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FUEL · 2022 · IF 8.035

Efficient 5-hydroxymethylfurfural synthesis from carbohydrates and food wastes in aqueous-natural deep eutectic solvent (A-NADES) with robust Al2O3 or Al(OH)3

Miao Zuo,Xinyu Wang,Wenlong Jia,Yanzhong Zhu,Xianhai Zeng,Lu Lin

As one of the essential building blocks for bio-chemicals and bio-fuels, the 5-Hydroxymethylfurfural (HMF) production is still challenging in a green and cheap way. This work developed a bio-derived aqueous-natural deep eutectic solvent (A-NADES) to synthesize HMF using α-Al 2 O 3 or Al(OH) 3 as robust catalysts, obtaining high yields of 67.1% and 63.6% HMF from glucose under mild reaction reactions, respectively. Different kinds of starches and starchy food waste also exhibited high conversion efficiency in the A-NADES system. The mechanistic study indicated that the in-situ formed Al (III) site of α-Al 2 O 3 during the reaction was critical for converting glucose-based carbohydrates. A-NADES could be effectively reused six times with a more convenient direct reuse method without significant activity loss. This study suggested a novel A-NADES reaction media in the synergistic reaction with robust aluminum-based catalysts for HMF synthesis, and proposed a novel process of food waste utilization in green solvents.

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MOLECULES · 2022 ·Vol. 27 ·期 13 ·4019 · IF 4.927

Ultrasensitive and Specific Detection of Anticancer Drug 5-Fluorouracil in Blood Samples by a Surface-Enhanced Raman Scattering (SERS)-Based Lateral Flow Immunochromatographic Assay

Hanwen Liu,Ying Liu,Ting Zhou,Penghui Zhou,Jianguo Li,Anping Deng

5-Fluorouracil (5-FU) is an effective anticancer drug widely used in the world. To improve therapy efficiency and reduce side effects, it is very important to frequently detect the concentration of 5-FU in blood samples of patients. In this work, a new type of lateral flow immunochromatographic assay (LFIA) based on surface-enhanced Raman scattering (SERS) for ultrasensitive and specific detection of 5-FU in blood samples was developed. Au@Ag/Au nanoparticles (NPs) employing Au particles as the core and Ag/Au alloy as the shell were synthesized, characterized and used as the substrate in SERS-LFIA due to their high SERS enhancement and biocompatibility. The immunoprobe was made in the form of AuMBA@Ag/Au-Ab in which mercaptobenzoic acid (MBA, a common Raman active reporter) was embedded in the core–shell layer and the monoclonal antibody (mAb) against 5-FU was immobilized on the surface. The performance of SERS-LFIA was similar to that in colloidal gold based-LFIA, and the entire assay time was within 20 min. According to the color intensity on the testing (T) lines of LFIA strips visualized by eyes, the contents of 5-FU in the samples could be qualitatively or semi-quantitatively identified. Furthermore, by measuring the characteristic Raman intensities of MBA on T lines, quantitative detection of 5-FU in the samples were achieved. The IC50and limit of detection (LOD) of the LFIA for 5-FU were found to be 20.9 pg mL−1and 4.4 pg mL−1, respectively. There was no cross-reactivity (CR) of the LFIA with nine relative compounds, and the CR with cytosine, tegafur and carmofur were less than 4.5%. The recoveries of 5-FU from spiked blood samples were in the range of 78.6~86.4% with the relative standard deviation (RSD) of 2.69~4.42%. Five blood samples containing 5-FU collected from the Cancer Hospital were measured by SERS-LFIA, and the results were confirmed by LC-MS/MS. It was proven that the proposed method was able to simply and rapidly detect 5-FU in blood samples with high sensitivity, specificity, accuracy and precision.Keywords:surface-enhanced Raman scattering (SERS);lateral flow immunochromatographic assay (LFIA);5-fluorouracil (5-FU);anticancer drug;blood samples

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ACS ES&T Engineering · 2022 · IF 0

Insight into the Role of Cerium in the Enhanced Performances during Catalytic Combustion of Acetonitrile over Core–Shell-like Cu–Ce/ZSM-5 Catalysts

Yaoyu Zhang,Yuxiong Wang,Yue Liu,Huimin Xu,Qingji Ying,Zhongbiao Wu

Cerium-modified Cu/ZSM-5 catalysts were employed for the selective catalytic combustion of acetonitrile. It was obtained that cerium addition effectively improved the mineralization rate of acetonitrile and nitrogen selectivity as well. The optimal Cu5Ce8/ZSM-5 sample exhibited 100% mineralization rate and higher than 95% nitrogen selectivity within 325–500 °C. The strong interaction between Cu and Ce species was induced in a core–shell-like structure of Cu–Ce/ZSM-5 samples, where the Cu–Ce/ZSM-5 core was wrapped with a Cu–Ce mixed oxide layer. The external mixed oxides exhibited enhanced reducibility and increased active oxygen species. In situ diffuse reflectance infrared Fourier transform spectroscopy and density functional theory simulations revealed that surface cerium species strengthened the hydrolysis reaction path of acetonitrile as ceria could effectively promote the dissociation of water and the hydrolysis of cyano groups, thereby generating a sufficient amount of NHx species. As a result, the NOx from acetonitrile overoxidation would be eliminated through internal selectivity catalytic reduction over the Cu–Ce/ZSM-5 core.

CAS / MDL: 10294-41-4 10031-43-3
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Nanomaterials · 2022 ·Vol. 12 ·期 4 ·696 · IF 5.719

Affibody Modified G-quadruplex DNA Micelles Incorporating Polymeric 5-Fluorodeoxyuridine for Targeted Delivery of Curcumin to Enhance Synergetic Therapy of HER2 Positive Gastric Cancer

Chao Zhang,Shuangqing Fu,Fanghua Zhang,Mengnan Han,Xuming Wang,Jie Du,Honglei Zhang,Wei Li

Combination chemotherapy is emerging as an important strategy for cancer treatment with decreased side effects. However, chemotherapeutic drugs with different solubility are not easy to realize co-delivery in traditional nanocarriers. Herein, an affibody modified G-quadruplex DNA micellar prodrug (affi-F/GQs) of hydrophilic 5-fluorodeoxyuridine (FUdR) by integrating polymeric FUdRs into DNA strands is developed for the first time. To achieve synergistic efficacy with hydrophobic drugs, curcumin (Cur) is co-loaded into affi-F/GQs micelles to prepare the dual drug-loaded DNA micelles ([email protected]/GQs), in which affibody is employed as a targeting moiety to facilitate HER2 receptor-mediated uptake.[email protected]/GQs have a small size of approximately 130 nm and exhibit excellent stability. The system co-delivers FUdR and Cur in a ratiometric manner, and the drug loading rates are 21.1% and 5.6%, respectively. Compared with the physical combination of FUdR and Cur,[email protected]/GQs show higher cytotoxicity and greater synergistic effect on HER2 positive gastric cancer N87 cells. Surprisingly,[email protected]/GQs significantly enhance the expression and activity of apoptosis-associated proteins in Bcl-2/Bax-caspase 8, 9-caspase 3 apoptotic pathway, which is the main factor in the death of tumor cells induced by FUdR. Overall, this nanoencapsulation is a promising candidate for the targeted co-delivery of drugs with significant differences in solubility.Keywords:G-quadruplex;DNA micelles;affibody;5-fluorodeoxyuridine;curcumin;synergetic therapy

CAS / MDL: 458-37-7 129-00-0
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CHINESE JOURNAL OF CHEMICAL ENGINEERING · 2021 · IF 3.171

Fabricating amide functional group modified hyper-cross-linked adsorption resin with enhanced adsorption and recognition performance for 5-hydroxymethylfurfural adsorption via simple one-step

Lei Hu,Shunhui Tao,Junting Xian,Xiaodong Zhang,Yao Liu,Xiaojie Zheng,Xiaoqing Lin

In this study, three kinds of amide functional group modified hyper-cross-linked adsorption resin were synthesized by alternating radical copolymerization in simple one-step and applied for 5-hydroxymethylfurfural (5-HMF) adsorption. The successful synthesis and properties of adsorbents were evaluated with Fourier transform infrared spectroscopy, scanning electron microscopy, nitrogen adsorption–desorption isotherms, thermogravimetric analysis, and elemental analysis. Poly ( N , N ′-4,4′-diphenylmethane-bismaleimide-alt-divinylbenzene) (poly (BDM-alt-DVB)) resin exhibited highest adsorption capacity for 5-HMF (64.0 mg·g −1 wet resin) and excellent adsorption selectivity ( α 5-HMF/LA  = 2.71 ± 0.12, α 5-HMF/FA  = 13.88 ± 0.15, α 5-HMF/Glucose  = 11.91 ± 1.11) in the multi-component solution at 25 °C. Langmuir isotherm model well fitted the equilibrium adsorption data within the initial 5-HMF concentration range of 0.5–10.0 g·L −1 with highest correlation coefficient. Furthermore, the thermodynamic parameters demonstrated that the adsorption of 5-HMF onto poly (BDM-alt-DVB) resin was spontaneous and exothermic. Kinetic study revealed that the adsorption process was fast, reaching equilibrium within 12 min. Importantly, the poly (BDM-alt-DVB) resin also demonstrated excellent reusability. In summary, the poly (BDM-alt-DVB) resin will be useful in 5-HMF hydrolysate separation applications.

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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Azo-based hypoxic-activated 6-diazo-5-oxo-L-norleucine (DON) prodrug combined with vascular disrupting agent nanoparticles for tumor-selective glutamine metabolism blockade

Hang Xu,Mengfei Zheng,Chenguang Yang,Kun Wang,Zheng Lv,Zhilin Liu,Zhaohui Tang,Xuesi Chen

Glutamine antagonists, such as 6-diazo-5-oxo-L-norleucine (DON), have demonstrated remarkable anti-tumor effects by blocking tumor glutamine metabolism, but their use is frequently causing toxicity. Despite the existence of multiple glutamine antagonist prodrug designs, a tumor-selective prodrug has yet to be developed. Herein, a novel prodrug of DON, Azo-DON, has been developed, which remains stable and inactive in normal tissues with sufficient oxygen levels, while can be selectively reduced to DON by highly expressed azo-reductase in hypoxic tumor environments. This leads to blockade of glutamine metabolism in cancer cells and promotes cell death without affecting T cell proliferation. In a high-hypoxic H22 hepatoma cancer model, Azo-DON showed a 1.8-fold enhancement in glutamine blockade compared to the control group, resulting in a tumor suppression rate (TSR) of 84.2% in vivo with no significant weight loss. In a low-hypoxic CT26 colon cancer model, when combined with vascular disrupting agent nanoparticles (CBP) to induce a hypoxic environment, Azo-DON exhibited a 4.6-fold enhancement in glutamine blockade over the control group, resulted in a remarkable TSR of 96.6% in vivo . This innovative approach represents a promising strategy for the application of broad-spectrum metabolic inhibitors in the field of precision cancer treatment.

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EUROPEAN JOURNAL OF MEDICINAL CHEMISTRY · 2022 · IF 7.088

Discovery of N-(3-bromo-1H-indol-5-yl)-quinazolin-4-amine as an effective molecular skeleton to develop reversible/irreversible pan-HER inhibitors

Qidong Tang,Ting Peng,Jie Hu,Tao Zhang,Pengqin Chen,Daoxing Chen,Yunjie Wang,Lingfeng Chen,Linjiang Tong,Yi Chen,Hua Xie,Guang Liang

Pan-HER inhibitors exhibit extensive biological activity and offer unique advantages and usually bind to targets in an irreversible manner. Owing to the off-target toxicity of irreversible inhibitors, reversible pan-HER inhibitors are desirable. Herein, we describe the process of N -(ring structure fused phenyl)quinazoline-4-amine-based design, synthesis, and biological evaluation of pan-HER inhibitors in vitro and in vivo . Compound C5 , with the molecular skeleton of N -(3-bromo-1 H -indol-5-yl)-quinazolin-4-amine, displayed irreversible binding just like other effective pan-HER inhibitors. To our surprise, compound C6, which possessed the same skeleton, was found to be a high-strength reversible pan-HER inhibitor. This compound was capable of inhibiting HER1s (such as EGFR T790M/L858R and WT), HER2, and HER4 and can be considered as a breakthrough in the development of pan-HER inhibitors. Altogether, N -(3-bromo-1 H -indol-5-yl)-quinazolin-4-amine can serve as an effective molecular skeleton for developing both reversible and irreversible pan-HER inhibitors in the following discovery of antitumor drugs .

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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2023 · IF 8.2

Folic acid-coupled bovine serum albumin-modified magnetic nanocomposites from quantum-sized Fe3O4 and layered double hydroxide for actively targeted delivery of 5-fluorouracil

Zhaoyun Liu,Xi Wang,Chen Zhang,Kui Lin,Jian Yang,Yi Zhang,Jia Hao,Fei Tian

The development of multifunctional magnetic nanocomposites as a drug delivery system for cancer therapy is highly desirable in current nanomedicine. Herein, folic acid-bovine serum albumin conjugate (FA-BSA) was modified on nanocomposites by combining quantum-sized Fe 3 O 4 and layered double hydroxide (LDH) to obtain a novel FA-BSA/Fe 3 O 4 @LDH for the delivery of the anticancer drug 5-Fluorouracil (5-Fu). The prepared nanocomposites showed good dispersibility, colloidal stability, magnetic property and erythrocyte compatibility. FA-BSA/Fe 3 O 4 @LDH/5-Fu showed pH responsiveness, with both the amount and duration of release of FA-BSA/Fe 3 O 4 @LDH/5-Fu being significantly higher in pH 5.0 release medium than in pH 7.4 release medium. The cellular experiments implied that no significant cytotoxicity of FA-BSA/Fe 3 O 4 @LDH, particularly due to the presence of FA-BSA, which further enhanced the biocompatibility of the nanocomposite. Furthermore, FA-BSA/Fe 3 O 4 @LDH/5-Fu could specifically target the 2D HepG2 cells model and 3D hepatoma cell microspheres model in vitro , and efficient internalization through folate receptor-mediated endocytosis , showing excellent anti-cancer cell activity in a concentration-dependent manner. Therefore, the constructed FA-BSA/Fe 3 O 4 @LDH was able to provide a potential novel multifunctional nanocomposite for magnetic-targeting drug delivery and pH-responsive release of drugs to enhance the efficiency of cancer therapy.

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ChemCatChem · 2021 ·Vol. 13 ·期 8 ·2074-2085 · IF 5.686

Direct Amination of Biomass-based Furfuryl Alcohol and 5-(Aminomethyl)-2-furanmethanol with NH3 over Hydrotalcite-derived Nickel Catalysts via the Hydrogen-borrowing Strategy

Kuo Zhou,Ruihong Xie,Meiting Xiao,Darun Guo,Zhuodi Cai,Shimin Kang,Yongjun Xu,Jinjia Wei

Graphical Hydrogen borrowing : An efficient NiAl hydrotalcite-derived nickel catalyst has been developed for the direct amination of biomass-based furfuryl alcohol and 5-(aminomethyl)-2-furanmethanol with NH 3 via the “hydrogen borrowing” strategy. The synergistic catalysis of Ni 0 and Al δ+ -Al-O δ− site was of vital importance for the amination of alcohols into corresponding primary amines. A series of hydrotalcite-derived nickel catalysts were synthesized and employed for the direct amination of biomass-based furfuryl alcohol with NH 3 via the hydrogen borrowing strategy. The effects of the Ni/Al molar ratio and calcination temperature of the NiAl hydrotalcite-like precursors on the performance of the Ni x Al-CT catalyst were investigated. The systematic characterization showed that the synergistic catalysis of the metal and acid-base sites was of vital importance for the amination of alcohols. In particular, the Ni 2 Al-600 catalyst with high amount of Ni 0 sites (1.26 mmol g −1 ) and suitable density of acid-base sites (0.71 mmol g −1 and 1.10 mmol g −1 , respectively) exhibited the best dehydrogenation capability and therefore excellent catalytic activity. An 84.1 % yield of furfurylamine with complete conversion of furfuryl alcohol was obtained under the reaction conditions of 180 °C and 0.4 MPa NH 3 in 36 h. The presence of Ni 3 N in the spent catalyst, confirmed by XRD, TEM and XPS characterizations, was demonstrated to be responsible for the deactivation of the Ni x Al-CT catalyst. In addition, the Ni 2 Al-600 catalyst exhibited satisfactory performance toward another important biomass-related transformation of 5-(aminomethyl)-2-furanmethanol to 2,5-bis(aminomethyl)furan, with a yield of 70.5 %.

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ACS Applied Materials & Interfaces · 2021 · IF 9.229

Racing Crystallization Mechanism for Economical Design of Single-Crystal Hollow ZSM-5 with the Broken Limit of Si/Al Ratio and Improved Mass Transfer

Yi Zhai,Xubin Zhang,Fumin Wang,Guojun Lv,Tao Jiang,Yuzhou Wu,Mengyue Li,Mengyao Li,Qing Zhang,Yongkui Liu

Development of economic strategy to synthesize hollow zeolite with widely tunable Si/Al ratios providing variable acidity is of great significance in industry. Here, a one-step and low-cost strategy without mesoporogen was successfully developed to synthesize single-crystal hollow ZSM-5 containing mesopores/macropores, with variable Si/Al ratios of about 14–∞ and 114–∞ at critical TPA+/SiO2 ratios of 0.05–0.1 and 0.05, respectively. This is the first time the usage of a large amount of TPAOH was avoided while breaking the traditional limitation of Si/Al ratio (25–50). The component of synthesis system and crystallization temperature acting as the vital roles in hollow structure has been confirmed by a series of characterization. Moreover, according to the investigation of the evolution process, a novel racing crystallization mechanism based on the competition relationship between surface crystallization and the internal dissolution rate was proposed for the first time. The racing crystallization mechanism and internal nonprotective aluminum become the crucial factors for synthesis. The prepared hollow ZSM-5 zeolites exhibit superior catalytic performance in the different acidity-catalyzed condensation involving large molecules between benzaldehyde and n-butyl alcohol as well as 2-hydroxyacetophenone, which is mainly attributed to the property acidity, more accessible active Al sites on the surface, and shorter diffusion path. By calculating, the effectiveness factor (η) of hollow zeolite is close to 1, further confirming its better mass transfer ability. The strategy has also been successfully extended to the synthesis of high-amount Fe-doped, Ga-doped, and B-doped hollow silicate-1.

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Biomaterials Science · 2021 ·Vol. 9 ·期 6 ·2279-2294 · IF 6.843

Cetuximab functionalization strategy for combining active targeting and antimigration capacities of a hybrid composite nanoplatform applied to deliver 5-fluorouracil: toward colorectal cancer treatment

Ranran Chen,Yuanjian Huang,Lu Wang,Jiahui Zhou,Yuqian Tan,Chaofan Peng,Peng Yang,Wen Peng,Jie Li,Qiou Gu,Yuchen Sheng,Yan Wang,Guoqiang Shao,Qing Zhang,Yueming Sun

Antibody-functionalized targeted nanocarriers to deliver chemotherapeutics have been widely explored. However, it remains highly desirable to understand and apply the antitumor potential of antibodies integrated in hybrid composite nanoplatforms. Herein, mesoporous silica nanoparticles, a supported lipid bilayer and cetuximab were integrated to fabricate a hybrid nanoplatform for effectively encapsulating and selectively delivering 5-fluorouracil (5-FU) against colorectal cancer (CRC) cells. The specially designed nanoplatform exhibited superior properties, such as satisfying size distribution, dispersity and stability, drug encapsulation, controlled release, and cellular uptake. Interestingly, the modification of cetuximab onto nanoplatforms without drug loading can significantly inhibit the migration and invasion of CRC cells through suppressing the epidermal growth factor receptor (EGFR)-associated signaling pathway. Furthermore, delivery of 5-FU by using this nanoplatform can remarkably induce cytotoxicity, cell cycle arrest, and cell apoptosis for CRC cells with high EGFR expression. Overall, this nanostructured platform can dramatically improve the tumor killing effects of encapsulated chemotherapeutics and present antimigration effects derived from the antibody modified on it. Moreover, in vivo biodistribution experiments demonstrated the superior tumor targeting ability of the targeted nanoparticles. Thus, this targeted nanoplatform has substantial potential in combinational therapy of antibodies and chemotherapy agents against colorectal cancer.

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ENERGY & FUELS · 2020 · IF 3.421

One-Pot Synthesis of the Biofuel 5-Ethoxymethylfurfural from Carbohydrates Using a Bifunctional Catalyst Prepared through a Pickering HIPE Template and Pore-Filled Strategy

Yao Chen,Wen Guan,Yunlei Zhang,Changhao Yan,Bing Li,Yanan Wei,Jianming Pan,Yongsheng Yan

As a very promising biofuel or fuel additive, the synthesis of 5-ethoxymethylfurfural (EMF) directly from renewable carbohydrates is an important biomass transformation process. Herein, a novel bifunctional catalyst has been successfully synthesized via a Pickering high internal phase emulsion (HIPE) template and pore-filled strategy and employed for the production of EMF from glucose in a one-pot manner. Catalytic results indicated that the grafted Cr3+ by the atom transfer radical polymerization (ATRP) method smoothly processed the isomerization of glucose to intermediate fructose and that the accessible −SO3H and Cr3+ active sites coexisted in the obtained bifunctional catalyst possessing synergistic effects. A high EMF yield of 48.1% was achieved under optimal reaction conditions in an ethanol/tetrahydrofuran (THF) medium. Besides, employing inulin, sucrose, cellobiose, maltose, and starch as the starting materials excellent EMF yields were also obtained over the developed bifunctional catalyst. This study offers new insights into the design of functional catalysts anchoring desirable active sites, and also highlights their applications for biomass transformation.

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