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MICROCHIMICA ACTA · 2023 ·Vol. 190 ·期 9 ·1-10 · IF 5.7

Covalent organic framework in situ grown on the metal–organic framework as fiber coating for solid-phase microextraction of polycyclic aromatic hydrocarbons in tea

Xu Li,Hu Wei,Luo Xiaogang,Zhang Juan

A novel MIL-88-NH 2 @COF composite was produced by in situ growth of covalent organic framework (COF) on the metal–organic framework (MOF) surface. To obtain a coating fiber for solid-phase microextraction (SPME), the MIL-88-NH 2 @COF composite physically adhered to the stainless steel wire. Combined with gas chromatography-flame ionization detection (GC-FID), various analytes such as chlorophenols (CPs), phthalates (PAEs), and polycyclic aromatic hydrocarbons (PAHs) were extracted and determined to evaluate the extraction performance of MIL-88-NH 2 @COF coated fibers and explore their extraction mechanism. This composite exhibit excellent extraction performance and adsorption capacity for various analytes, especially for PAHs with enrichment factor up to 9858. The SPME-GC-FID method based on MIL-88-NH 2 @COF fiber was established for the determination of five PAHs after the main extraction conditions were optimized. Under optimal conditions, the proposed technique showed a wide linear range (1–150 ng mL −1 ) with a low limit of detection (0.019 ng mL −1 ) and a high coefficient of determination ( R 2  > 0.99). The developed SPME-GC-FID method was used to determine PAHs in green tea and black tea samples, with good recoveries of 51.70–103.64% and 68.56–103.64%, respectively. It is worth mentioning that this is the first time MIL-88-NH 2 @COF composites have been prepared and applied to SPME. The preparation method of the composite provides a new idea in adsorbent preparation, which will contribute to the field of SPME. Graphical abstract

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Nature Communications · 2023 ·Vol. 14 ·期 1 ·1-10 · IF 16.6

A stretchable, mechanically robust polymer exhibiting shape-memory-assisted self-healing and clustering-triggered emission

Wang Xiaoyue,Xu Jing,Zhang Yaoming,Wang Tingmei,Wang Qihua,Li Song,Yang Zenghui,Zhang Xinrui

Self-healing and recyclable polymer materials are being developed through extensive investigations on noncovalent bond interactions. However, they typically exhibit inferior mechanical properties. Therefore, the present study is aimed at synthesizing a polyurethane–urea elastomer with excellent mechanical properties and shape-memory-assisted self-healing behavior. In particular, the introduction of coordination and hydrogen bonds into elastomer leads to the optimal elastomer exhibiting good mechanical properties (strength, 76.37 MPa; elongation at break, 839.10%; toughness, 308.63 MJ m −3 ) owing to the phased energy dissipation mechanism involving various supramolecular interactions. The elastomer also demonstrates shape-memory properties, whereby the shape recovery force that brings damaged surfaces closer and facilitates self-healing. Surprisingly, all specimens exhibite clustering-triggered emission, with cyan fluorescence is observed under ultraviolet light. The strategy reported herein for developing multifunctional materials with good mechanical properties can be leveraged to yield stimulus-responsive polymers and smart seals.

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Nature Communications · 2023 ·Vol. 14 ·期 1 ·1-14 · IF 16.6

Bioinspired “cage traps” for closed-loop lead management of perovskite solar cells under real-world contamination assessment

Luo Huaiqing,Li Pengwei,Ma Junjie,Li Xue,Zhu He,Cheng Yajie,Li Qin,Xu Qun,Zhang Yiqiang,Song Yanlin

Despite the remarkable progress made in perovskite solar cells, great concerns regarding potential Pb contamination risk and environmental vulnerability risks associated with perovskite solar cells pose a significant obstacle to their real-world commercialization. In this study, we took inspiration from the ensnaring prey behavior of spiders and chemical components in spider web to strategically implant a multifunctional mesoporous amino-grafted-carbon net into perovskite solar cells, creating a biomimetic cage traps that could effectively mitigate Pb leakage and shield the external invasion under extreme weather conditions. The synergistic Pb capturing mechanism in terms of chemical chelation and physical adsorption is in-depth explored. Additionally, the Pb contamination assessment of end-of-life perovskite solar cells in the real-world ecosystem, including Yellow River water and soil, is proposed. The sustainable closed-loop Pb management process is also successfully established involving four critical steps: Pb precipitation, Pb adsorption, Pb desorption, and Pb recycling. Our findings provide inspiring insights for promoting green and sustainable industrialization of perovskite solar cells.

CAS / MDL: 67-63-0 7681-82-5
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JOURNAL OF NANOBIOTECHNOLOGY · 2023 ·Vol. 21 ·期 1 ·1-17 · IF 10.2

3-Bromopyruvate-loaded bismuth sulfide nanospheres improve cancer treatment by synergizing radiotherapy with modulation of tumor metabolism

He Yiman,Chen Huawan,Li Wenbo,Xu Lu,Yao Huan,Cao Yang,Wang Zhigang,Zhang Liang,Wang Dong,Zhou Di

Background Radiotherapy (RT) is one of the most mainstream cancer therapeutic modalities. However, due to the lack of specificity of the radiation adopted, both normal and cancerous cells are destroyed indiscriminately. This highlights the crucial need to improve radiosensitization. This study aims to address this issue by constructing a multifunctional nanospheres that can sensitize multiple aspects of radiotherapy.Results Nanospheres containing high atomic element Bi can effectively absorb ionizing radiation and can be used as radiosensitizers. Cell viability after Bi2S3 + X-ray treatment was half that of X-ray treatment alone. On the other hand, exposed 3-bromopyruvate (3BP) could reduce the overactive oxygen (O2) metabolism of tumor cells and alleviate tumor hypoxia, thereby promoting radiation-induced DNA damage. The combination index (CI) of 3BP and Bi2S3-based RT in Bi2S3-3BP + X-ray was determined to be 0.46 with the fraction affected (fa) was 0.5 via Chou-Talalay’s isobolographic method, which indicated synergistic effect of 3BP and Bi2S3-based RT after integration into Bi2S3-3BP + X-ray. Under the combined effect of 3BP and RT, autophagy was over-activated through starvation-induced and redox homeostasis dysregulation pathways, which in turn exhibited pro-death effects. In addition, the prepared nanospheres possess strong X-ray attenuation and high near-infrared (NIR) optical absorption, thus eliminating the need for additional functional components and could serve as bimodal contrast agents for computed tomography/photoacoustic (CT/PA) imaging.Conclusion sThe rational design of multifunctional nanospheres with the unique properties provided a novel strategy to achieving high therapeutic efficacy in RT. This was accomplished through simultaneous activation of multiple sensitization pathways by increasing ionizing radiation, reducing tumor oxygen consumption, inducing pro-death autophagy, and providing multiple-imaging guidance/monitoring.

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Cell Communication and Signaling · 2023 ·Vol. 21 ·期 1 ·1-18 · IF 8.4

Myofiber directs macrophages IL-10-Vav1-Rac1 efferocytosis pathway in inflamed muscle following CTX myoinjury by activating the intrinsic TGF-β signaling

Liao Zhaohong,Lan Haiqiang,Jian Xiaoting,Huang Jingwen,Wang Han,Hu Jijie,Liao Hua

Background To explore the role of skeletal muscle specific TGF-β signaling on macrophages efferocytosis in inflamed muscle caused by Cardiotoxin (CTX) injection. Methods CTX myoinjury was manipulated in TGF-βr2 flox/flox (control) mice or transgenic mice with TGF-β receptor 2 (TGF-βr2) being specifically deleted in skeletal muscle (SM TGF-βr2 −/− ). Gene levels of TGF-β signal molecules, special inflammatory mediators in damaged muscle or in cultured and differentiated myogenic precursor cells (MPC-myotubes) were monitored by transcriptome microarray or qRT-PCR. TGF-β pathway molecules, myokines and embryonic myosin heavy chain in regenerating myofibers, the phenotype and efferocytosis of macrophages were evaluated by immunofluorescence, immunoblotting, Luminex, or FACS analysis. In vitro apoptotic cells were prepared by UV-irradiation. Results In control mice, TGF-β-Smad2/3 signaling were significantly up-regulated in regenerating centronuclear myofibers after CTX-myoinjury. More severe muscle inflammation was caused by the deficiency of muscle TGF-β signaling, with the increased number of M1, but the decreased number of M2 macrophages. Notably, the deficiency of TGF-β signaling in myofibers dramatically affected on the ability of macrophages to conduct efferocytosis, marked by the decreased number of Annexin-V − F4/80 + Tunel + macrophages in inflamed muscle, and the impaired uptake of macrophages to PKH67 + apoptotic cells transferred into damaged muscle. Further, our study suggested that, the intrinsic TGF-β signaling directed IL-10-Vav1-Rac1 efferocytosis signaling in muscle macrophages. Conclusions Our data demonstrate that muscle inflammation can be suppressed potentially by activating the intrinsic TGF-β signaling in myofibers to promote IL-10 dependent-macrophages efferocytosis. Video Abstract

CAS / MDL: 30525-89-4
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Nature Communications · 2023 ·Vol. 14 ·期 1 ·1-12 · IF 16.6

Halide-assisted differential growth of chiral nanoparticles with threefold rotational symmetry

Zheng Jiapeng,Boukouvala Christina,Lewis George R.,Ma Yicong,Chen Yang,Ringe Emilie,Shao Lei,Huang Zhifeng,Wang Jianfang

Enriching the library of chiral plasmonic nanoparticles that can be chemically mass-produced will greatly facilitate the applications of chiral plasmonics in areas ranging from constructing optical metamaterials to sensing chiral molecules and activating immune cells. Here we report on a halide-assisted differential growth strategy that can direct the anisotropic growth of chiral Au nanoparticles with tunable sizes and diverse morphologies. Anisotropic Au nanodisks are employed as seeds to yield triskelion-shaped chiral nanoparticles with threefold rotational symmetry and high dissymmetry factors. The averaged scattering g -factors of the l - and d -nanotriskelions are as large as 0.57 and − 0.49 at 650 nm, respectively. The Au nanotriskelions have been applied in chiral optical switching devices and chiral nanoemitters. We also demonstrate that the manipulation of the directional growth rate enables the generation of a variety of chiral morphologies in the presence of homochiral ligands.

CAS / MDL: 7681-11-0
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Nano Research · 2023 ·Vol. 16 ·期 8 ·11042-11047 · IF 9.9

A new FTO/TiO2/PbO2 electrode for eco-friendly electrochemical determination of chemical oxygen demand

Wang Lei,Zhang Yuehan,Sun Xiaoxuan,Li Yunhui,Zhai Junfeng,Dong Shaojun

Eco-friendly chemical oxygen demand (COD) sensors are highly desired with respect to the importance of COD determination in environmental protection. In this work, a new FTO/TiO 2 /PbO 2 (FTO = fluorine-doped tin oxide) electrode was fabricated with a two-step method and used as an eco-friendly electrochemical COD sensor. The interlayer TiO 2 was employed to strengthen the adhesion of PbO 2 on the FTO substrates by providing a large TiO 2 /PbO 2 interface area. The effects of the factors including applied potential, supporting electrolyte concentration and stirring speed on the sensing performance were investigated. Under the optimized conditions, linear responses to the COD of water with different COD sources were achieved, and a linear range from 5 to 120 mg/L was obtained in the case of sucrose as the COD source. The relative standard deviations (RSD) were determined to be less than 9% for the glucose solutions with the COD of 7.5, 12.5 and 17.5 mg/L. For real sample analysis, the obtained results were comparable with those measured with the conventional dichromate method, with a relative error less than 11%.

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JOURNAL OF APPLIED PHYCOLOGY · 2023 · IF 3.3

Efficient preparation and production of ulvan oligosaccharides by using a new PL25 family ulvan lyase from Alteromonas sp. 76–1

Tang Tiancheng,Li Chen,Zhu Benwei,Yao Zhong

Ulvan lyase is a useful tool which can degrade ulvan into oligosaccharides with a range of biological activities. In this study, the ulvan lyase ULA-3 from Alteromonas sp. 76–1, which was a 1467-bp encoded 489-amino acid residue protein, has been cloned, heterologously expressed and biochemically characterized. ULA-3 showed the maximum activity at 45 ˚C and pH 9.0. The K m is 1.879 mg mL −1 and V max is 2.597 µmol min −1  mL −1 . Its enzyme activity was outstanding at 11.754 U mg −1 . Moreover, its metal ion stability is exceptionally good and most metal ions at a concentration of 1 mM have no inhibitory effect on its activity. It can endolytically degrade ulvan into oligosaccharides with a degree of polymerization (Dp) of 2–4 and with unsaturated double bond through the β -elimination reaction, which mainly cleaves the glycosidic bond between rhamnose and uronic acids. All in all, our study has increased the ulvan lyase database and offers the opportunity to fully utilize ulvan, a green biomass resource from marine algae.

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Journal of Central South University · 2023 ·Vol. 30 ·期 5 ·1523-1538 · IF 4.4

Pyrolysis characteristics of waste printed circuit boards and distribution pattern of their valuable liquid products

Xu Jia-qi,Liu Wei,Jiao Fen,Han Jun-wei,Qin Wen-qing,Cai Can

Pyrolysis is a promising technology to treat waste printed circuit boards (WPCBs) with significant advantages of full source utilization, high separation efficiency and scarce pollutant emissions. In this work, TG and DTG analyses were performed to determine pyrolysis characteristics. The kinetic analysis adopting the Starink Kissinger-Akahira-Sunose (SKAS) model was conducted to confirm the apparent activation energy ( E α ). Pyrolysis products were collected using a lab-scale pyrolyzer. GC-MS analysis coupled with MS-DIAL data processing was applied to clarify the distribution pattern of valuable liquid products. The results indicated that the main thermal decomposition of WPCBs occurred within the temperature range of 157–664 °C, with E α ranging from 80.70 to 279.46 kJ/mol. During pyrolysis, the WPCBs were converted into three kinds of products, in which solid and gas products could be applied in the field of materials and energy. The composition of WPCBs oil products was complicated and sensitive to the pyrolysis temperature. The largest proportion of valuable liquid products (82.94%) was obtained at 600 °C, containing 52.87% monocyclic aromatic phenols, 4.39% polycyclic aromatic phenols, 3.07% brominated phenols, and 22.61% hydrocarbons, respectively. These valuable liquid products would be an attractive alternative as raw materials for the synthesis of phenolic resins and the production of petrochemicals.

CAS / MDL: 13127-88-3 67-64-1
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Nature Communications · 2023 ·Vol. 14 ·期 1 ·1-10 · IF 16.6

Lean-water hydrogel electrolyte for zinc ion batteries

Wang Yanbo,Li Qing,Hong Hu,Yang Shuo,Zhang Rong,Wang Xiaoqi,Jin Xu,Xiong Bo,Bai Shengchi,Zhi Chunyi

Solid polymer electrolytes (SPEs) and hydrogel electrolytes were developed as electrolytes for zinc ion batteries (ZIBs). Hydrogels can retain water molecules and provide high ionic conductivities; however, they contain many free water molecules, inevitably causing side reactions on the zinc anode. SPEs can enhance the stability of anodes, but they typically possess low ionic conductivities and result in high impedance. Here, we develop a lean water hydrogel electrolyte, aiming to balance ion transfer, anode stability, electrochemical stability window and resistance. This hydrogel is equipped with a molecular lubrication mechanism to ensure fast ion transportation. Additionally, this design leads to a widened electrochemical stability window and highly reversible zinc plating/ stripping. The full cell shows excellent cycling stability and capacity retentions at high and low current rates, respectively. Moreover, superior adhesion ability can be achieved, meeting the needs of flexible devices.

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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2023 ·Vol. 415 ·期 22 ·5353-5363 · IF 4.3

Hexafluorobutanol primary alcohol ethoxylate-based supramolecular solvent formation and their application in direct microextraction of malachite green and crystal violet from lake sediments

Yu Yang,Pai Nanya,Chen Xiaoya,Wang Baoling,Gao Shulin,Ge Dandan

A new type of hexafluorobutanol (HFB) primary alcohol ethoxylate (AEO)-based supramolecular solvent (SUPRAS) with density higher than water was prepared for the first time. HFB acted as AEO micelle-forming agent and density-regulating agent for SUPRAS formation. The prepared SUPARS was applied as extraction solvent for vortex-assisted direct microextraction of malachite green (MG) and crystal violet (CV) from lake sediment followed by high-performance liquid chromatographic determination. In the present work, SUPRASs prepared from AEO with different carbon chains as the amphiphiles and various coacervation agents were investigated. SUPARS formed from MOA-3 and HFB provided better extraction efficiency in comparison with other SUPRASs. Parameters influencing the extraction recovery of target analytes including the type and volume of AEO, volume of HFB, and vortex time were investigated and optimized. Under optimized conditions, linearity in the range of 2.0–400 μg g −1 for MG and 2.0–500 μg g −1 for CV with a correlation coefficient higher than 0.9947 was obtained. Limits of detection of 0.5 μg g −1 and relative standard deviations in the range of 0.9–5.8% were obtained. Compared to conventional extraction techniques for analysis of analytes in solid samples, the proposed method reduced sample usage and eliminated a primary extraction process by using a toxic organic solvent. The proposed method is simple, fast, and green and can be used for the analysis of target analytes in solid samples. Graphical Abstract

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Nano Research · 2023 ·Vol. 16 ·期 10 ·12270-12280 · IF 9.9

Core-shell Cu@SiO2/SiO2 catalyst for 1,6-hexanediol dehydrogenation to ε-caprolactone: High activity and stability from core-shell nanostructure

Jiang Fengyang,Lan Tian,Sun Jiaqiang,Zhao Guofeng,Lu Yong

The gas-phase dehydrogenation of 1,6-hexanediol (1,6-HDO) to ε-caprolactone (ε-CL) over the high-performance Cu-based catalysts is highly desirable, but with grand challenges, because the Cu nanoparticles (NPs) are easy to be sintered with the low Hüttig temperature (< 150 °C vs. > 250 °C of reaction temperature). Herein, we report a highly efficient silica-encapsulated nano-Cu catalyst (Cu@SiO 2 /SiO 2 ) prepared via a complexation-impregnation method for the dehydrogenation of 1,6-HDO, exhibiting a 1,6-HDO conversion of 95.3% and ε-CL selectivity of 80.0% at 270 °C. The catalyst also has the outstanding thermal stability (without sintering up to 270 °C for 100 h on stream), which can be attributed to the effective encapsulation of the SiO 2 shell. In addition, the reaction network of 1,6-HDO dehydrogenation is proved. Finally, the pyridine-diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and in-situ X-ray photoelectron spectroscopy (XPS) reveal that the Cu 0 species favor the conversion of 1,6-HDO to ε-CL. The synergistic effect of Cu + and Cu 0 benefits the conversion of ε-CL to 2-methylcyclopentanone (2-MCPN). This study is beneficial for designing the high-performance Cu-based catalysts for 1,6-HDO to ε-CL, understanding the reaction network of 1,6-HDO dehydrogenation over the Cu-based catalysts, and offering a strong foundation for the large-scale production of ε-CL.

CAS / MDL: 919-30-2 7631-86-9
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