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JOURNAL OF RADIOANALYTICAL AND NUCLEAR CHEMISTRY · 2023 ·Vol. 332 ·期 10 ·4167-4177 · IF 1.6

Efficient removal of Co(II) from aqueous solution by one-step preparation of heterocyclic ligand-functionalized MOFs: study on adsorption properties and irradiation stability

Peng Yinyin,Pan Ting,Chen Chuang,Zhou Mi,Liu Derong,Feng Jian,Xiong Wei,Liu Ning,Yuan Guoyuan

In this work, MOFs materials functionalized (HC-MOFs) with heterocyclic ligands (thiophene-TPC, pyrrole-PCA and furfural-FUR) were prepared by a one-step method and used for cobalt ion separation studies. The results showed that the maximum adsorption of cobalt ions by the three adsorbents was 141.0 mg/g (UiO-66-TPC), 146.0 mg/g (UiO-66-PCA), and 150.6 mg/g (UiO-66-FUR), respectively, at pH 8.3 and a temperature of 298 K. In addition, The HC-MOFs showed good stability under different doses (0 ~ 200 kGy) of γ-ray irradiation and have great potential for application in the separation of practical radioactive wastewater containing 60 Co.

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JOURNAL OF MATERIALS SCIENCE-MATERIALS IN MEDICINE · 2023 ·Vol. 34 ·期 7 ·1-13 · IF 3.7

Beta-TCP scaffolds with rationally designed macro-micro hierarchical structure improved angio/osteo-genesis capability for bone regeneration

Feng Jianlang,Liu Junjie,Wang Yingqu,Diao Jingjing,Kuang Yudi,Zhao Naru

The design of hierarchical porous structure in scaffolds is crucial for bone defect regenerative repair. However, bioceramic materials present a challenge in precisely constructing designed micropores owing to the limitation of forming process. To investigate micropore shape influences bone regeneration in bioceramic scaffolds with macropores, hierarchical porous scaffolds with interconnective macropores (~400 μm) and two types of micropores (spherical and fibrous) were prepared using a combination of direct ink writing (DIW) and template sacrifice methods. Compared to the scaffold with spherical micropores, the scaffold with highly interconnected fibrous micropores significantly improved cell adhesion and upregulated osteogenic and angiogenetic-related gene expression in mBMSCs and HUVECs, respectively. Furthermore, in vivo implantation experiments showed that hierarchical scaffolds with fibrous micropores accelerated the bone repair process significantly. This result can be attributed to the high interconnectivity of fibrous micropores, which promotes the transportation of nutrients and waste during bone regeneration. Our work demonstrates that hierarchical porous scaffold design, especially one with a fibrous micropore structure, is a promising strategy for improving the bone regeneration performance of bioceramic scaffolds. Graphical Abstract

CAS / MDL: 78-10-4
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CELLULOSE · 2023 ·Vol. 30 ·期 12 ·7575-7589 · IF 5.7

A novel strategy for highly efficient conversion of cellulose into 5-hydroxymethylfurfural using green and effective stepwise catalytic systems

Wang Tao,Zhang Cailiang,Feng Hui,Zou Qingjun,Huang Wenrui,Wu Jiacong,Han Juan,Wang Yun

In this study, a green and effective stepwise catalytic system for cellulose conversion to 5-hydroxymethylfurfural (HMF) is reported. In a pretreatment process, very fast (15 min) dissolution of cellulose was achieved at a low temperature of 70 °C, utilizing ZnBr 2 ·4H 2 O as the best dissolution solvent, which to improve the reactivity of cellulase for raw cellulose and increase efficiency of cellulose degradation. Enzyme-inorganic hybrid nanoflowers (Cellulase@β-glucosidase/Zn 3 (PO 4 ) 2 -NF and Glucose isomerase@Zn 3 (PO 4 ) 2 -NF) with different morphological structures were prepared to act as biocatalyst in the sequential conversion of pretreated cellulose to glucose and glucose to fructose. HCl was applied catalyst for dehydration of fructose to 5-HMF in a water/tert-butanol biphasic system. Under optimal reaction conditions, the yield of 5-HMF for the overall reaction from cellulose was about 21.6%. A feasibility route for green conversion of cellulose to 5-HMF is reported. Graphical abstract

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CATALYSIS LETTERS · 2023 · IF 2.8

High-Efficient Hydrogenolysis of Xylose to Polyols Over Ni-W/CeO2 Catalysts

Zhu Peng,Han Chunyang,Xia Haian

Catalytic hydrogenolysis of xylose to ethylene glycol (EG) and 1,2-propanediol (1,2-PG) is an important way for the high-value valorization of biomass. Herein, Ni-W/CeO 2 catalysts prepared by incipient-wetness impregnation method were used for the hydrogenolysis of xylose to EG and 1,2-PG. Several characterizations such as X-ray diffraction (XRD), Transmission electron microscopy (TEM) and X-ray photoelectronic spectroscopy (XPS) were used to analyze the physicochemical properties of the catalysts. The effects of different Ni/W ratios and reaction conditions on the hydrogenolysis performance of the catalyst were investigated. The doping of W promoted the selective cleavage of C–C and C-O bonds of xylose, thus improved the yield of EG 1,2-PG. The doping of W can form interactions with Ni and increase the oxygen vacancy concentration of CeO 2 , which have a significant impact on the catalyst activity. When the Ni: W ratio is around 1:1, the catalyst has the best activity, and the total yield of diols can reach about 43.2%.. When xylan was used as the substrate, the total yield of diols can reach to 58.7%. The possible reaction mechanism of xylose hydrogenolysis was also discussed. This work developed a new catalyst system for the directional conversion of xylose to EG and 1,2-PG, which provided a new idea for the design of catalyst to converting lignocellulose, especially carbohydrate into high-value chemicals. Graphical Abstract Ni-W/CeO 2 with different Ni/W ratio are efficient catalysts for hydrogenolysis of xylose to EG and 1,2-PG.

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TRANSACTIONS OF TIANJIN UNIVERSITY · 2023 ·Vol. 29 ·期 4 ·293-303 · IF 7.1

Proximity Effect of Fe–Zn Bimetallic Catalysts on CO2 Hydrogenation Performance

Liu Shengkun,Zhao Qiao,Han Xiaoxue,Wei Chongyang,Liang Haoting,Wang Yidan,Huang Shouying,Ma Xinbin

The interaction between a promoter and an active metal crucially impacts catalytic performance. Nowadays, the influence of promoter contents and species has been intensively considered. In this study, we investigate the effect of the iron (Fe)–zinc (Zn) proximity of Fe–Zn bimetallic catalysts on CO 2 hydrogenation performance. To eliminate the size effect, Fe 2 O 3 and ZnO nanoparticles with uniform size are first prepared by the thermal decomposition method. By changing the loading sequence or mixing method, a series of Fe–Zn bimetallic catalysts with different Fe–Zn distances are obtained. Combined with a series of characterization techniques and catalytic performances, Fe–Zn bimetallic proximity for compositions of Fe species is discussed. Furthermore, we observe that a smaller Fe–Zn distance inhibits the reduction and carburization of the Fe species and facilitates the oxidation of carbides. Appropriate proximity of Fe and Zn (i.e., Fe 1 Zn 1 -imp and Fe 1 Zn 1 -mix samples) results in a suitable ratio of the Fe 5 C 2 and Fe 3 O 4 phases, simultaneously promoting the reverse water–gas shift and Fischer–Tropsch synthesis reactions. This study provides insight into the proximity effect of bimetallic catalysts on CO 2 hydrogenation performance. Graphical Abstract

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Science China-Chemistry · 2023 · IF 9.6

Raman imaging analysis of intracellular biothiols independent of the aggregation of sensing substrates

Zhang Min,Li Zijun,Zhang Mengyang,Heng Hang,Xu Shiying,Wang Zhaoyin,Dai Zhihui

The content of biothiols in cells is highly associated with the occurrence and development of several diseases. However, due to their active chemical properties, thiol-contained molecules are normally volatile during the detection process, rendering precise analysis of intracellular biothiols challenging. In this study, 5,5′-dithiobis-(2-nitrobenzoic acid) (DTNB) is covalently modified on the surface of gold nanorods (AuNRs), constructing sensing substrates for in situ Raman imaging analysis of biothiols in cells. AuNRs are able to serve as ideal surface-enhanced Raman scattering substrates, and thus Raman signals of DTNB are greatly amplified by AuNRs. Meanwhile, the disulfide bond of DTNB can be broken by thiols, thereby releasing part of DTNB from the surface of AuNRs. As a result, three kinds of main biothiols are sensitively quantified with DTNB-modified AuNRs according to the variation of Raman signals, and DTNB-modified AuNRs exhibit far better analytical performance than a commercial probe. In addition, the sensing substrates can be readily delivered to cytoplasm with the transmembrane of AuNRs, and are capable of responding to biothiols in cells. Notably, the Raman approach is established by the breaking of chemical bonds rather than the aggregation of substrates, which is more inclined to analyze intracellular biothiols with a desirable spatial resolution. Therefore, fluctuation of biothiols in glioma cells is evidently observed via Raman imaging. Overall, this work provides an alternative strategy for designing Raman sensors to visualize active molecules in cells.

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CHINESE JOURNAL OF POLYMER SCIENCE · 2023 ·Vol. 41 ·期 12 ·1889-1901 · IF 4.3

MOF-derived Porous Carbon Nanofiber Assembly as High Efficiency ORR Electrocatalysts for Zinc-air Batteries

Ma Jin-Liang,Liu Long-Long,Zhao Ren-Hai,Yuan Ding,Ning Xin

Reasonable construction of high activity and low cost non-noble metal oxygen reduction reaction (ORR) catalyst is of great importance for the wide application of zinc-air batteries (ZABs). Using bimetallic MOF as a precursor combined with electrospinning, high-temperature carbonization and electrodeposition, we successfully developed a porous carbon nanofiber (Co@Fe-CNFs-1000) with bimetallic active center as an efficient catalyst for ORR. The successful construction of this special core-shell structure directly explores the synergy between different active centers. The results showed that the synthesized Co@Fe-CNFs-1000 catalyst exhibited ORR performance comparable to that of Pt/C in 0.1 mol/L KOH electrolyte, high half-wave potential ( E 1/2 =0.81 V) and limiting current density ( J L =5.4 mA-cm −2 ). In addition, homemade liquid ZABs with Co@Fe-CNFs-1000 as the air cathode showed excellent power density (155.8 mW·cm −2 ), specific capacity (780.6 mAh·g Zn −1 ) and long-term stability (over 100 h at 2 mA·cm −2 ), surpassing even Pt/C-based batteries. In addition, the flexible solid-state ZABs assembled based on Co@Fe-CNFs-1000 demonstrates excellent flexibility and durability. This work provides a new idea for constructing ORR catalysts with high activity centers.

CAS / MDL: 693-98-1 25014-41-9
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Nature Protocols · 2023 ·Vol. 18 ·期 8 ·2579-2599 · IF 14.8

Fabrication of electron tunneling probes for measuring single-protein conductance

Jiang Tao,Yi Long,Liu Xu,Ivanov Aleksandar P.,Edel Joshua B.,Tang Longhua

Studying the electrical properties of individual proteins is a prominent research area in the field of bioelectronics. Electron tunnelling or quantum mechanical tunnelling (QMT) probes can act as powerful tools for investigating the electrical properties of proteins. However, current fabrication methods for these probes often have limited reproducibility, unreliable contact or inadequate binding of proteins onto the electrodes, so better solutions are required. Here, we detail a generalizable and straightforward set of instructions for fabricating simple, nanopipette-based, tunnelling probes, suitable for measuring conductance in single proteins. Our QMT probe is based on a high-aspect-ratio dual-channel nanopipette that integrates a pair of gold tunneling electrodes with a gap of less than 5 nm, fabricated via the pyrolytic deposition of carbon followed by the electrochemical deposition of gold. The gold tunneling electrodes can be functionalized using an extensive library of available surface modifications to achieve single-protein–electrode contact. We use a biotinylated thiol modification, in which a biotin–streptavidin–biotin bridge is used to form the single-protein junction. The resulting protein-coupled QMT probes enable the stable electrical measurement of the same single protein in solution for up to several hours. We also describe the analysis method used to interpret time-dependent single-protein conductance measurements, which can provide essential information for understanding electron transport and exploring protein dynamics. The total time required to complete the protocol is ~33 h and it can be carried out by users trained in less than 24 h.

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JOM · 2023 ·Vol. 75 ·期 12 ·5167-5175 · IF 2.6

Phase and Structure Optimizations of MoS2 Concentrate Pellets with Al2O3-SiO2 Additives During Oxidative and Volatilizing Roasting Process

Li Guanghui,Huang Jiahao,Sun Hu,Mang Changye,Hou Yanrui,Luo Jun

The novel one-step oxidation–volatilization process for separating MoO 3 from pelletized MoS 2 concentrate supported on a porous Al 2 O 3 -SiO 2 skeleton has been demonstrated to have superior diffusion efficiency compared to the traditional two-step oxidative roasting-sublimation approach. Optimal control of pellet phase and micro-structure evolutions is crucial for maintaining a stable and breathable pellet bed throughout the roasting process, which is essential for industrial application of the new process. This work determined the phase transformations of MoS 2 concentrate pellets during roasting, revealed the formation mechanisms of mullite whiskers from MoS 2 -Al 2 O 3 -SiO 2 system and thus achieved toughening control of roasted MoS 2 concentrate pellets with temperature programmed roasting (TPR). It is found that the intermediate product Al 2 (MoO 4 ) 3 can induce the low-temperature formation of mullite whisker. With TPR, the volatilization rate of molybdenum is 97.2%, and the compressive strength of mullite pellets reach 124.8 N. This study puts forward a feasible route with industrial significance.

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CHEMICAL RESEARCH IN CHINESE UNIVERSITIES · 2023 ·Vol. 39 ·期 4 ·647-653 · IF 3.1

pH-Induced Size Regulation of Ru Nanocrystals and the Applications Towards Proton Exchange Membrane Water Electrolysis

Li Miao,Hao Yashi,Yang Zuobo,Yun Jimmy,Liang Xin

Ruthenium(Ru) and its derivatives have been widely studied as oxygen evolution reaction(OER) electrocatalysts in acidic water electrolysis due to their inherent electronic properties and high oxygen evolution activity. A facile pH-induced size regulation approach for Ru nanocrystals has been developed by introducing NaOH and CH 3 COOH in a polyol system. The size of Ru particles decreases with the increase of the dosage of NaOH and increases at a certain dosage of CH 3 COOH. The formation mechanism of ruthenium nanocrystals was investigated through a series of characterizations and kinetic experiments. The electrocatalytic activities of the electrocatalysts derived from these Ru particles were studied toward OER to investigate the influence of particle size on their electrocatalytic properties. Moreover, the prepared electrocatalysts were applied as anodic materials in the proton exchange membrane(PEM) electrolysis cell and demonstrated excellent performance.

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MICROCHIMICA ACTA · 2023 ·Vol. 190 ·期 7 ·1-10 · IF 5.7

Detection of L-cysteine in urine samples based on CdS/TiO2-modified extended-gate field-effect transistor photoelectrochemical sensor

Zhang Yujie,Yu Jiarui,Huang Wanjin,Jin Zhenhuan,Li Jianping

A novel extended-gate field-effect transistor (FET) photoelectrochemical (EGFET PEC) sensor was designed for highly sensitive detection of L-cysteine (L-Cys). TiO 2 was initially modified on the ITO electrode by the sol–gel dip-coating method and calcined to produce TiO 2 /ITO. Then, CdS was synthesized on the TiO 2 surface by hydrothermal method to obtain the CdS–TiO 2 heterojunction material. CdS/TiO 2 /ITO was connected to the gate of the FET to obtain an EGFET PEC sensor. Under the irradiation of a xenon lamp simulating visible light, the CdS/TiO 2 heterojunction composite absorbs light energy to produce photogenerated electron–hole pairs, which have strong photocatalytic oxidation activity and oxidize L-Cys covalently identified by Cd(II) through CdS covalent. These pairs generate a photovoltage that controls the current between the source and the drain to detect L-Cys. Under the optimized experimental conditions, the optical drain current ( I D ) of the sensor exhibited a good linear relationship with the logarithm of L-Cys in the range of 5.0 × 10 −9 –1.0 × 10 −6 mol/L, and the detection limit was 1.3 × 10 −9 mol/L (S/N = 3), which is lower than the values reported by other detection methods. Results showed that the CdS/TiO 2 /ITO EGFET PEC sensor revealed high sensitivity and good selectivity. The sensor has been used to determine L-Cys in urine samples. Graphical abstract

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MOLECULAR IMAGING AND BIOLOGY · 2023 ·Vol. 25 ·期 6 ·1125-1134 · IF 3.1

Preliminary Evaluation of 18F-Labeled Benzylguanidine Analogs as NET Tracers for Myocardial Infarction Diagnosis

Yang Liping,Yin Liping,Hu Mei,Zhao Weiling,Wang Changjiang,Chen Yue,Li Zibo,Wang Li

Purpose Heart failure (HF) remains a major cause of late morbidity and mortality after myocardial infarction (MI). To date, no clinically established 18 F-labeled sympathetic nerve PET tracers for monitoring myocardial infarction are available. Therefore, in this study, we synthesized a series of 18 F-labeled benzyl guanidine analogs and evaluated their efficacy as cardiac neuronal norepinephrine transporter (NET) tracers for myocardial imaging. We also investigated the preliminary diagnostic capabilities of these tracers in myocardial infarction animal models, as well as the structure-activity relationship of these tracers. Procedures Three benzyl guanidine-NET tracers, including [ 18 F] 1 , [ 18 F] 2, and [ 18 F] 3 , were synthesized and evaluated in vivo as PET tracers in a myocardial infarction mouse model. [ 18 F]LMI1195 was used as a positive control for the tracers. H&E staining of the isolated myocardial infarction heart tissue sections was performed to verify the efficacy of the selected PET tracer. Results Our data show that [ 18 F] 3 had a moderate decay corrected labeling yield (~10%) and high radiochemical purity (>95%) compared to other tracers. The uptake of [ 18 F] 3 in normal mouse hearts was 1.7±0.1%ID/cc at 1 h post-injection (p. i.), while it was 2.4±0.1, 2.6±0.9, and 2.1±0.4%ID/cc in the MI mouse hearts at 1, 2, and 3 days after surgery, respectively. Compared with [ 18 F]LMI1195, [ 18 F] 3 had a better myocardial imaging effect in terms of the contrast between normal and MI hearts. The area of myocardial infarction shown by PET imaging corresponded well with the infarcted tissue demonstrated by H&E staining. Conclusions With an obvious cardiac uptake contrast between normal mice and the myocardial infarction mouse model, [ 18 F] 3 appears to be a potential tool in the diagnosis of myocardial infarction. Therefore, it is necessary to conduct further structural modification studies on the chemical structure of [ 18 F] 3 to improve its in vivo stability and diagnostic detection ability to achieve reliable and practical imaging effects.

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