEA down to the picomolar level is determined. It is expected that this kind of biosensors fabricated by D-A type conducting polymers will open new avenues toward the early diagnosis, real-time monitoring and treatment of future cancer diseases.



Efficient Construction of a Polyaniline-coated DNA Nanoparticle for Photothermal Therapy

AQIB Raja Muhammad, YANG Changping, WU Xiaohui, WANG Yuang, FAN Jing, SHANG Yingxu, LIU Jianbing, and DING Baoquan

2023, 39(6):  884-890.  doi:10.1007/s40242-023-3122-1

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Photothermal therapy is a direct and non-invasive therapeutic strategy. Herein, we report a general strategy for the construction of polyaniline-coated DNA nanoparticles for efficient photothermal therapy. In our design, two G4/hemin-based DNAzymes are precisely organized in a DNA template to mimic the function of horseradish peroxidase (HRP) for the catalytic oxidation of aniline. After polymerization, the polyaniline-coated DNA nanoparticles (PANI/DNA NPs) can be efficiently obtained as the photothermal agent to elicit a pronounced photothermal effect. After cellular uptake, the noticeable photothermal effect from 808 nm laser irradiation can achieve an efficient proliferation inhibition of tumor cells. This rationally developed photothermal agent based on DNA template-assisted polymerization presents a new avenue for the development of photothermal therapy.



Vertical 3D Printed Pd/TiO₂ Arrays for High Efficiency Photo-assisted Catalytic Water Treatment

FU Chenhao, LI Dan, ZHANG Jianwei, GUO Wei, YANG He, ZHAO Bo, CHEN Zhaomin, FU Xin, LIANG Zhiqiang, and JIANG Lin

2023, 39(6):  891-901.  doi:10.1007/s40242-023-3182-2

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Catalytic degradation of organic contaminants is at the frontier of water treatment due to its selectivity, energy savings, and ability to convert harmful contaminants into harmless or even valuable chemical products for recycling. However, achieving sufficiently high performance in the catalytic removal of organic contaminants for practical application is still extremely challenging. Herein, we report a Pd-decorated TiO₂ (Pd/TiO₂) hierarchical vertical array for fast and efficient catalytic water treatment. Such a forest- like Pd/TiO₂ vertical array demonstrates the following distinct advantages over conventional planar or bulk catalytic systems: 1) abundant anchoring sites for nanocrystals loading; 2) high sunlight absorption; 3) efficient mass transfer channels for the reactants and products. As a proof of concept, the Pd/TiO₂ array demonstrated rapid and efficient photo-assisted catalytic reduction of high concentrations of 4-nitrophenol wastewater (2 g/L, ca. 14.38 mmol/L) and its feasibility for continuous flow wastewater treatment. The turnover frequency (TOF) value of the Pd/TiO₂ array was up to 8.00 min^-1, which was approximately 4.2 times that of planar Pd/TiO₂ film with the same area (1.91 min^-1). Our strategy of incorporating nanocatalysts with a hierarchical vertical array provides a promising approach to boosting the catalytic performance of catalysts for different chemical reactions.



Ordered Arrangement of Different Metals in Discrete and Infinite Building Blocks for Heterometallic Metal-Organic Frameworks Construction

XU Huoshu, YAN Yu, WU Yichen, WANG Junyi, TANG Yi, and LI Qiaowei

2023, 39(6):  902-906.  doi:10.1007/s40242-023-3200-4

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Construction of sophisticated metal-organic frameworks (MOFs) with multiple kinds of metals is essential for further advancement of porous materials toward various applications. Order and arrangement of the metals in the secondary building units (SBUs) greatly influence the MOF structures outcome. While most of the previous heterometallic MOFs either have multiple kinds of discrete SBUs with different metals, or single kind of SBU with mixed metals inside, other forms of metal distribution still need further exploration. Herein, a bifunctional linker is applied to achieving differential coordination toward different metals. With Ce and Cu serving as the carboxylate-philic and pyrazole-philic metal ions, three heterometallic MOFs (FDM-121—FDM-123) are synthesized. In addition to the common metal arrangement modes, the new MOFs provide a joint reticulation of a discrete SBU and an infinite chain-like SBU featuring different metals in FDM-121, and an assembly from heterometallic infinite chain-like SBU in FDM-122. This study demonstrates the potential of bifunctional linkers for the design and synthesis of heterometallic MOFs and opens up the possibilities to create MOFs with tailored properties for specific applications.



Atomically-precise Au₂₄Ag₁ Clusterzymes with Enhanced Peroxidase-like Activity for Bioanalysis

WANG Shuna, LI Zhe, XIA Mingyuan, ZHAO Xiaoxue, CHEN Chuanxia, JIANG Yuanyuan, NI Pengjuan, and LU Yizhong

2023, 39(6):  907-914.  doi:10.1007/s40242-022-2259-7

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Atomically-precise clusterzymes have been widely studied for their special physicochemical properties, but it is still a challenge to enhance their peroxidase-like activity. Herein, we demonstrated that by substituting a single Ag atom into Au₂₅ nanoclusters to form Au₂₄Ag₁ nanoclusters, the peroxidase-like activity was enhanced greatly. In the presence of H₂O₂, Au₂₄Ag₁ could produce reactive oxygen species (ROS) to oxidize colorless 3,3'5,5'-tetramethylbenzidine (TMB) to the blue oxidized TMB (oxTMB). It is worth mentioning that pyrophosphate compounds inhibit the activity of Au₂₄Ag₁. Since alkaline phosphatase (ALP) can dephosphorylate the substrate phosphate compound, that is, remove the phosphate group on the substrate by hydrolysis, the enzymatic activity of the clusterzyme is restored. Based on this, we have developed a sensitive and reliable colorimetric sensing system for the detection of pyrophosphate ion (PPi), adenosine triphosphate (ATP), adenosine diphosphate (ADP) and ALP, respectively. Importantly, the detection limit of the assay system is lower than those of most of the assays that have been reported. In addition, we also built a simple optical logic gate on this basis, further extending the application of metal nanoclusters as peroxidase mimics in bioanalysis. This work could help to shed light on the structure-activity relationship of nanozyme.



A Multifunctional Cobalt (II) Metal-Organic Framework with Nanoporous Channels for Gas and Dye Absorption, and Magnetic Performance

CAO Weiwei, MA Zhilong, and TIAN Li

2023, 39(6):  915-920.  doi:10.1007/s40242-022-2263-y

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Coordination polymer {[Co(BTIA)(H₂O)_0.5]·1.5CH₃OH}_n (Co-1) was synthesized from Co(NO₃)₂·6H₂O and multidentate ligand 4,6-bis-(4H-1,2,4-triazol-1-yl)-isophthalic acid (H2BTIA) under solvothermal conditions. Crystal analysis found that Co-1 was a (4⁴·6²)2(4¹⁶·6¹²) 3D framework with one dimensional channels, which gives it good adsorption performance for greenhouse gas CO2 and anionic dyes CR^2- and TY^-. In particular for the large-size CR^2-, it behaves a very fast removal rate. In addition, magnetic analysis discloses that antiferromagnetic (AF) coupling exists in binuclear cobalt unit.



In situ Synthesis of Ultrasmall Au Clusters on Thiol-modified CeO₂ with Enhanced Stability and CO Oxidation Activity

LI Lingling, XU Jinhui, LIANG Xi, WU Xueting, WANG Xiao, SONG Shuyan, and ZHANG Hongjie

2023, 39(6):  921-927.  doi:10.1007/s40242-022-2267-7

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Gold (Au) nanoclusters supported on various supports have been widely used in the fields of energy and catalysis. However, the poor thermal stability of Au nanoclusters on the support interface usually leads to a reduction or even loss of catalytic activity. Herein, we used an in situ reduction method to synthesize Au nanoclusters on ceria (CeO₂) carriers. In this method, sulfhydryl groups were used to modify CeO₂ nanospheres first, and then Au clusters with an average diameter of 1.5 nm were grown on the surface of ceria reduced with sodium borohydride. The presence of the Au-S-Ce structure enhances the electron transfer efficiency, making the material exhibit high CO oxidation activity at room temperature. Furthermore, due to the strong binding energy of S and Au, the material exhibits a high stability for long time running process. This strategy provides an idea for designing stable and active supported ultrasmall Au nanoclusters catalytic materials.



Efficient Visible Light Hydrogen Evolution Catalyst Composed of Non-noble Metal Nitride (Ni₃N) Cocatalyst and Zn_0.5Cd_0.5S Solid Solution

XU Zhonghang, WU Yuanyu, TAO Ran, JIN Zhanbin, and FANG Xuedong

2023, 39(6):  928-932.  doi:10.1007/s40242-022-2274-8

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In recent years, many effective photocatalysts have been developed to solve the problem of environmental pollution and clean energy shortage. In this paper, non-noble metal cocatalyst Ni₃N nanoparticles supported Zn_0.5Cd_0.5S (ZCS) nanorods (Ni₃N/ZCS) composites were successfully synthesized by ultrasonic method. The hydrogen production efficiencies of the photocatalysts were tested under visible light, which was found that when the loading of Ni₃N was 2% of the mass of ZCS, and the Ni₃N/ZCS composite had the best hydrogen evolution performance, which could reach 70.3 mmol·h^-1·g^-1. In addition, the quantum efficiency under 420 nm monochromatic light irradiation was 27.2%. Through different characterization analyses, such as X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV-Vis diffuse reflectance spectra (DRS), a possible photocatalytic mechanism was proposed, providing some reference values for non-precious metals as cocatalysts.



Electrophilic Halogen Reagents-mediated Halogenation: Synthesis of Halogenated Dihydro-1,3-oxazine Derivatives

QI Liang, QIN Yuji, WANG Xueqing, CHAI Hongli, ZHU Weiwei, and ZHOU Yifeng

2023, 39(6):  933-947.  doi:10.1007/s40242-022-2289-1

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Halogenation of N-cinnamylbenzamides and N-[(2H- chromen-3-yl)methyl]benzamides using electrophilic halogen source was reported. Various halogenated dihydro- 1,3-oxazine derivatives (45 examples) were synthesized in high to excellent yields (up to 98% yields), as well as halogenated dihydrochromeno-1,3-oxazine derivatives (56 examples, up to 96% yields). The properties of mild conditions, metal-free and high efficiency of the reaction made it a promising strategy in future applications for the construction of carbon-halogen (fluorine, F; chlorine, Cl; bromine, Br; iodine, I) bond and 1,3-oxazine derivatives.



Ball-milling Synthesis of Single-atom Cu Anchored on N-Doped Carbon for Mimicking Peroxidase

XU Henan, ZHANG Lingling, WANG Huilin, ZHANG Shaopeng, LI Wei, WANG Xiao, SONG Shuyan, WANG Daguang, and SHI Zhan

2023, 39(6):  948-953.  doi:10.1007/s40242-023-2305-0

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Nanozymes have shown great potential for life sciences owing to their distinct advantages, such as low cost and high stability, compared with natural enzymes. Despite significant progress, state-of-art nanozymes commonly suffer from relatively low specific activities. Herein, we propose a promising to address this issue by creating single-atom nanozymes. A ball- milling-assisted strategy has been developed to induce the transformation of Cu species from bulk to single atoms. The highly- simplified steps allow a large-scale synthesis, that over 4.2 g of single-atom Cu-N doped carbon nanozymes can be achieved in one pot. It exhibits a remarkably improved peroxidase-like activity and stability compared with N doped C anchored Cu nanoparticles. Further experimental firmly reveals the crucial role of the single-atom Cu site that can generate more active ·OH species for boosting the catalytic process.



Face-directed Strategy for the Construction of Polyoxovanadate-based Metal-Organic Tetrahedra

CHEN Huiping, GONG Yaru, CHU Qiangqiang, PANG Xiao, HUANG Xiaojing, TIAN Xudong, YANG Weiting, PAN Qinhe, SU Zhongmin, and WANG Xinlong

2023, 39(6):  954-959.  doi:10.1007/s40242-023-2335-7

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Polyoxometalate-based metal-organic polyhedra (MOPs) were of particular concern because of the various exquisite building blocks and the suitable constructional characteristics. To further understand the design and particularity of polyoxovanadate-based MOPs, (NH₂Me)₈{[V₆O₆(OCH₃)₉(C₆H₅PO₃)]₄· (BPT)₄}·2DMF (HNU-74) and (NH₂Me)₁₂{[V₆O₆(OCH₃)₉(C₆H₅PO₃)]₄· (HBCBAIP)₄}(SO₄)₂·MeOH·DMF (HNU-75) were constructed by a face-directed synthesis strategy. Both structures were assembled with four secondary building units as vertexes and four organic ligands served as faces. Different from HNU-74, HNU-75 showed a carboxyl group free during the coordination process, resulting in the pore channels being blocked and the free carboxyl group linking outwards, paving the way for the formation of the 3D structure. Due to the pore channels of HNU-74, the adsorption of I2 was studied and the adsorption capacity was 148 mg/g.



Multifunctional AIE Molecules Possessing Long-lasting Room Temperature Phosphorescence, Thermally Activated Delayed Fluorescence and Dual-mode Mechanochromism

ZHANG Xiaokun, LI Xiaolong, WANG Zonghao, BAI Lulu, QU Hongmei, and XU Songlin

2023, 39(6):  960-967.  doi:10.1007/s40242-023-2339-3

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Two simple donor-acceptor multifunctional pure organic light-emitting molecules [(9H-carbazol-9-yl)(4-hydroxyphenyl)- methanone (CzMP) and (4-hydroxyphenyl)(10H-phenothiazin- 10-yl)methanone (PTZMP)] with distinct aggregation-induced emission (AIE) properties were synthesized. Surprisingly, CzMP showed a long room temperature phosphorescence lifetime (>900 ms), and PTZMP exhibited triple emission of prompt fluorescence (PF), room temperature phosphorescence (RTP) and thermally activated delayed fluorescence (TADF). Furthermore, CzMP effectively responded to mechanical external forces and solvent fumigation, exhibiting dual-mode mechanochromic luminescence (MCL) including multiple fluorescence color shifts and phosphorescence switching. Time-dependent density functional theory (TDDFT) calculations were investigated to explain different luminescence properties of the two molecules, and the single crystal of CzMP was obtained and analyzed to demonstrate the unique molecular stacking pattern and strong intermolecular interactions in close association with phosphorescence emission. The multifunctional luminescent properties of the emitters explored in this work could be more effectively applied to a wide range of applications, such as information encryption and anti-counterfeiting.



Synthesis, Spectral Analysis and Antimicrobial Activity of New Pd (II) Complexes Involving 5,6-Dimethylbenzimidazole

Murat TÜRKYILMAZ, Murat DÖNMEZ, and Özlen ALTUN

2023, 39(6):  968-975.  doi:10.1007/s40242-023-2355-3

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In this study, firstly, 3-bromopropanenitrile (2a), ethyl bromoacetate (2b), and 2-bromoethan-1-amine (2c) were added to 5,6-dimethylbenzimidazole (1) and symmetrically- connected N-heterocyclic carbenes (NHC) [(3a-3c)] were synthesized. Then, the NHC precursor compounds were reacted with PdCl₂ and Pd (II)-NHC complexes [(4a—4c)] were obtained. The synthesized NHC precursors (3a-3c) and Pd (II)-NHC complexes (4a—4c) were characterized by different spectroscopic methods. The antibacterial activities of these products were measured against bacteria and fungus with the disc diffusion method. Pd (II)-NHC complexes had higher antibacterial activity than the NHC precursors. The synthesized compounds showed antimicrobial activity with different properties from each other. In vitro biological activities of salts and metal complexes on selected bacteria were determined by the broth dilution method based on Clinical and Laboratory Standards Institute guidelines. 1,3-Bis-(2-hydroxyethyl) imidazolinium bromide and 3-(2-ethoxy-2-oxoethyl)-1-(3- aminopropyl)-1H-imidazole-3-ium bromide had activity against Escherichia coli.



Electrochemical Chiral Recognizing Tryptophan Enantiomers Based on Chiral Metal-Organic Framework D-MOF

HOU Huipeng, TANG Shanshan, WANG Wei, LIU Miao, LIANG Axin, XIE Bingteng, YI Yue, and LUO Aiqin

2023, 39(6):  976-984.  doi:10.1007/s40242-023-3004-6

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In this work, an electrochemical chiral sensor of a nanowire-like chiral metal-organic framework/multiwalled carbon nanotube- chitosan/glassy carbon electrode (D-MOF/MWCNTs-CS/GCE) was proposed for the enantiorecognition of L/D-tryptophan (L/D-Trp). The asymmetrical spatial structure of D-MOF provides the feasibility for the enantiorecognition of Trp enantiomers. Moreover, differential pulse voltammetry (DPV) was carried out to be the detection method and the DPV peak potential difference (ΔE_p) between L-Trp and D-Trp was referred as the index of the enantiorecognition performance. Several parameters, such as mass ratios and drop-coated volume of MWCNTs-CS, drop-coated volume and concentration of D-MOF, pH and detection temperature of D-MOF/MWCNTs-CS/GCE were optimized for the largest ΔE_p value. And the molecular dynamics (MD) simulation was used to elucidate the enantiorecognition mechanism. Furthermore, the proportions of D-Trp (D-Trp%) in Trp mixtures were detected in a good linear relationship with the DPV peak potentials (E_p), and the proposed electrochemical chiral sensor exhibited good reproducibility, stability and enantiorecognition ability. Additionally, the proposed electrochemical chiral sensor (D-MOF/MWCNTs-CS/GCE) has a good application prospect in the fields of biomedicine, clinical diagnosis, chemical production, pharmaceuticals safety and so on.



Spatial Correlation in Typical Binary Polycondensation Systems: An Essential Extension of the Kirkwood-Buff Theory

GU Fang, LI Jiangtao, HONG Xiaozhong, and WANG Haijun

2023, 39(6):  985-991.  doi:10.1007/s40242-023-3005-5

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We present the isothermal susceptibility (X_T) for the typical binary polycondensation system of A_f -B_g type, and relate X_T to the weight-average degree of polymerization in terms of the Kirkwood-Buff (KB) theory. The investigation is based on a new expression of X_T for mixtures, which is still expressed by the KB integrals (KBIs) but endowed with an explicit physical interpretation. For polymerization systems, it is proposed that the KBIs can be further decomposed according to whether there exists a bond between particles when conversions (extents of reaction) of functional groups are incorporated into the KBIs. In this way, X_T is directly decomposed into its relevant components as well. This is especially useful to reveal the relationship between local structures and average properties of various polymerization systems. As a consequence, the effect of polymerization on X_T is greatly simplified in comparison with the free energy route. Therefore, we have provided a very simple method to carry out some thermodynamic properties of polymerization systems.



Thermo-sensitive Porous Polymer Membrane-immobilized Cellulose as a Switchable Enzyme Reactor for Tuning Its Enzymolysis via Variation Temperature

QIAO Juan, ZHANG Xinya, CHENG Cheng, and QI Li

2023, 39(6):  992-997.  doi:10.1007/s40242-023-3026-0

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Immobilization of enzymes onto porous membranes has attracted considerable attention in recent years. However, enhancing the enzymolysis efficiency of the resulting enzyme reactors by varying the environmental conditions poses a great challenge. In this work, poly(styrene-maleic anhydride-N,N-dimethylacrylamide) was prepared and utilized to construct a thermo-sensitive porous polymer membrane-based enzyme reactor (TS-PPMER) after cellulase was immobilized onto the support by covalent bonding. The catalytic activity of the nano-reactor was evaluated by measuring the yield of the product, glucose, at different temperatures with carboxymethylcellulose as the substrate. Interestingly, the polymer chains coiled and formed numerous nano-pores at a high temperature, which induced the confine effect and greatly boosted the enzymolysis efficiency of TS-PPMER. Furthermore, the proposed TS-PPMER was applied in the hydrolysis of green plant leaves in Epipremnum aureum. This work shows great potential in obtaining biological resources by an environmentally friendly approach using smart polymer-based nano-reactors.



Equation-of-motion/Linear-response Coupled Cluster Methods with an Approximate Treatment on Triples for Singly-excited States with Pronounced Double Excitation Character

HU Yanmei, LU Yanzhao, WANG Zhifan, and WANG Fan

2023, 39(6):  998-1004.  doi:10.1007/s40242-023-3035-z

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In this work, we investigate the performance of various equation- of-motion/linear-response coupled cluster (EOM/LR-CC) methods with an approximate treatment for triples on excitation energies (EEs) by comparing with EOM-CCSDT (SDT=single, double, triple excitations) results. The focus of this work is on singly-excited states with percentages of the single excitation part (R₁, %) from CC3 between 50% and 80%, i.e., excited states with a pronounced double excitation character. CC3 is shown to provide EEs that agree well with EOM-CCSDT results for such excited states. Moreover, reliable EEs can be obtained with EOM-CCSD (T) (a)^* and CCSDR (3) for excited states with R₁ from CC3 larger than 80%. As for singly-excited states with R₁ from CC3 between 80% and 50%, EEs with EOM-CCSD^*, CCSDR (T) and δ-CR-EOM-CC (2,3)-D agree reasonably well with those of EOM-CCSDT. However, it is too costly to choose a proper method for singly-excited states based on R₁ of CC3 since CC3 is a rather expensive method. On the other hand, our results show that difference between EEs with EOM-CCSD and EOM-CCSD (T) (a)^* [ΔE_{(T) (a)^*}] correlates well with R₁ from CC3 and ΔE_{(T) (a)^*} is about 0.25 eV when R₁ (CC3) is 80%. Appropriate methods to obtain reasonable EEs for singly-excited state can be chosen based on whether ΔE_{(T) (a)^*} is larger than 0.25 eV



A Fluorescent In (III) Metal-Organic Framework for Explosives Detection

LI Wen, LIU Xinyao, LI Guanghua, and LIU Yunling

2023, 39(6):  1005-1009.  doi:10.1007/s40242-023-3058-5

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Anovel metal-organic framework {[In₃(TATAT)₂]·3CH₃NH₃· 7NMF·8H₂O}[JLU-MOF101, H₆TATAT=5,5’,5’’-(1,3,5-triazine- 2,4,6-triyl)tris-(azanediyl)triisophthalate, NMF=N-methyl- formamide] with cor topology has been synthesized under solvothermal conditions. The framework of JLU-MOF101 is constructed by {In(COO)₄}^- nodes and a hexacarboxylic organic ligand. JLU-MOF101 exhibits excellent fluorescence properties in N,N-dimethylformamide (DMF) solution, and its emission spectrum can be greatly overlapped with the ultraviolet absorption spectra of trinitrophenol (TNP) and 2,4-dinitrophenol (2,4-DNP). As a result, JLU-MOF101 exhibits excellent performance of fluorescence quenching for TNP and 2,4-DNP. In addition, we demonstrate the selective detection capability of JLU-MOF101 through a large number of anti-interference tests.



Mechanistic Insights into the Catalytic Condensation of Methyl Ketones on MgO Surfaces

ZHOU Mingxia, Larry A. CURTISS, and Rajeev S. ASSARY

2023, 39(6):  1010-1016.  doi:10.1007/s40242-023-3074-5

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Ketone coupling via aldol condensation is one of the promising routes to produce cyclic and value-added precursors for renewable hydrocarbon biofuels. A first-principles-based microkinetic modeling is performed to evaluate the surface- mediated reaction mechanisms and the role of water molecules in the observed activities for 2-pentanone and 3-pentanone aldol condensation on dehydroxylated MgO (111) surface and hydroxylated terminated surface [OH-MgO (111)]. We have identified the enhancement of the surface OH group to MgO (111) surface catalytic activity by destabilizing the binding strength of reaction intermediates and reducing the energy barriers of rate- determining steps (proton transfer and dehydration steps). The 2- pentanone has one elementary step less in the complete reaction mechanism of aldol condensation and preferable energy barrier for proton transfer and dehydration steps, revealing 2-pentanone as terminal ketone is more reactive than 3-pentanone as central ketone. The water molecules dominated the OH-MgO (111) surface after further addition of water, leading to the reduction of turnover frequency of the aldol condensation dimer product as the loss of aldol condensation reaction intermediates in competitive adsorption with water molecules.



Study on the Host-Guest Interactions Between Tetramethyl Cucurbit[6]uril and Benzimidazole Derivatives

YANG Naqin, DAI Xue, MA Yue, YANG Xinan, and MA Peihua

2023, 39(6):  1017-1022.  doi:10.1007/s40242-023-3078-1

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In this paper, ¹H NMR spectroscopy, isothermal titration calorimetry, X-ray crystallography and other characterization methods were used to investigate the interaction modes of tetramethyl cucurbit[6]uril (TMeQ[6]) and three benzimidazole derivatives in an aqueous solution-solid state. The results showed that the aromatic ring moieties in the three derivatives all entered the cavity of TMeQ[6] and their substituents were located at the port of TMeQ[6], forming 1:1 host-guest inclusion complexes. The crystal structures showed that the aromatic part of the benzimidazole derivatives interacted with the cavity of TMeQ[6] via hydrogen bond interactions and the N atoms on the benzimidazole ring formed hydrogen bonds with the carbonyl oxygen of TMeQ[6]. The ion-dipole interactions between [ZnCl₄]^2- and TMeQ[6] formed supramolecular self-assembly entities.



PCL-based and Hirudin-containing Composite Nanofibers for Prolonged Anticoagulation Effect

ZHENG Zhiwen, DAI Xin, LI Xueyang, and DU Chang

2023, 39(6):  1023-1030.  doi:10.1007/s40242-023-3080-7

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More and more concerns about health bring the increasing demand for blood contact tissue engineering alternatives. In this paper, nanoparticles of poly(lactic- co-glycolic acid)/polyethyleneimine mixed with recombinant hirudin (rHNPs) were prepared by a double emulsion solvent volatilization method, which were then loaded onto the polycaprolactone (PCL) with polydopamine (PDA) coating to form the composite nanofibers of PCL/PDA/rHNPs. The hydrophilicity and mechanical properties of the composite nanofibers were improved significantly compared with pure PCL. The morphology kept almost unchanged after 30 d of degradation in phosphate buffer saline (PBS). The anticoagulant molecule of hirudin could be gradually released from the composite scaffolds through the degradation of rHNPs in vitro. When the concentration of rHNPs suspension was 5.0 mg/mL, the composite nanofibers could better promote the growth and proliferation of human umbilical vein endothelial cells (HUVECs). The anticoagulant ability of the composite nanofibers was also significantly improved in comparison with that of pure PCL. The design of controlled release anticoagulant materials would alleviate the sudden release of simple fixed hirudin, which could also provide a new idea for the development of novel blood contact materials.



CV-etched Nanostructured Ag Foils for Efficient Electrochemical CO₂ Reduction

MAO Yuanxin, CHEN Shi, JIA Zihan, DONG Xufeng, and MAO Qing

2023, 39(6):  1031-1036.  doi:10.1007/s40242-023-3088-z

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Electrochemical reduction of CO₂ has attracted wide attention because it can realize an artificial carbon cycle. The key step to achieving efficient electrochemical conversion of CO₂ is the preparation of catalysts with multiple active sites, prepared without additional strong alkaline solutions. In this work, the surfaces of Ag foils were nanosized by simple cyclic voltammetry (CV) pretreatment, which can supply an abundant specific surface area for the CO₂ reduction reaction (CO₂RR). The results indicated that the CO₂RR performance of Ag catalysts was boosted, and the competitive reaction of H₂ evolution was suppressed. For this catalyst, at -0.92 V vs. RHE (reversible hydrogen electrode), the current density of CO achieved 12.31 mA/cm², a significant increase compared to that of the untreated Ag foils (0.81 mA/cm²). The outstanding electrochemical properties are ascribed to the rich nanostructures on Ag foils after the CV pretreatment. The nanostructure has a very high specific surface area, so it can supply more reactive active sites in the process of CO₂RR.



TEGDME Electrolyte Additive for High-performance Zinc Anodes

ZHANG Weiguo, ZHANG Chong, WANG Hongzhi, and WANG huanhuan

2023, 39(6):  1037-1043.  doi:10.1007/s40242-023-3099-9

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Aqueous zinc ion batteries (AZIBs) are expected to have a wide range of applications for large-scale electrochemical energy storage systems, but their practical application is severely limited by the presence of zinc dendrites, hydrogen evolution reactions (HER), corrosion reactions, and other problems. Electrolyte optimization is considered to be one of the most effective methods for improving zinc anodes due to its simplicity, low production cost and remarkable effectiveness in suppressing zinc dendrite growth. In this paper, a tetra (ethylene glycol) dimethyl ether (TEGDME) electrolyte additive was used to improve the stability of the zinc anode by adding 0.1 g/L TEGDME to the conventional ZnSO₄ electrolyte to prepare a mixed electrolyte. The effect of TEGDME on the side reactions of zinc anode was first assessed by linear sweep voltammetry (LSV) and potentiodynamic polarization. The effect of TEGDME on the structure and morphology of zinc surfaces was observed using an X-ray diffractometer (XRD) and a scanning electron microscope (SEM). And finally, the electrochemical performance of Zn|Zn symmetric cells, Zn||Ti asymmetric cells and Zn-MnO₂ full cells with ZnSO₄ + TEGDME electrolyte was tested by cyclic voltammetry (CV) and galvanostatic cycling. The results show that the addition of TEGDME improves the surface wettability of the Zn anode and reduces the growth of dendrites through solvation structure modulation to suppress HER and zinc corrosion. Thus, TEGDME keeps the Zn anode to maintain a flat surface during charging and discharging, improving the reversibility of plating/stripping. The cycle life of the Zn||Ti asymmetric cell was improved and the Coulombic efficiency was 100% after 100 cycles. The Zn||Zn symmetric cells can be cycled stably for 1800 h at a current density of 1 mA/cm² and a fixed capacity of 1 mA·h/cm², while the capacity retention of the Zn-MnO₂ full cell can be effectively improved from 51.46% to 68.29% at 100 cycles. By using TEGDME electrolyte additives, the cycle life of aqueous zinc ion batteries can be effectively improved, providing a new idea for the development of highly reversible zinc anodes.



Synthesis of a Magnetic Core-shell Fe₃O₄@Cu₃(BTC)₂ Catalyst and Its Application in Aerobic Olefin Epoxidation

HOU Junying, HOU Chuanyuan, LI Jianchang, and HAO Jianjun

2023, 39(6):  1044-1050.  doi:10.1007/s40242-023-3106-1

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Olefin epoxidation is a fundamental reaction in organic chemistry. Herein, a novel magnetic core-shell Fe₃O₄@Cu₃(BTC)₂ metal-organic framework (MOF) heterogeneous catalyst was synthesized for the use in olefin epoxidation. Additionally, the size selectivity of the Fe₃O₄@Cu₃(BTC)₂ catalyst in olefin epoxidation was investigated. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) results indicated that Fe₃O₄@Cu₃(BTC)₂ presented a microsphere morphology, and Cu₃(BTC)₂ MOFs were well dispersed on the Fe₃O₄(PAA) surface after 10 cycles of the synthesis process. The synthesized magnetic core-shell Fe₃O₄@Cu₃(BTC)₂ heterogeneous catalyst could facilitate efficient aerobic olefin epoxidation. Furthermore, the catalyst was used in the aerobic oxidation of alcohols and was found to exhibit excellent activity for primary alcohols.



Photographic Analysis and Optical Diagnosis of Kilowatt Microwave Plasma Torch with Air Carrier Gas

YU Dengjie, YU Bingwen, ZHANG Xuchen, HUANG Shiluo, YING Yangwei, YAN Yuwei, JIN Yining, and JIN Wei

2023, 39(6):  1051-1057.  doi:10.1007/s40242-023-3110-5

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The spatiotemporal motion characteristics of the kilowatt argon microwave plasma torch with the air carrier gas (kW-AC-ArMPT) and the behavior of the plasma filaments are investigated with a digital single-lens reflex (SLR) camera and a high-speed camera. Along with the introduction of the air, both the volume of the central channel and the rotational frequency of the plasma filament are increased. Besides, the excitation temperature (T_exc), rotational temperature (T_rot), and density of electron number (n_e) of the kW-AC-ArMPT are measured with optical diagnosis. It is clearly shown that the introduction of air contributed to the rise of T_rot and n_e of the plasma, which is beneficial to improving the analytical performance of the plasma. Then the detection limits of some heavy metal elements are measured by kW-AC-ArMPT, which are in the ppb range. The experimental results show that the kW-ArMPT has a high tolerance to air injection at least 1.0 L/min, which allows the direct extraction of air from the environment for analysis and therefore has the potential for online and in-situ detection of ambient air quality and industrial exhaust gases.



Supramolecular Self-assembly Formed from Cucurbit[8]uril and p-Hydroxybenzoic Acid

WANG Chenghui, YU Zhichao, BAI Qinghong, PAN Dingwu, PRIOR Timothy J., TAO Zhu, REDSHAW Carl, and XIAO Xin

2023, 39(6):  1058-1063.  doi:10.1007/s40242-023-3119-9

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The binding behavior of cucurbit[8]uril (Q[8]) and p-hydroxybenzoic acid (p-HBA) has been investigated using ¹H NMR titration experiments, UV-Vis absorption, isothermal titration calorimetry (ITC), and X-ray crystallography. Results revealed that the Q[8] can accommodate two p-HBA molecules to form a 1:2 host-guest inclusion complex in solution, namely (p-HBA)₂@Q[8]. From a poorly scattering crystal, we were able to identify two symmetry unique Q[8] rings, but with different p-HBA fillings. The structure can be represented as Q[8]+1.5 p-HBA, which gives Q[8]@(p-HBA)₂∙Q[8]@p-HBA as the structural formula. This supramolecular structure was screened for its ability to capture iodine. The experimental results showed that the adsorption efficiency of the supramolecular organic framework material for iodine capture was 43.8%, with an equilibrium adsorption capacity of 223.3 mg/g.



Promoting Effect of ZnO on the Catalytic Performance of CoZSM-5 for CO₂-Assisted Dehydrogenation of Ethane

HE Huan, ZOU Zhengxi, HUA Weiming, YUE Yinghong, and GAO Zi

2023, 39(6):  1064-1069.  doi:10.1007/s40242-023-3131-0

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Aseries of ZnO-modified cobaltous ion exchanged ZSM-5 catalysts is prepared using incipient wetness impregnation and characterized by X-ray diffraction (XRD), N₂ adsorption, transmission electron microscopy (TEM), UV-Vis diffuse reflectance spectroscopy (DR UV-Vis), X-ray photoelectron spectroscopy (XPS), pyridine-adsorbed Fourier transform infrared (Py-IR) and Raman. Their catalytic performance towards CO₂-assisted dehydrogenation of ethane to ethylene has been evaluated. The addition of ZnO onto CoZSM-5 obviously improved the yield of ethylene as well as the conversion of CO₂. The promoting effect is attributed to the good activity of ZnO for the reverse water gas shift (RWGS) reaction, which enhances the coupling between RWGS and ethane dehydrogenation.



Improving PSCs' Short-circuit Current by Adding NaErF₄: 0.5%Tm@NaLuF₄ Up-conversion Nanoparticles Insertion Layer

LIU Deye, LU Yang, LI Xu, LIU Fengmin, LIU Xiaomin, and LU Geyu

2023, 39(6):  1070-1076.  doi:10.1007/s40242-023-3146-6

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In this study, we synthesized a core-shell structure of up-conversion nanoparticles (UCNPs) and deposited it on the surface of fluorine-doped tin oxide (FTO). Subsequently, we assembled a series of perovskite solar cells with FTO/UCNPs/ c-TiO₂/mp-TiO₂/MAPbI₃/Spiro-OMeTAD/Au structures with an effective area of 0.04 cm². To optimize the devices, we adjusted the concentration of UCNPs precursor. The optimized device showed a power conversion efficiency (PCE) of 16.73% and a short-circuit current density (J_sc) of 26.94 mA/cm² at AM 1.5. These values are 9.20% and 10.47% higher than those of the best performing control device (15.32% for PCE and 24.12 mA/cm² for J_sc), respectively. Furthermore, we characterized the perovskite layer, charge transport layer, and perovskite solar cells using various analytical methods. The results showed that the addition of UCNPs not only improved the charge extraction and transfer, but also enhanced the stability of electron transport layer devices. In conclusion, our findings offer a process for optimizing perovskite cells using UCNPs and preliminarily analyzing their principles.



Highly-selective Pt/PAA@MIL-125 Catalyst for Hydrosilylation of γ-(2,3-Epoxypropoxy) Trimethoxysilane

ZHU Yahui, LUO Yanping, ZHU Fangyu, LIANG Qiuhong, YUAN Mingwei, ZHANG Bingzhen, SHI Shunli, WANG Shuhua, and CHEN Chao

2023, 39(6):  1077-1083.  doi:10.1007/s40242-023-3152-8

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γ-(2,3-Epoxypropoxy) trimethoxysilane is a crucial silicone product synthesized by hydrosilylation. Its derived downstream silicone products have galvanized the development of silicone industry. However, the Speier's or Karstedt's catalysts commonly utilized in its industrial process are homogeneous, leading to complications, such as low catalytic selectivity and recycling difficulty. Herein, a new heterogeneous platinum catalyst was developed by using a titanium-based metal organic framework (MIL-125) composite with polylactic acid (PAA) as the support. The as-synthesized Pt/PAA-2@MIL-125 catalyst exhibited impressive catalytic performance, producing a 97% yield in β-product, and maintained recyclability for the synthesis of γ-(2,3-epoxypropoxy) trimethoxysilane. Further characterization analyses revealed that the introduction of PAA resulted in the formation of a defective mesoporous MIL-125, which accelerated the transmission efficiency of reactants. Moreover, the abundant carboxylic acid groups in the MIL-125/PAA composite could interact strongly with Pt active species, thereby enhancing the catalytic performance and minimizing the loss of Pt, ultimately improving its cycling performance. The comprehensive experiments demonstrated the potential of this catalyst as an effective and versatile heterogeneous catalyst not only for the hydrosilylation of various olefins, but also for the hydrosilyation of silanes.



Highly Durable MIL-96 Membranes via a One-step Active γ-Alumina Conversion Strategy for Gas Separation

GAO Zhuangzhuang, LI Baoju, OU Shuxian, LI Dongsheng, FANG Qianrong, QIU Shilun, and XUE Ming

2023, 39(6):  1084-1091.  doi:10.1007/s40242-023-3177-z

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Metal-organic frameworks (MOFs) are attractive in membrane separation due to their special pore structure and suitable aperture size. The fabrication of defect-free and robust MOF membranes with excellent durability is highly demanded but remains challenging. In this work, we report a one-step active γ-alumina conversion strategy for the facile and reliable fabrication of an MIL-96 membrane. In this case, the γ-Al₂O₃ sol was dip-coated and sintered on the α-Al₂O₃ disc as the active aluminum source and substrate for the nucleation and growth of MOF. A continuous and well-intergrown MIL-96 membrane was generated with exceptional stability due to the strong adhesion to the substrate. The resultant MIL-96 membrane yielded a satisfactory H₂/CO₂ permselectivity and high-temperature resistance, delivering a selectivity of 12.35 with H₂ permeance of 6.20×10⁻⁷ mol·m⁻²·s⁻¹·Pa⁻¹ at 150 ℃. Moreover, the probe membrane presented remarkable durability and recyclability under harsh hydrothermal conditions. This method paves the way for constructing highly stable and selective MOF membranes and could accelerate the development of advanced membrane separation technologies for gas purification and recycling in addressing the severe energy and environmental problems.



Colorimetric Recognition of 3,4-Dihydroxy-D,L-phenylalanine with Tetrapeptide-modified Copper Nanoparticles as Chiral Nanozymes

TIAN Lin, CHENG Cheng, ZHAO Zhenwen, LIU Wei, and QI Li

2023, 39(6):  1092-1099.  doi:10.1007/s40242-023-3193-z

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The construct of artificial nanocatalyts by simulating natural enzymes and thereby bringing new properties for practical applications is still a challenging task to date. In this study, chiral tetrapeptide (L-phenylalanine-L-phenylalanine-L-cysteine-L-histidine)-engineered copper nanoparticles (FFCH@CuNPs) were fabricated as an artificial peroxidase (POD). More interestingly, the nano-catalysts exhibited chiral identification function. In comparison with other nanocatalysts like L-cysteine-, L-histidine-, chiral dipeptide (L-cysteine-L-histidine)-, or chiral tripeptide (L-phenylalanine-L-cysteine-L-histidine)-modified CuNPs, FFCH@CuNPs demonstrated higher POD-mimetic catalytic activity in the 3,3',5,5'-tetramethylbenzidine (TMB)-H₂O₂ system and stronger enantioselectivity in the recognition of 3,4-dihydroxy-D,L-phenylalanine (D,L-DOPA) enantiomers. Considering the strength difference between the intermolecular hydrogen bonding and the π-π interactions, the principle behind the chiral discrimination of D,L-DOPA was explored. Furthermore, higher contents of surface Cu²⁺ ions and hydroxyl radicals were found in the FFCH@CuNPs-D-DOPA-TMB-H₂O₂ system than in the FFCH@CuNPs-L-DOPA-TMB-H₂O₂ system. Based on these results, a protocol for distinguishing between D,L-DOPA enantiomers through colorimetric recognition was established. This study provides a new insight into the design and fabrication of oligopeptides@CuNPs-based chiral nanozymes with improved catalytic performance and features additional to those of natural enzymes.



Hierarchical Ti₃C₂/TiO₂/MoS₂ Composite as an Anode Material for Sodium-ion Batteries

BAI Yulin, FENG Rong, YAN Tao, LIU Yusi, CUI Li, and WANG Kaixue

2023, 39(6):  1100-1105.  doi:10.1007/s40242-023-3196-9

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MoS₂ with a large interlayer spacing of 6.24 Å (1 Å=0.1 nm) and a high theoretical capacity of 678 mA·h·g^‒1 is recognized as a potential electrode candidate for sodium-ion batteries. However, its agglomeration tendency and volume change upon the charge/discharge cycling lead to fast capacity decay and poor cyclic stability. In this work, a hierarchical Ti₃C₂/TiO₂/MoS₂ composite was prepared to improve the electrochemical performance of MoS₂. Ti₃C₂T_x MXene was used as a conductive agent and mechanical support, while zero-strain TiO₂ generated through the in-situ oxidization of Ti₃C₂T_x MXene was utilized as a structural stabilizer. Compared with Ti₃C₂/TiO₂, Ti₃C₂, and MoS₂, the Ti₃C₂/TiO₂/MoS₂ composite exhibited excellent electrochemical performance: a high specific capacity of 413.6 mA·h·g^‒1 was retained after charge/discharge at 0.1 A/g for 100 cycles and a high rate capacity of 302.2 mA·h·g^‒1 was achieved at 8.0 A/g as an anode material for sodium-ion batteries. Therefore, this work sheds light on the development of MoS₂-based materials for anodes of sodium-ion batteries.



Extension of Highly Efficient Alcohol-promoted Rearrangement into One-pot Domino Palladium-catalyzed Carbonylation for Sterically Crowded Aromatic Six-membered Imides

GUO Rong, ZHANG Jingmei, JIA Xiaohui, SHI Chunfeng, QIE Fengxiang, and ZHEN Yonggang

2023, 39(6):  1106-1110.  doi:10.1007/s40242-023-3209-8

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Aromatic six-membered imides suffer the introduction of bulky substituents at the imide positions due to the formation of isoimides and low reactivity, preventing from the investigation of the intrinsic molecular properties. Here, we found a highly efficient alcohol-promoted rearrangement from isonaphthalimide to naphthalimide under acid or basic nonaqueous conditions, which can be regarded as model compounds for aromatic six-membered imides. We proposed two-step nucleophilic substitutions in the isomerization mechanistic pathways that were verified by the separation of a key intermediate. Furthermore, in-situ ¹H NMR exhibited the first-order kinetics for the isoimide loss process. Finally, the alcohol-promoted isoimide-imide rearrangement was extended to a palladium-catalyzed one-pot domino carbonylation reaction toward sterically crowded aromatic six-membered imides.



Enhanced Removal of Phenols by MIZ-Cu Nanozyme Exhibiting Laccase-like Activity and Broader Adaptability to Temperature and pH Conditions

WANG Yunlong, SUN Yue, WANG Le, ZHANG Hao, HU Jiakang, and LI Yongxin

2023, 39(6):  1111-1118.  doi:10.1007/s40242-023-3224-9

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Phenolic compounds, classified as persistent organic pollutants, pose a significant threat to both human health and environmental safety. Therefore, the efficient removal of phenolic substances from water is of paramount importance. Laccase, a multicopper oxidase, is commonly utilized for the efficient removal of phenolic contaminants from water due to its highly effective catalytic activity towards phenolic compounds. However, natural laccase exhibits certain limitations that impede its practical implementation in industrial settings, including a restricted pH activity range, diminished enzymatic efficacy at elevated temperatures, and substantial cost implications. In this work, we prepared a nanozyme (MIZ-Cu, MIZ: 2-methylimidazole) with laccase-like activity by coordinating 2-methylimidazole and copper. This nanozyme overcomes the deactivation issues observed in natural laccase under high temperature and alkaline conditions. The catalytic activity of the MIZ-Cu towards phenolic compounds surpasses that of natural laccase across a wide range of temperature and pH conditions. Under pH=9, 80 ℃, and 500 mmol/L NaCl conditions, the removal rate of four phenols (catechol, hydroquinone, resorcinol, and phloroglucinol) by MIZ-Cu was much higher than that of natural laccase. The results also demonstrate exceptional removal rates in natural aquatic environments, thereby presenting a promising approach for the treatment of phenol- containing wastewater originating from industrial facilities.