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ANALYST · 2021 ·Vol. 146 ·期 13 ·4188-4194 · IF 4.616

Glucose oxidase decorated fluorescent metal–organic frameworks as biomimetic cascade nanozymes for glucose detection through the inner filter effect

Wenjie Jing,Fanbo Kong,Sijia Tian,Mincong Yu,Yunchao Li,Louzhen Fan,Xiaohong Li

Metal–organic frameworks (MOFs) as a peroxidase mimic have been integrated with glucose oxidase (GOx) to achieve one-step glucose detection. However, limited by the loading amount of GOx, the performances of the developed glucose sensing assays still remain to be further improved to meet sensing requirements in diverse biological samples. Herein, with Fe3+ as the metal ion and 2-amino-benzenedicarboxylic acid as a ligand, a fluorescent Fe-based organic framework (NH2-MIL-101) with peroxidase-like activity was synthesized. Due to the large specific surface area (791.75 m2 g−1), 68 μg mg−1 GOx could be immobilized through the amidation coupling reaction, and the product was designated GOx@NH2-MIL-101. With OPD as the substrate, Gox@NH2-MIL-101 achieved highly efficient biomimetic cascade catalysis for one-step glucose detection through an inner filter effect: upon reacting with glucose, GOx@NH2-MIL-101 catalytically oxidized glucose using dissolved O2, and the produced H2O2 concurrently oxidized o-phenylenediamine (OPD) to oxidized OPD (oxOPD), accompanied by the fluorescence of GOx@NH2-MIL-101 at 456 nm being quenched and that of oxOPD at 565 nm being enhanced. With the fluorescent ratio F565/F456 used as a readout signal, a wide linear range of 0.1–600 μM was obtained, and the detection limit was 0.0428 μM. Based on the excellent selectivity and high stability of GOx@NH2-MIL-101, the developed assay was successfully applied to glucose detection in human serum and saliva, presenting potential applications in diverse biological samples and even medical diagnosis.

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Journal of Materials Chemistry B · 2020 ·Vol. 8 ·期 37 ·8599-8606 · IF 5.344

A facile route for constructing Cu–N–C peroxidase mimics

Zhen Lin,Linlin Zheng,Wensong Yao,Shijun Liu,Yemei Bu,Qi Zeng,Xiaomin Zhang,Haohua Deng,Xinhua Lin,Wei Chen

Nanozymes have emerged as enzyme-mimicking nanomaterials to overcome the low stability and high cost of some natural enzymes. The design and fabrication of nanozymes with superior performance to natural enzymes are in urgent demand. Single-atom catalysts offer the unique characteristics of maximum atomic utilization, and are an excellent candidate for nanozymes. However, most of the reported synthesis methods for single-atom catalysts require the preparation of supports for single-atom catalysts in advance, which requires multiple steps and calcination in a high temperature atmosphere. Herein, Cu–N–C single-atom nanozymes (Cu–N–C SAzymes) were successfully designed via a one-pot solvothermal method. Cu–N–C SAzymes exhibited excellent peroxidase-mimicking activity that is superior to some other related nanoparticles. The mechanism study revealed that H2O2 was catalyzed by Cu–N–C SAzymes to generate reactive oxygen species. Furthermore, based on the excellent peroxidase-mimicking activity of the Cu–N–C SAzymes, a simple and sensitive detection method for H2O2 and glucose has been developed.

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ENERGY & FUELS · 2020 · IF 3.421

Conversion of Glucose into 5-Hydroxymethylfurfural and Levulinic Acid Catalyzed by SO42–/ZrO2 in a Biphasic Solvent System

Yang Qu,Yuan Zhao,Shanshan Xiong,Chenguang Wang,Shurong Wang,Lingjun Zhu,Longlong Ma

5-Hydroxymethylfurfural (HMF) and levulinic acid (LA) are two important platform compounds that can be produced by the dehydration of hexoses from hydrolysis of cellulose. In this study, glucose dehydration was catalyzed by the SO42–/ZrO2 catalyst in the NaCl–THF/H2O biphasic solvent system. Complete conversion of glucose was achieved at 160 °C. The highest HMF yield and LA yield were 61.84% and 29.68%, respectively. The results showed that the conversion and product distribution were influenced by catalyst acidity, solvent composition, temperature, and time. The SO42– load greatly changed the acidity of the catalyst, thus affecting the product distribution. By changing the composition of the catalyst and the biphasic solvent system, different yields of HMF and LA could be obtained, so as to realize directional synthesis of the target products.

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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2020 · IF 3.807

Glucose-sensing abilities of mixed-metal (NiCo) Prussian blue analogs hollow nanocubes

Qiangqiang Niu,Wenbo Lu,Cancan Bao,Ming Wei,Zi-Ang Chen,Jianfeng Jia

Ni Co Prussian blue analogs (PBA) with a structure of hollow nanocubes (Ni Co PBA HNCs) are successfully prepared by simple static settlement at room temperature and ammonia etching method. The Ni Co PBA HNCs exhibit an enhanced catalytic activity towards glucose oxidation . The three-dimensional Ni Co PBA HNCs modified electrode form a novel glucose sensor which not involved the enzyme. The properties of glucose sensor based on Ni Co PBA HNCs are explored by electrochemical technique, for instance, cyclic voltammetry (CV), differential impulse voltammetry (DPV) and typical amperometric-time method (i-t). As compared to pure Ni PBA HNCs and pure Co PBA HNCs, the Ni Co PBA HNCs exhibit outstanding catalytic performance for electro-oxidation of glucose. The bimetal synergetic catalyst of Ni and Co in the Ni Co PBA HNCs causes this sensor with superior oxidation capacity for glucose. The analysis of the experimental data prove that this glucose sensor based on Ni Co PBA HNCs possesses wide linear range: 0.002 mM – 3.79 mM, low detection limit: 1.2 μM (S/N = 3), high sensitivity: 149 μA·mM −1 ·cm −2 , as well as good selectivity. We further find that the proposed glucose sensors can be successfully applied to detect glucose levels in drinks experiment.

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INDUSTRIAL CROPS AND PRODUCTS · 2020 · IF 4.244

Efficient catalytic conversion of corn stover to furfural and 5-hydromethylfurfural using glucosamine hydrochloride derived carbon solid acid in Ƴ-valerolactone

Tao Yang,Wenzhi Li,Ajibola T. Ogunbiyi,Shengxin An

A novel solid acid catalyst (SO 3 H-NG-C) was synthesized from biomass-derived glucosamine hydrochloride by carbonization, activation and sulfonation processes. The SO 3 H-NG-C was characterized by SEM, TEM, N 2 adsorption-desorption, elemental analysis, XRD, FTIR, Py-IR and XPS to reveal its physical and chemical properties. The SO 3 H-NG-C was used as a catalyst for converting corn stover into furfural and 5-hydromethylfurfural (5-HMF) via a one-step process. The effects of reaction temperature and time, solvent types, water concentrations, corn stover concentration, catalyst loading and catalyst stability were investigated systematically. 53 % furfural yield and17 % 5-HMF yield were obtained from 200 mg corn stover at 190 °C in 80 min using 100 mg SO 3 H-NG-C in Ƴ-valerolactone (GVL). Moreover, the used catalyst was separated from corn stover residue via sieve, and the catalyst showed reasonable stability for corn stover conversion.

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FOOD CHEMISTRY · 2020 · IF 6.306

A simple and sensitive sensor for lactose based on cascade reactions in Au nanoclusters and enzymes co-encapsulated metal-organic frameworks

Manli Guo,Jingtian Chi,Chi Zhang,Minglin Wang,Hui Liang,Juying Hou,Shiyun Ai,Xiangyang Li

In this work, one kind of zeolite imidazole frameworks containing bovine serum albumin stabilized Au nanoclusters (AuNCs), β-galactosidase (β-Gal) and glucose oxidase (GOx) (AuNCs/β-Gal/GOx@ZIF-8) were obtained to detect lactose. Compared with other fluorescent nano-materials, AuNCs show distinct advantages as a guest species in ZIF-8, specifically their extremely small size (<1 nm), simple synthesis, excellent biocompatibility and high stability. Furthermore, the bovine serum albumin on their surfaces can promote the formation of ZIF-8 coating; thus, AuNCs were co-encapsulated in ZIF-8 with the enzymes together. X-ray diffraction (XRD) analysis indicates the composite possesses the similar crystalline structure with pure ZIF-8. Fluorescence microscope images, Fourier transform infrared spectra and energy dispersive X-ray spectroscopy indicate the presence of AuNCs in the composite. Owing to the high local concentrations of the fluorescent probe and the quenching agent in AuNCs/β-Gal/GOx@ZIF-8, the quenching rate was enhanced 3.4-fold that of free AuNCs and enzymes in solution.

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Waste and Biomass Valorization · 2020 ·Vol. 12 ·期 6 ·3271-3286 · IF 2.851

Conversion of Glucose to 5-Hydroxymethylfurfural by Co-catalysis of p-Toluenesulfonic Acid (pTSA) and Chlorides: A Comparison Based on Kinetic Modeling

Sajid Muhammad,Bai Yuchen,Liu Dehua,Zhao Xuebing

Abstract Hydroxymethylfurfural (HMF) has been considered as one of the most promising biomass derived precursors for producing bio-based materials. Lewis acids are usually used to facilitate the isomerization of glucose to fructose in order to improve the HMF yield. In this study, glucose was converted to HMF with p -toluenesulfonic acid ( p TSA) and chlorides as Brønsted and Lewis acids catalysts in the DMSO medium at 120 °C under atmospheric pressure. Kinetic modeling of the process was investigated with consideration of glucose isomerization, dehydration of fructose, rehydration of HMF and formation of humin. NH 4 Cl was screened as the most efficient co-catalyst for glucose conversion with HMF yield of 47%. The developed model could be well used to simulate the process with satisfying goodness of fit. The activation energies for glucose isomerization, condensation, dehydration of fructose, and rehydration of HMF were determined to be 39.8, 18.1, 55.2, and 19.0 kJ/mol, respectively. However, because the fructose concentration was very low and the reaction rate of fructose dehydration was much higher than that of glucose isomerization, a pseudo-steady state assumption could be employed, by which the observed activation energy for a lumped reaction of glucose to HMF conversion ( E HMF ) was determined as 45.6 kJ/mol. The developed observed kinetic model could be well used to describe the kinetics of p TSA and chloride co-catalyzed conversion of HMF. Isomerization of glucose to fructose, condensation of glucose to form humin, dehydration of fructose to form HMF, and rehydration of HMF to LA were the major reactions in the system. To improve the HMF selectivity, efforts should be made to reduce the rate of glucose condensation to form humin Graphic Abstract

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ACS Applied Bio Materials · 2020 · IF 0

A Hybrid of FeS2 Nanoparticles Encapsulated by Two-Dimensional Carbon Sheets as Excellent Nanozymes for Colorimetric Glucose Detection

Wei Ding,Haibo Liu,Weiwen Zhao,Jie Wang,Linlin Zhang,Yuewei Yao,Cheng Yao,Chan Song

Recently, the development of nanozymes with high catalytic performance is gaining more and more attention due to the ever-growing demands for their practical applications. The elaborate design of its morphology has demonstrated to be an effective approach to improve the performance of these nanozymes. Herein, a hybrid of iron disulfide nanoparticles (FeS2 NPs) encapsulated by two-dimensional (2D) carbon nanosheets (NSs), denoted as FeS2@C NSs, demonstrates both superior peroxidase-like activity and excellent stability. The incorporation of 2D carbon sheets endows the proposed FeS2@C nanozymes with high specific surface area, providing abundant active sites to facilitate the contact with substrates. Moreover, the embedded FeS2 NPs are kept from aggregation due to the encapsulation and confinement of 2D carbon sheets, avoiding the conventional failure of single-component nanozymes. Based on glucose oxidase (GOx) and the elaborately designed FeS2@C nanozymes, a colorimetric method for glucose detection is then developed with excellent simplicity and sensitivity. The detection limit of the sensing platform is as low as 0.19 μM for a glucose assay. More notably, this method can be successfully employed for the glucose assay in some real samples, indicating the great potential of this FeS2@C NS-based nanozymes in the fields of biotechnology and clinical diagnostics.

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Green Energy & Environment · 2021 · IF 8.207

Synthesis of ordered hierarchically mesoporous/microporous carbon materials via compressed CO2 for fructose-to-HMF transformation

Sen Luan,Wei Li,Zanwu Guo,Wenxiu Li,Xiaojian Hou,Yi Song,Ran Wang,Qian Wang

Well-ordered hierarchically mesoporous/microporous carbon materials have been successfully fabricated by using dual soft-templating approach through compressed CO 2 . Pluronic F127 and different type of surfactants, including nonionic, cationic, and anionic surfactants, were used as dual templates to investigate the influence on the morphology and nanostructure of the as-prepared carbon samples. TEM, SEM, N 2 sorption, wide-angle and small-angle XRD analysis were employed to reveal the well-ordered hierarchically micro-mesoporous structure with 2D hexagonal symmetry by using compressed CO 2 . The prepared HPC samples with different pressures as the catalyst carriers have been functioned by chlorosulfonic acid for the fructose conversion into HMF. Chlorosulfonic acid concentration, catalyst dosage and reaction temperature have been optimized for fructose-to-HMF transformation with the obtained catalyst. The performances of as-made HPC–SO 3 H samples in HMF yield and reaction rate of fructose-to-HMF transformation have been investigated. The stability of the samples was also conducted in the dehydration of fructose to HMF for five cycles. The possible catalytic mechanism by using hierarchically porous carbon materials as catalyst support for fructose-to-HMF transformation was proposed.

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ACTA BIOCHIMICA ET BIOPHYSICA SINICA · 2020 ·Vol. 52 ·期 12 ·1420-1426 · IF 2.836

Development of a dual-fluorescence reporter system for high-throughput screening of L-aspartate-α-decarboxylase

Fei Mingyue,Mao Xudan,Chen Yiyang,Lu Yalan,Wang Lin,Yang Jie,Qiu Juanping,Sun Dongchang

β-Alanine (3-aminopropionic acid) holds great potential in industrial application. It can be obtained through a chemical synthesis route, which is hazardous to the environment. It is well known that l-aspartate-α-decarboxylase (ADC) can convert l-aspartate to β-alanine in bacteria. However, due to the low activity of ADC, industrial production of β-alanine through the green biological route remains unclear. Thus, improving the activity of ADC is critical to reduce the cost of β-alanine production. In this study, we established a dual-fluorescence high-throughput system for efficient ADC screening. By measuring the amount of β-alanine and the expression level of ADC using two different fluorescence markers, we can rapidly quantify the relative activity of ADC variants. From a mutagenesis library containing 2000 ADC variants, we obtained a mutant with 33% increased activity. Further analysis revealed that mutations of K43R and P103Q in ADC significantly improved the yield of β-alanine produced by the whole-cell biocatalysis. Compared with the previous single-fluorescence method, our system can not only quantify the amount of β-alanine but also measure the expression level of ADC with different fluorescence, making it able to effectively screen out ADC variants with improved relative activity. The dual-fluorescence high-throughput system for rapid screening of ADC provides a good strategy for industrial production of β-alanine via the biological conversion route in the future.

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FUEL PROCESSING TECHNOLOGY · 2020 · IF 4.982

Al-modified heteropolyacid facilitates alkyl levulinate production from cellulose and lignocellulosic biomass: Kinetics and mechanism studies

Chaonan Tao,Lincai Peng,Junhua Zhang,Liang He

Efficient production of fuels and chemicals from lignocellulosic biomass is the main goal of biorefinery processes. Herein, the metal-modified heteropolyacids with tunable Lewis and Brønsted acid sites were designed as the monolithic multifunctional catalyst for valorizing cellulose and lignocellulosic biomass to alkyl levulinate, a versatile platform molecule. Among them, Al-exchanged two protons of H 4 SiW 12 O 40 (Al 2/3 H 2 SiW 12 O 40 ) was found to be uniquely effective. The kinetic behavior describing the conversion of cellulose to ethyl levulinate was investigated to monitor the process, and compared between parent H 4 SiW 12 O 40 and Al 2/3 H 2 SiW 12 O 40 to understand the mechanistic role of Al 3+ . The introduction of Al 3+ substantially facilitated cellulose depolymerization and glucose-to-fructose isomerization , leading to a high rate and product selectivity. The estimated activation energies for cellulose degradation and glucopyraoside alcoholysis decreased by 50.6 kJ/mol and 40.9 kJ/mol, respectively. 50–72% yields of ethyl levulinate were accomplished from cellulosic biomasses such as pine wood, eucalyptus, bamboo, bagasse and Napier grass. Al 2/3 H 2 SiW 12 O 40 allowed cellulose conversion in various linear alcohols producing high-yield alkyl levulinate, and could be reused multiple times with a good stability. This study opens a reliable and promising avenue for one-pot transformation of cellulose and raw lignocellulosic biomass to ester compounds.

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NEW JOURNAL OF CHEMISTRY · 2020 ·Vol. 45 ·期 4 ·1959-1966 · IF 3.288

Separation and purification of horseradish peroxidase from horseradish roots using a novel integrated method

Wei Ji,Wenmei Ao,Mengqiu Sun,Chunlai Feng,Yun Wang

The aim of the present work was to develop a novel method integrating two-step aqueous two-phase extraction and temperature-controlled affinity precipitation for the separation and purification of horseradish peroxidase (HRP) from horseradish roots. First, a two-step aqueous two-phase extraction (ATPE) process was used as a primary separation process to remove sugars and pigments, and then a temperature-controlled affinity precipitation process based on a thermosensitive triblock copolymer (PEG113-b-PVBA49-b-PNIPAM105) was exploited as a further purification process to selectively isolate HRP from other impurity proteins. The optimum PEG4000 (0.20, w/w) − (NH4)2SO4 (0.18, w/w) aqueous two-phase system (ATPS) was obtained by studying the liquid–liquid equilibrium of PEG (400/1000/2000/4000) + (NH4)2SO4/K3C6H5O7/K2HPO4 ATPSs and the distribution behaviors of 9 kinds of model compounds in these PEG-salt ATPSs. The successful isolation of HRP from horseradish roots was achieved by the integrated method without having a negative effect on the structure of HRP, and the extraction efficiency and purification factor of HRP reached 84.26 ± 0.15% and 9.15 ± 0.10, respectively. The integrated method shows outstanding separation and purification performances and has good prospects for the industrial production of plant glycoprotein.

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