Chemical Research in Chinese Universities

Special Column on Biomolecular Recognition and Functional Regulation

YUAN Quan, TAN Jie

2022, 38(4): 1-2. doi:10.1007/s40242-022-4000-y

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Current Advances in Aptamer-based Biomolecular Recognition and Biological Process Regulation

CHEN Sisi, ZHANG Lei, YUAN Quan, TAN Jie

2022, 38(4): 847-855. doi:10.1007/s40242-022-2087-9

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The interaction between biomolecules with their target ligands plays a great role in regulating biological functions. Aptamers are short oligonucleotide sequences that can specifically recognize target biomolecules via structural complementarity and thus regulate related biological functions. In the past ten years, aptamers have made great progress in target biomolecule recognition, becoming a powerful tool to regulate biological functions. At present, there are many reviews on aptamers applied in biomolecular recognition, but few reviews pay attention to aptamer-based regulation of biological functions. Here, we summarize the approaches to enhancing aptamer affinity and the advancements of aptamers in regulating enzymatic activity, cellular immunity and cellular behaviors. Furthermore, this review discusses the challenges and future perspectives of aptamers in target recognition and biological functions regulation, aiming to provide some promising ideas for future regulation of biomolecular functions in a complex biological environment.

Programmable Oligonucleotide-Peptide Complexes:Synthesis and Applications

XU Min, ZHOU Baomei, DING Yan, DU Shanshan, SU Mengke, LIU Honglin

2022, 38(4): 856-865. doi:10.1007/s40242-021-1265-5

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Nucleic acids form biological blueprint and polypeptides assist life activities, both of which are indispensable to organisms. Recently, oligonucleotide-peptide complexes (OPCs) have shown great potential in biomedicine, material chemistry and other fields due to their considerable stability and programmability. It remains a huge challenge to stably and facilely constructing OPCs that also limits the wide applications. This tutorial review first summarizes the synthesis strategies of OPC conjugation and the corresponding characteristics in detail, then gives examples of the applications of OPCs, and finally presents a prospective overview on challenges and future perspectives of OPCs. This review aims to help researchers understand the current situation and challenges in this field, thereby furthering interests in developing novel OPC synthesis techniques.

Recent Progress on Highly Selective and Sensitive Electrochemical Aptamer-based Sensors

TANG Tianwei, LIU Yinghuan, JIANG Ying

2022, 38(4): 866-878. doi:10.1007/s40242-022-2084-z

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Highly selective, sensitive, and stable biosensors are essential for the molecular level understanding of many physiological activities and diseases. Electrochemical aptamer-based (E-AB) sensor is an appealing platform for measurement in biological system, attributing to the combined advantages of high selectivity of the aptamer and high sensitivity of electrochemical analysis. This review summarizes the latest development of E-AB sensors, focuses on the modification strategies used in the fabrication of sensors and the sensing strategies for analytes of different sizes in biological system, and then looks forward to the challenges and prospects of the future development of electrochemical aptamer-based sensors.

Aptamers as Recognition Elements for Electrochemical Detection of Exosomes

CHANG Kaili, SUN Peng, DONG Xin, ZHU Chunnan, LIU Xiaojun, ZHENG Dongyun, LIU Chao

2022, 38(4): 879-885. doi:10.1007/s40242-022-2088-8

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Exosome analysis is emerging as an attractive noninvasive approach for disease diagnosis and treatment monitoring in the field of liquid biopsy. Aptamer is considered as a promising molecular probe for exosomes detection because of the high binding affinity, remarkable specificity, and low cost. Recently, many approaches have been developed to further improve the performance of electrochemical aptamer based(E-AB) sensors with a lower limit of detection. In this review, we focus on the development of using aptamer as a specific recognition element for exosomes detection in electrochemical sensors. We first introduce recent advances in evolving aptamers against exosomes. Then, we review methods of immobilization aptamers on electrode surfaces, followed by a summary of the main strategies of signal amplification. Finally, we present the insights of the challenges and future directions of E-AB sensors for exosomes analysis.

Recent Progress in Mass Spectrometry-based Metabolomics for Colorectal Cancer

XIAO Chulei, CHI Quan, WANG Xian

2022, 38(4): 886-893. doi:10.1007/s40242-022-2119-5

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Metabolomics, one of the latest omics technologies, is employed to reveal overall metabolic trajectories, identify disease causative mechanisms and provide information for preventive diagnosis and drug targeting. Cancer is a disease known to alter cellular metabolism and so metabolomics can play an important role in the early diagnosis of cancer and in the evaluation of medical interventions and treatments for cancer. Many metabolomics studies rely on high-sensitive and high-throughput mass spectrometry platforms. In recent years, various mass spectrometry(MS) methodologies have been developed and enriched the scope of metabolite detection, contributing to disease studies, such as diabetes, cancer, and depression. Colorectal cancer is the third most diagnosed cancer worldwide and its incidence ranked third in China. This review focuses on the mass spectrometry technologies in metabolomics and summarizes the progress of metabolomics research in colorectal cancer.

Progress in DNA Aptamers as Recognition Components for Protein Functional Regulation

HU Lingling, LIU Ke, REN Guolan, LIANG Jiangong, WU Yuan

2022, 38(4): 894-901. doi:10.1007/s40242-022-2124-8

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Proteins play a central role in all domains of life, and precise regulation of their activity is essential for understanding the related biological processes and therapeutic functions. Nucleic acid aptamers, the molecular recognition components derived from systematic evolution of ligands by exponential enrichment(SELEX), can specifically identify proteins with antibody-like recognition characteristics and help to regulate their activity. This minireview covers the SELEX-based selection of protein-binding aptamers, membrane protein analytical techniques based on aptamer-mediated target recognition, aptamer-mediated functional regulation of proteins, including membrane receptors and non-membrane proteins(thrombin as a model), as well as the potential challenges and prospects regarding aptamer-mediated protein manipulation, aiming to supply some useful information for researchers in this field.

Caging-Decaging Strategies to Realize Spatiotemporal Control of DNAzyme Activity for Biosensing and Bioimaging

ZHANG Qian, LIANG Yuyan, XING Hang

2022, 38(4): 902-911. doi:10.1007/s40242-022-2137-3

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DNAzymes with RNA-cleaving activity have been widely used as biosensing and bioimaging tools for detection of metal ions. Despite the achievements, DNAzyme-based biosensors sometime suffer from false positive signals and unexpected off-target turn-on in biological environments, which are likely due to the unstable nature of the RNA site. Ways to control DNAzyme activity in order to improve the sensing performance remain a significant challenge. To meet the challenge, there is growing interest to develop synthetic strategies that can cage native DNAzyme under undesired conditions and reactivate it in target environment in order to function in a controlled manner. A variety of caging-decaging strategies have been developed to realize spatiotemporal control of the DNAzyme activity, improving its specificity and sensitivity as well as extending its application regimes. In this review, we focus on strategies to regulate the catalytic activity of DNAzyme, highlight the nucleic acid modification chemistries, and summarize three strategies to cage DNAzyme functions. Examples of using caged DNAzyme for bio-applications have also been reviewed in detail. Finally, we provide our perspectives on the potential challenges and opportunities of this emerging research topic that could advance the DNAzyme field.

Functional Xeno Nucleic Acids for Biomedical Application

TU Tingting, HUAN Shuangyan, KE Guoliang, ZHANG Xiaobing

2022, 38(4): 912-918. doi:10.1007/s40242-021-2186-7

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Functional nucleic acids(FNAs) refer to a type of oligonucleotides with functions over the traditional genetic roles of nucleic acids, which have been widely applied in screening, sensing and imaging fields. However, the potential application of FNAs in biomedical field is still restricted by the unsatisfactory stability, biocompatibility, biodistribution and immunity of natural nucleic acids(DNA/RNA). Xeno nucleic acids(XNAs) are a kind of nucleic acid analogues with chemically modified sugar groups that possess improved biological properties, including improved biological stability, increased binding affinity, reduced immune responses, and enhanced cell penetration or tissue specificity. In the last two decades, scientists have made great progress in the research of functional xeno nucleic acids, which makes it an emerging attractive biomedical application material. In this review, we summarized the design of functional xeno nucleic acids and their applications in the biomedical field.

Cu/CuO-Graphene Foam with Laccase-like Activity for Identification of Phenolic Compounds and Detection of Epinephrine

ZHU Junlun, CUI Qian, WEN Wei, ZHANG Xiuhua, WANG Shengfu

2022, 38(4): 919-927. doi:10.1007/s40242-022-2114-x

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Although great progress has been made in the advancement of nanozymes, most of the studies focus on mimicking peroxidase, oxidase, and catalase, while relatively few studies are used to mimic laccase. However, the use of nanomaterials to mimic laccase activity will have great potential in environmental and industrial catalysis. Herein, Cu/CuO-graphene foam with laccase-like activity was designed for the identification of phenolic compounds and the detection of epinephrine. In a typical experiment, the formation mechanism of Cu/CuO-graphene foam was investigated during the pyrolysis process by thermogravimetric-mass spectrometry. As a laccase mimic, Cu/CuO-graphene foam exhibited excellent catalytic activity with a Michaelis-Menten constant and a maximum initial velocity of 0.17 mmol/L and 0.012 mmol∙L^-1∙s^-1, respectively. Based on this principle, Cu/CuO-graphene foam nanozyme could differentially catalyze phenolic compounds and 4-aminoantipyrine for simultaneous identification of phenolic compounds. Furthermore, a colorimetric sensing platform was fabricated for the quantitative determination of epinephrine, showing linear responses to epinephrine in the range of 3 mg/mL to 20 mg/mL with the detection limit of 0.2 mg/mL. The proposed Cu/CuO-graphene foam nanozyme could be applied for the identification of phenolic compounds and the detection of epinephrine, showing great potential applications for environmental monitoring, biomedical sensing, and food detection fields.

A DNA Nano-train Carrying a Predefined Drug Combination for Cancer Therapy

HUANG Qin, LIU Xin, ZHANG Pengge, WU Zhan, ZHAO Zilong

2022, 38(4): 928-934. doi:10.1007/s40242-022-2116-8

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Herein, we reported a tumor cell-targeting aptamer-nano-train to deliver paclitaxel(PTX) and combretastatin A4(CA4) at a predefined ratio to cancer cells based on DNA nanotechnology. Such a drug-carrying aptamer-nano-train(aptamer-NT-PTX/CA4) was prepared via self-assembly of two DNA hairpins, which were conjugated with PTX and CA4, respectively, induced by aptamer trigger. Our research revealed that the aptamer-NT-PTX/CA4 could specifically recognize CD71-positive cancer cells, but not CD71-negative healthy normal cells, and achieve synergistic therapeutic effect on cancer cells. The aptamer-nano-train-based strategy is simple and efficient, and provides a new platform for drug combination cancer therapy.

Plasmonic Gold Chip for Multiplexed Detection of Ovarian Cancer Biomarker in Urine

CHEN Minwen, LIAO Tao, ZENG Linsheng, ZENG Zhongyi, YANG Qinglai, WANG Guoxin

2022, 38(4): 935-940. doi:10.1007/s40242-022-2117-7

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Human epididymal protein 4(HE4), carbohydrate antigen 125 (CA125) and osteopontin(OPN) are three key biomarkers in detecting ovarian cancer. To explore the diagnosis value of combined detection of these three biomarkers for ovarian cancer, we developed a multiplexed assay on a plasmonic gold(pGOLD) platform for measuring HE4, CA125 and OPN in urine. The receiver operator characteristic(ROC) curve was drawn, and the diagnosis values of each biomarker alone or in combination for ovarian cancer were evaluated. In the analysis to distinguish ovarian cancer from other gynecological cancers, ovarian cysts and healthy people, the sensitivities of HE4, CA125 and OPN were 72.55%, 52.82% and 68.63%, the specificity values were 95.06%, 87.65% and 90.12%, while the areas under the curve(AUC) were 0.85, 0.75 and 0.77, respectively. The sensitivity and specificity for combination detection of the three markers were 90.20% and 80.25%. The detection methods of HE4, CA125 and OPN based on plasma fluorescence enhanced chip showed good analytic and diagnostic performance, and provided a non-invasive method for the diagnosis of ovarian cancer.

Polypyrrole Hollow Nanotubes Loaded with Au and Fe₃O₄ Nanoparticles for Simultaneous Determination of Ascorbic Acid, Dopamine, and Uric Acid

SHEN Congcong, CHEN Yuehua, FENG Beidou, CHI Hongying, ZHANG Hua

2022, 38(4): 941-948. doi:10.1007/s40242-022-2120-z

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An ultrasensitive electrochemical biosensor was fabricated for electroanalytical determination of ascorbic acid(AA), dopamine(DA) and uric acid(UA) individually and simultaneously based on polypyrrole hollow nanotubes loaded with Au and Fe₃O₄ nanoparticles(NPs) uniformly(PPy@Au-Fe₃O₄). The PPy@Au-Fe₃O₄ nanotubes were synthesized in one-pot using MoO₃ nanorods as templates and the polymerization of Py, the formation of Au and Fe₃O₄ NPs and the removel of MoO₃ templates took place stimultaneously. Electrochemical studies reveal that PPy@Au-Fe₃O₄modified glassy carbon electrode(GCE) possesses excellent electro-catalytic activities toward the oxidation of AA, DA and UA. Their oxidation peak currents increase linearly in the concentration ranges of 1-2000 μmol/L for AA, 0.01-25 and 25-300 μmol/L for DA and 0.1-300 μmol/L for UA. Their detection limit values(S/N=3) were calculated as 0.45, 0.0049, and 0.051 μmol/L for AA, DA and UA in the individual detection. By changing the concentrations simultaneously, the calibration curves showed linearity to 1000, 200, and 200 μmol/L with detection limit of 0.39, 0.0060, and 0.060 μmol/L for AA, DA, and UA, respectively. Finally, the obtained biosensor was successfully applied to the detection of AA, DA, and UA with satisfactory results on actual samples.

Dual Diomarkers Triggered Prodrugs for Precise Treatment of Melanoma:Design, Synthesis and Activities

RUAN Yawen, HUANG Peiling, YAN Jiangyu, LI Guorui, HUANG Jing

2022, 38(4): 949-956. doi:10.1007/s40242-022-2121-y

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Targeted prodrug strategy, which utilizes the endogenous biomarkers in cancer cells as activators to release the active drug, has been well established either in the fundamental research or the clinical treatment. However, many prodrugs suffer from safety concern due to "off-target activation". Dual or multiple biomarkers triggered prodrug may provide an effective strategy to overcoming the "off-target effect". Melanoma cells have both high levels of reactive oxygen species(ROS) and tyrosinase(TYR), which makes them significantly different from other tumor cells and normal cells. Here we reported a series of quinazolinone-aryl boronic acid/ester-based prodrugs, which can be activated by the cascade of ROS and TYR and selectively kill melanoma cells. The structure-activity relationship(SAR) analysis revealed that mitochondria-targeting property was vital for their cytotoxicity and the dual activated effector played a significant role in their selectivity towards melanoma cells. Among these candidates, compound 4b showed the highest toxicity to B16, leading to an imbalance of the redox system in melanoma cells, causing mitochondrial DNA damage, and then promoting melanoma cells death.

Particle-Wave Dualism in Nanoconfined Space:Ultrafast Substance Flow

GAO Pengcheng, MA Qun, LIU Rui, LOU Xiaoding, HUANG Yu, ZHANG Baocheng, XIA Fan

2022, 38(4): 957-960. doi:10.1007/s40242-021-1290-4

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Many researchers, however, found that (1) the flow of both liquid and gas through nanoscale pores is one to even seven orders of magnitude faster than that would be predicted from the classic Newton's mechanic theories, such as the Hagen-Poiseuille equation, the Bernoulli's principle, the Knudsen theory; (2) the seeming contradiction that K⁺ channels conduct K⁺ ions at maximal throughput rates while not permeating slightly smaller Na⁺ ions, which have perplexed scientists for decades. Herein we propose a possible explanation for the above phenomena based on the Wave-Particle Dualism. The quantum effect on ultrafast flow could possibly provide a new perspective for studying the nature of the ion and molecule channels, which are the backbones for the biology, and possibly promote the development of new methods for energy conversion, desalination of sea water and even information systems.

Highly Active Electrocatalyst Derived from ZIF-8 Decorated with Iron(III) and Cobalt(III) Porphyrin Toward Efficient Oxygen Reduction in Both Alkaline and Acidic Media

ZHENG Ruonan, ZHAI Zihui, QIU Chenxi, GAO Rui, LV Yang, SONG Yujiang

2022, 38(4): 961-967. doi:10.1007/s40242-021-1199-y

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Zeolite imidazole frameworks 8(ZIF-8) and modified ones after pyrolysis are highly promising toward oxygen reduction reaction(ORR). Especially, the compositional modification of ZIF-8 is crucial to the enhancement of ORR performance, yet limited to the substitution of skeletal Zn(II) with other cations or simple physical adsorption of cations. Herein, we report the decoration of ZIF-8 with ORR active hemin(FeP) and Co(III) protoporphyrin(CoP) via the coordination between the peripheral carboxylic group of FeP and CoP with skeletal Zn(II). This allows well control over the quantity of loaded FeP and CoP, critical to the synthesis of advanced electrocatalysts. Subsequent pyrolysis of FeP and CoP co-decorated ZIF-8 leads to highly active ORR electrocatalysts with a half-wave potential(E_1/2) of 0. 913 V(vs. RHE) in 0.1 mol/L KOH aq. and an E_1/2 of 0.803 V(vs. RHE) in 0.1 mol/L HClO₄ aq. Moreover, our electrocatalyst shows much more improved and comparable durability in alkaline and acidic media, respectively, during 3000 cycles of cyclic voltammetry(CV) scanning relative to commercial Pt/C.

Flexible Self-healing Cross-linked Polyamides Synthesized Through Bulk Michael Addition, Polycondensation, and Diels-Alder Reaction

YANG Shengqing, ZHAO Jinnan, CHEN Shuo, ZHAO Jingbo

2022, 38(4): 968-973. doi:10.1007/s40242-021-1202-7

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Three new thermally responsive self-healing cross-linked polyamides(cPA-FU-DAs) with good tensile strength and toughness were synthesized through bulk Michael addition, polycondensation, and Diels-Alder reaction. Unlike common stable polymers, cPA-FU-DAs can seal cracks by mere heating. First, the Michael addition of methyl acrylate and furfurylamine was conducted, and a furfurylamine-diester(FU-DE) was prepared. FU-DE was transformed into polyamide prepolymers that contained furfuryl pendant groups(PA-FUs) through bulk polycondensation with a poly(propylene glycol)(PPG) diamine and a PPG triamine. PA-FUs were crosslinked by bismaleimide, and cPA-FU-DAs were prepared. The Michael addition was monitored by Fourier transform infrared spectroscopy and electrospray ionization mass spectroscopy. The reverse DA reaction of the cPA-FU-DAs was demonstrated by differential scanning calorimetry and dissolution property. Their thermally self-healing properties were verified by polarizing optical microscopy and tensile test. The cPA-FU-DAs exhibited good mechanical properties and high self-healing efficiency. They self-healed at 130℃. The tensile strength after repairing was up to 19 MPa with self-healing efficiency reaching 92%.

Modulation of the Second Order Nonlinear Optical Properties of Helical Graphene Nanoribbons Through Introducing Azulene Defects or/and BN Units

ZHENG Xuelian, LIU Ling, YANG Cuicui, HE Yuanyuan, CHEN Jiu, TIAN Wei Quan

2022, 38(4): 974-984. doi:10.1007/s40242-021-1213-4

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The current study has obtained excellent potential nonlinear optical(NLO) materials by combining density functional theory methods with sum-over-states model to predict the second order NLO properties of helical graphene nanoribbons(HGNs) through introducing azulene defects or/and BN units. The introduction of these functional groups deforms the pristine HGN (compression or tension) and enhances obviously the static first hyperpolarizability(<b₀>) of system by up to two orders of magnitude. The tensor components along the helical axis of HGNs play a dominant role in the total <b₀>. The azulene defects and the BN units polarize the pristine HGN to different degrees, and the azulenes and contiguous benzenes are involved in the major electron excitations with significant contributions to <b₀> but the BN units are not. The BN-doped chiral HGNs have good kinetic stability and strong second order NLO properties(6.84×10⁵×10^-30 esu), and can be a potential candidate of high-performance second order NLO materials. The predicted two-dimensional second order NLO spectra provide useful information for further exploration of those helicenes for electro-optic applications.

Colorimetric Detection of Glucose Using WO₃ Nanosheets as Peroxidase-mimetic Enzyme

SHI Rui, WEI Shuxian, CHENG Shiqi, ZENG Jinmin, WANG Yilin, SHU Xin

2022, 38(4): 985-990. doi:10.1007/s40242-021-1215-2

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In the present work, WO₃ nanosheets(WO₃ NSs) were prepared by a facile method at room temperature. The obtained WO₃ NSs showed peroxidase-like activity, which could catalyze 3,3',5,5'-tetramethylbenzidine(TMB) to form a blue oxidation product(ox TMB) in the presence of H₂O₂. Based on this, convenient and sensitive colorimetric methods for the detection of H₂O₂ and glucose were established. The linear ranges for detecting H₂O₂ and glucose were 1-200 μmol/L and 1-100 μmol/L, respectively. The limits of the detection of H₂O₂ and glucose were as low as 0.79 and 0.96 μmol/L, respectively. This method was also successfully applied to the detection of glucose in urine samples. The detection result was consistent with that of the value detected by the clinical method, indicating the potential in clinical diagnosis and biomedical detection.

A Chemical Dealloying Approach for Pt Surface-enriched Pt₃Co Alloy Nanoparticles as Oxygen Reduction Reaction Electrocatalysts

CHEN Yu, CHEN Yongting, LIAO Yuxiang, CHEN Shengli

2022, 38(4): 991-998. doi:10.1007/s40242-021-1238-8

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Pt-based alloys are the optimal electrocatalysts for oxygen reduction reaction(ORR) currently. Dealloying of Pt-based alloys has shown to be an effective approach to improving ORR activity. Electrochemical dealloying is controllable for morphology by changing electrochemical parameters but is difficult to scale up due to complex operation and energy consumption. Chemical dealloying is suitable for a large scale but it is not easy to control the morphology because highly corrosive acids(HNO₃ or H₂SO₄) are commonly used. In this work, a facile chemical dealloying method for Pt₃Co/C has been employed to synthesize elec-trocatalysts for ORR using weak acids and buffer solutions of different pH, which could slow down the dissolution rate for Co atoms and increase the diffusion time for Pt atoms to improve ORR activity. It can be observed that the mass activities(MA) of the Pt₃Co/C alloy after dealloying with H₃PO₄ and NaH₂PO₄/Na₂HPO₄ buffer solution of pH=6 are close to that after electrochemical dealloying process, and are more than two times that of commercial Pt/C. In addition, Pt₃Co/C after dealloying with a buffer solution of pH=6 only showed a slight degradation in the half-wave potential and electrochemical surface area(ECSA) after stability test for 5000 cycles, which is more stable than commercial Pt/C. It shows that by controlling pH of the solvent, the ORR activity can be further increased. This facile approach provides a new strategy to control morphology of Pt-based electrocatalysts by chemical dealloying, which can contribute to promising application for cathodic electrocatalysts design of proton exchange membrane fuel cells (PEMFCs).

Fabrication of Mesoporous SiO₂@CaSiO₃ Hollow Spheres as Carriers for pH-sensitive Drug Delivery

YUAN Mingwei, SHI Shunli, LUO Yanping, YU Ying, WANG Shuhua, CHEN Chao

2022, 38(4): 999-1004. doi:10.1007/s40242-021-1248-6

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Hollow mesoporous silica(HM-SiO₂) was prepared by the improved stober method. On this basis, HM-SiO₂ was dispersed in an alkaline solution for surface etching. Meanwhile, calcium source was introduced to combine with on the surface to form a CaSiO₃shell layer and an unprecedent SiO₂@CaSiO₃sphere with a hollow double-shell structure was obtained. The as-synthesized SiO₂@CaSiO₃ was characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), N₂-BET, IR and UV-Vis techniques, and its sustained release capacity of doxorubicin(DOX) loading was investigated. The drug loading capacity can be achieved to 0.692 mg DOX/mg SiO₂@CaSiO₃, exhibiting pH-responsivity under low pH conditions.

Piezoelectric Nanogenerator Based on Electrospun Cellulose Acetate/Nanocellulose Crystal Composite Membranes for Energy Harvesting Application

SUN Bolun, CHAO Danming, WANG Ce

2022, 38(4): 1005-1011. doi:10.1007/s40242-021-1252-x

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Nanogenerators, as the typical conversion of mechanical energy to electrical energy devices, have great potential in the application of providing sustainable energy sources for powering miniature devices. In this work, cellulose acetate/cellulose nanocrystal(CA/CNC) composite nanofiber membranes were prepared by electrospinning method and then utilized to manufacture a flexible pressure-driven nanogenerator. The addition of CNC not only increased the content of piezoelectric cellulose I crystallization but also strengthened the mechanical deformation of the nanofiber membranes, which could greatly enhance the piezoelectric performance of CA/CNC composite membranes. The CA/CNC composite nanofiber membrane with 20%(mass fraction) of CNC(CA/CNC-20%) showed optimal piezoelectric conversion performance with the output voltage of 1.2 V under the force of 5 N(frequency of 2 Hz). Furthermore, the output voltage of the CA/CNC-20% nanogenerator device exhibited a linear relationship with applied impact force, indicating the great potential in pressure sensors.

Acidity Modification of ZSM-5 for Methane Conversion in Co-feeding Method with MTA Reaction

YU Yue, XI Zhixiang, ZHOU Bingjie, JIANG Binbo, LIAO Zuwei, YANG Yao, WANG Jingdai, HUANG Zhengliang, SUN Jingyuan, YANG Yongrong

2022, 38(4): 1012-1017. doi:10.1007/s40242-021-1253-9

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Acidity plays a vital role in methane conversion by co-feeding method, which is one of the best strategies to improve the utilization and gentle the reaction conditions of methane. In this work, Zn, Ni, Mo, La, Ga, Fe and Co-impregnated ZSM-5 zeolites have been prepared with the same substitutions to variate the acidities and tested in co-aromatization of methanol with methane. It is demonstrated that the new medium-strong acid sites formed by metal and strong acid sites are the key role to activate methane in co-reaction. Zn-modified ZSM-5 catalyst is preferred to exhibit the best methane conversion of 12%, whose aromatic selectivity increases from 27.2% to 52.2% compared with that of HZSM-5. Besides, the addition of methane further improves the production of high-valued aromatics compared with methanol to aromatics (MTA) reaction.

In vivo Toxicity Evaluation of a Nano-drug Delivery System Using a Caenorhabditis elegansModel System

HAN Wenzhao, LI Hui, YU Xiaoxuan, KE Junfeng, GUO Feng, WANG Liping

2022, 38(4): 1018-1024. doi:10.1007/s40242-021-1257-5

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Drug carrier materials need to possess good biological safety. Presently, most biosafety evaluation studies use rodent animal models, including rats and rabbits. However, the cost of raising these animals is relatively high and the experimental period is long. Caenorhabditis elegans(C. elegans) presents an ideal toxicological evaluation model due to its simple structure, easy cultivation, short life cycle, and evolutionary conservation. In this paper, we used C. elegans to test the biological safety of our pH-responsive carrier system(FFPFF self-assembling into a nanosphere structure, FFPFF Nps), which was designed for anti-tumor drug delivery. Our results showed that exposure to high doses of FFPFF Nps did not have a significant impact on the survival rate, growth, development, movement, and reproduction of C. elegans. The preliminary evaluation of the overall biological model of C. elegans shows that FFPFF Nps has good biological safety and warrants further study.

Photocatalytic HER Performance of TiO₂-supported Single Atom Catalyst Based on Electronic Regulation:A DFT Study

SONG Weiyu, LV Xintong, GAO Yang, WANG Lu

2022, 38(4): 1025-1031. doi:10.1007/s40242-021-1271-7

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Hydrogen is a kind of sustainable clean energy. Sunlight-driven hydrogen evolution reaction(HER) from water splitting assisted by photocatalysts is very crucial for developing clean energy technologies. Single-atom catalysts, such as atomically dispersed Pt on anatase(Pt₁/TiO₂) have exhibited excellent photocatalytic HER performance. However, the role of a single atom is still elusive. The mechanism of photocatalytic HER of TiO₂-supported noble metal single-atom catalysts has been studied. The supported single-atom Pt could narrow the bandgap of TiO₂, enhance the optical absorption properties, and promote the transfer of the excited electrons. Excited electrons do not participate in the process of O-H cleavage, but can participate in the process of proton reduction and greatly reduce the hydrogen evolution energy barrier. Therefore, the hydrogen evolution energy can be used as a descriptor to evaluate the activity of TiO₂-supported single-atom catalysts. The activity of hydrogen evolution is found to be related to the number of d-band electrons of the single noble atom on M₁/TiO₂(M=Pd, Pt, Rh, Ir). The increase of the number of d electrons in the single atom could reduce the hydrogen evolution energy and promote the hydrogen evolution process.

Improving Catalytic Stability and Coke Resistance of Ni/Al₂O₃ Catalysts with Ce Promoter for Relatively Low Temperature Dry Reforming of Methane Reaction

HE Lulu, CHEN Xin, REN Yuanhang, YUE Bin, TSANG Shik Chi Edman, HE Heyong

2022, 38(4): 1032-1040. doi:10.1007/s40242-021-1281-5

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Aseries of Ni catalysts supported on alumina with different Ce contents(1.0%-6.0%, mass fraction) was prepared by the impregnation method and used for dry reforming of methane(DRM) at a relatively low temperature of 650 ^oC. The promotion effect of Ce with different loading amounts on the physicochemical properties of the catalysts was systematically characterized by transmission electron microscopy(TEM), X-ray diffraction(XRD), N₂ adsorption-desorption, thermo elemental IRIS Intrepid inductively coupled plasma atomic emission spectrometer (ICP-AES), UV-visible diffuse reflectance spectroscopy(UV-Vis DRS), Fourier transformation infrared(FTIR) spectra, H₂-temperature programmed reduction(H₂-TPR) analysis, H₂-temperature programmed desorption(H₂-TPD), and the X-ray photoelectron spectroscopy(XPS) techniques. The results indicate that all the catalysts mainly exist in the NiAl₂O₄ phase after being calcined at 750 ^oC with small Ni particle sizes due to the strong metal-support interaction derived from the reduction of the NiAl₂O₄ phase. The Ce-promoted catalysts show better catalytic performance as well as the resistance against sintering of Ni particles and deposition of carbon compared to the Ni/Al₂O₃ catalyst. The Ni-6Ce/Al₂O₃ exhibits the best catalytic stability and coke resistance among the four catalysts studied, which is due to its small Ni nanoparticles sizes, excellent reducibility as well as high amount of active oxygen species. In a 400 h stability test for DRM reaction at 650 ^oC, Ni-6Ce/Al₂O₃ exhibits less coke deposition and small growth of Ni nanoparticles. This work provides a simple way to preparing the Ni-Ce/Al₂O₃ catalyst with enhanced catalytic performance in DRM. The Ni-6Ce/Al₂O₃ catalyst has great potential for industrial application due to its anti-sintering ability and resistance to carbon deposition.

Crystals Array via Oriented Nucleation and Growth Induced by Smectic E Mesophase of C7-T-BTBT

LI Hongxiang, WANG Sichun, LIU Xinyu, WU Fan, ZHANG Qiang, YUAN Jian, MA Wei, HAN Yanchun

2022, 38(4): 1041-1049. doi:10.1007/s40242-021-1283-3

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Long-range order crystalline thin films of organic semiconductors have attracted wide attention owing to their high charge carrier mobility. However, uncontrolled crystal nucleation and growth during the thin film drying process cause the formation of grain boundaries, thereby limiting the long-range order. Herein, we achieved the oriented nucleation and growth of organic semiconductors by off-centre spin-coating at the temperature of the smectic E(SmE) liquid crystal mesophase, and then followed by Ostwald ripening during solvent vapour annealing. The thin film of 2-(5-heptylthiophen-2-yl)[1]benzothieno[3,2-b] [1]benzothiophne (C7-T-BTBT) blended with 40%(mass fraction) poly(methyl methacrylate)(PMMA) was prepared by off-centrespin-coating at SmE mesophase(170℃), followed by solvent vapour annealing in chloroform for 24 h(chloroform is a good solvent for C7-T-BTBT and PMMA). The C7-T-BTBT molecules grew to rod-like crystals, which were mostly arranged parallel to each other. The crystal growth was perfect and resulted in a single crystal. The average length of the crystals was approximately 87 μm. Moreover, the highest charge carrier mobility is 1.62 cm²·V⁻¹·s⁻¹ as against that of the film prepared at 25℃(0.06 cm²·V⁻¹·s⁻¹).

ESIPT-regulated Mechanoresponsive Luminescence Process by Introducing Intramolecular Hydrogen Bond in Naphthalimide Derivatives

ZHANG Bingyi, ZHANG Xiaolei, SU Ruochen, SUN Yue and DUAN Lian

2022, 38(4): 1050-1056. doi:10.1007/s40242-021-1291-3

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Herein, two compounds, 4-2′-hydroxybenzylidenehydrazinyl-N-butyl-1,8-naphthalimide(BN-1) and 4-benzylidenehydra-zinyl-N-butyl-1,8-naphthalimide(BN-2), were synthesized to explore the hydrogen bonding effect on mechanoresponsive luminescent(MRL). The results showed that compound BN-1 exhibited strong emission in solution and solid-state compared with compound BN-2. After grinding, the emission intensity of compound BN-1 sharply decreased by as much as 15 times with an obvious red-shift from 552 nm to 577 nm. The control compound BN-2, by contrast, did not change so much before and after grinding. Single crystal analysis suggests that BN-1 molecule formed strong intramolecular interaction via ―N=N···H―O hydrogen bond with a distance of 0.2632 nm. An excited-state intramolecular proton transfer(ESIPT) based fluorophore featured this intramolecular hydrogen bond. The intramolecular hydrogen bond as well as other intermolecular interactions can rigidify the molecular conformation of compound BN-1 in solid-state, and thus suppress the nonradiative pathways, resulting in strong emission. These intra- and intermolecular interactions were destroyed by mechanical stimuli, accompanied by molecular conformation change that decreases the luminescence and blocks the ESIPT process. The MRL process was also demonstrated by scanning electron microscopy and powder X-ray diffraction. The molecular stacking mode changed from crystalline to a disordered amorphous state after grinding.

Quantitative Analysis of Methanol in Methanol Gasoline by Calibration Transfer Strategy Based on Kernel Domain Adaptive Partial Least Squares(kda-PLS)

XU Yanyan, LI Maogang, FENG Ting, JIAO Long, WU Fengtian, ZHANG Tianlong, TANG Hongsheng, LI Hua

2022, 38(4): 1057-1064. doi:10.1007/s40242-022-1327-3

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The application of near-infrared(NIR) spectroscopy combined with multivariate calibration methods can achieve the rapid analysis of methanol gasoline. However, instrumental or environmental differences found for spectra make it impossible to continuously apply the previously developed calibration model. Therefore, the calibration transfer technique would be required to solve the time-consuming and laborious problem of reestablishing a new model. In this work, a calibration transfer method named kernel domain adaptive partial least squares(kda-PLS) was applied to the calibration transfer from the primary instrument to the secondary ones. Firstly, wavelet transform(WT) and variable importance in projection(VIP) were employed to enhance the predictive performance of the kda-PLS transfer model. Then, the results found for the calibration transfer by piecewise direct standardization(PDS) and domain adaptive partial least squares(da-PLS) were compared to verify the calibration transfer(CT) effect of kda-PLS. The results point that the kda-PLS method can transfer the PLS model developed on the primary instrument to the secondary ones, and achieve results comparable to the those of reestablishing a new PLS model on the secondary instrument, with R₂^P=0.9979(R₂^P: coefficients of determination of the prediction set), RMSE_P=0.0040 (RMSE_P:root mean square error of the prediction set), and MRE_P=3.03%(MRE_P: mean relative error of the prediction set). Therefore, kda-PLS will provide a new method for quantitative analysis of methanol content in methanol gasoline.

Development of the Self-doping Porous Carbon and Its Application in Supercapacitor Electrode

YANG Zhichen, KANG Xiaoting, ZOU Bo, YUAN Xuna, LI Yajie, WU Qin, GUO Yupeng

2022, 38(4): 1065-1072. doi:10.1007/s40242-021-1360-7

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The massive discharge of biomass wastes not only causes waste of resources, but also pollutes the environment. Therefore, converting biomass wastes into carbon materials is an effective way to solve the above problems. Here, using biomass waste pig nails as raw materials and K₂CO₃ as chemical activators, the N-doped porous carbon(KPNC) is prepared by direct pyrolysis. As an electrode for supercapacitors, the electrochemical tests of KPNCs showed that they exhibited good electrochemical performance and excellent cycling stability. When the current density is 0.2 A/g, the specific capacitance is up to 344.6 F/g. Moreover, it still maintains 97.6% initial capacitance retention after 2000 cycles at a high current density of 5 A/g. Above exceptional electrochemical performances may be ascribed to an appropriate porous structure(S_micro/S_total=80.31%, V_micro/V_total=76.19%), high nitrogen contents(4.44%, atomic fraction), oxygen contents(9.13%, atomic fraction) as well as small internal resistance. The above experimental results show that the conversion of pig nails to porous carbon can reduce the waste of resources and alleviate environmental pollution.

An Efficient One-pot Synthesis of Certain Stereoselective Spiro[pyrazole-4,5'-isoxazoline]-5-one Derivatives: In vitro Evaluation of Antitumor Activities,Molecular Docking and In silico ADME Predictions

Ghadah F. ALJOHANI, Fatma A. A. EL-HAG, Mohamed S. BEKHEIT, Ewies F. EWIES, May A. EL-MANAWATY

2022, 38(4): 1073-1082. doi:10.1007/s40242-022-1408-3

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A library of novel spiro[pyrazole-4,5'-isoxazoline]-5-one derivatives were designed and synthesized using a concise and efficient one-pot reaction protocol through 1,3-dipolar cycloaddition between 4-benzylidene-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one and chlorooximes. The synthesized derivatives were elucidated and characterized based on their spectroscopic data, including infrared spectrometry(IR), ¹H NMR, ¹³C NMR, and elemental and mass spectral analysis. The synthesized compounds were evaluated for their antitumor inhibition potency against four human cancer cell lines, including human prostatic adenocarcinoma (PC3), human colorectal carcinoma(HCT116), human liver hepatocellular carcinoma(HepG2) and breast adenocarcinoma (MCF7). The outcomes were compared with the standard reference drug Doxorubicin. Among the synthesized chlorooximes, compounds 6d and 6e were the most active compounds on all cell lines. The spiro[pyrazole-4,5'-isoxazoline]-5-one derivatives 7a and 7c were active on the HepG2 liver cancer cell line. In comparison, compounds 7f and 7g were moderately active on the MCF7 cell line. The structure-activity relationship was explored for the synthesized compounds. Besides, in silico analysis of physicochemical, adsorption, distribution, metabolism, excretion and toxicity(ADMET) properties were done to determine the potential capacity of drug candidates. Molecular docking study onto the epidermal growth factor(EGF) tyrosine kinase receptor(3POZ) was done for the most active compounds to validate the reliability of in vitro anticancer screenings.

Functionalized Hierarchical ZSM-5 Zeolites for the Viscosity Reduction of Heavy Oil at Low Temperature

XIAO Peiwen, LI Hui, WANG Pingmei, LIU Bolun, JING Wendan, HE Lipeng, WANG Runwei, HAN Xue, ZHANG Zongtao, QIU Shilun, LUO Jianhui

2022, 38(4): 1083-1088. doi:10.1007/s40242-022-1425-2

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Herein, we propose a novel approach to reduce the viscosity of heavy oil by functional hierarchical CTMS-ZSM-5-PTMS zeolites. CTMS-ZSM-5-PTMS zeolites synthesized by asymmetric modification and selective alkali etching can reduce the viscosity of heavy oil through adsorbing asphaltenes. This method can reduce the viscosity of heavy oil from hundreds of thousands mPa·s to about ten thousand mPa·s. The work provides an economical and environmentally friendly candidate for heavy oil viscosity reduction under low-temperature conditions.

Maltol as a Novel Agent Protecting SH-SY5Y Cells Against Hemin-induced Ferroptosis

HUA Cong, WANG Xuanzhong, LIANG Shipeng, LI Chen, CHEN Xi, PIAO Meihua, WANG Zhenchuan, GE Pengfei, LUO Tianfei

2022, 38(4): 1089-1096. doi:10.1007/s40242-021-1438-2

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Ferroptosis triggered by hemin is regarded as a primary factor accounting for neuronal death secondary to intracerebral hemorrhage. Thus, compounds with inhibitory effect on hemin-induced ferroptosis might be potential medicines to prevent neuronal death caused by intracerebral hemorrhage. Herein, we investigate whether maltol could alleviate hemin-induced SH-SY5Y cell ferroptosis and its potential mechanisms. It is found that maltol effectively prevents hemin-induced SH-SY5Y cell ferroptosis via three pathways. The first one is inhibiting intracellular iron increase via preventing upregulation of transferrin receptor, the second one is alleviating lipid peroxidation via attenuating H₂O₂ generation by NOX4 and promoting H₂O₂ clearance by catalase, and the third one is to reduce peroxidized lipids via maintaining GPX4/GSH pathway. Therefore, maltol is a novel agent preventing hemin-induced SH-SY5Y cell ferroptosis.

Design and Preparation of Graphene/Fe₂O₃ Nanocomposite as Negative Material for Supercapacitor

GAO Wei, LI Yufeng, ZHAO Jitao, ZHANG Zhe, TANG Weiwei, WANG Jun, WU Zhenyu, LI Zhenyu

2022, 38(4): 1097-1104. doi:10.1007/s40242-022-1442-1

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The development of high specific capacitance electrode materials with high efficiency, scalability and economic feasibility is significant for the application of supercapacitors, however, the synthesis of electrode material still faces huge challenges. Herein, graphene(G)/Fe₂O₃ nanocomposite was prepared via a simple hydrothermal method connected with subsequent thermal reduction process. Scanning electron microscopy(SEM) and transmission electron microscopy(TEM) results showed rod-like Fe₂O₃ nanoparticles were prepared and well-dispersed on graphene layers, providing a rich active site and effectively buffering the aggregation of Fe₂O₃ nanoparticles in the process of electrochemical reaction. The specific capacitance of the obtained G/Fe₂O₃ nanocomposite as negative electrode for supercapacitor was 378.7 F/g at the current density of 1.5 A/g, and the specific capacitance retention was 88.76% after 3000 cycles. Furthermore, the asymmetric supercapacitor(ASC) was fabricated with G/Fe₂O₃ nanocomposite as negative electrode, graphene as positive electrode, which achieved a high energy density of 64.09 W∙h/kg at a power density of 800.01 W/kg, maintained 30.07 W∙h/kg at a power density of 8004.89 W/kg, and retained its initial capacitance by 78.04% after 3000 cycles. The excellent result offered a promising way for the G/Fe₂O₃ nanocomposite to be applied in high energy density storage systems.

Multi-functional Photoelectric Sensor Based on a Three-fold Interpenetrated Cd(II) Coordination Polymer for Sensitively Detecting Different Ions

WANG Yue, WANG Jinling, MA Jianxin, ZHANG Yue, XU Na, WANG Xiuli

2022, 38(4): 1105-1110. doi:10.1007/s40242-022-1445-y

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Athree-fold interpenetrated cadmium coordination polymer[Cd₃(BTC)₂(H₂O)₉]·2H₂O(CP 1)(H₃BTC=1,3,5-benzenetricar-boxylic acid) was selected and synthesized to investigate its photoelectric properties. CP 1 showed excellent sensitivity for Cr₂O₇^2- and Fe³⁺, low limit of detection(LOD:0.39 µmol/L for Cr₂O₇^2- and 1.72 µmol/L for Fe³⁺) and stability as electrochemical sensor. More importantly, fluorescence sensing studies indicated that CP 1 exhibits sensing activity for Fe³⁺, Fe²⁺, and MnO₄^- with good cyclic stability and selectivity. Low LOD and high-sensitivity capability of CP 1 make it a potential multifunctional photoelectric sensor.

Preparation of Poly(ε-caprolactone)/Poly(ester amide) Electrospun Membranes for Vascular Repair

ZHANG Xiangyu, BAI Shan, ZANG Leilei, CHEN Xiaoqi, YUAN Xiaoyan

2022, 38(4): 1111-1117. doi:10.1007/s40242-022-1480-8

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With adjustable amphiphilicity and anionic/cationic charge, biodegradability and biocompatibility, amino acid-based poly(ester amide)s(PEAs) have drawn attention in the research of tissue engineered vascular grafts. In this work, L-phenylalanine-based PEAs with or without L-lysine were synthesized through polycondensation, and ultrafine fibrous grafts consisted of PEAs and poly(ε-caprolactone)(PCL) in given mass ratios were further prepared via blend electrospinning. Surface characterizations by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy confirmed the chemical structure, and the wettability indicated that the prepared PCL/PEAs electrospun membranes exhibited less hydrophobic than PCL. Tensile results showed that the PCL/PEAs membranes possessed suitable mechanical properties, which could meet the requirements of artificial blood vessels. Cell culture and hemolytic tests exhibited that the PCL/PEAs electrospun membranes are biocompatible. In general, the electrospun grafts of PCL/PEAs could be applied for vascular repair.

Block Copolymer Supported Gold Nanoparticles Assemblies with Exposed Gold Surface

ZONG Chen, LIU Guangnan, XU Wenhao, CHEN Jie, TANG Yun

2022, 38(4): 1118-1122. doi:10.1007/s40242-022-1485-3

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Polymer-involved nanoparticles or nanoparticle assemblies are now facing a crossroad, where the exposure of nanoparticle and multiple nanoparticles cannot be obtained at the same time. Therefore, a new series of nanoparticle clusters is synthesized, where multiple gold nanoparticles assemble with amphiphilic block copolymers supporting inside. The exposure of gold nanoparticles of the structure is confirmed and increases the reduction rate of 4-nitrophenol by 60%. The assemblies can also be used as surface enhanced Raman scattering(SERS) probes with an enhancement factor(EF) as high as 3×10³.

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