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CHINESE JOURNAL OF CHEMICAL ENGINEERING · 2021 · IF 3.171

High-efficiency and safe synthesis of tonalid via two Friedel-Crafts reactions in continuous-flow microreactors

Yang Han,Yuanyuan Liu,Shiwei Wang,Xuehui Ge,Xiaoda Wang,Ting Qiu

Tonalid, an important fragrance ingredient with widespread application, was synthesized via two Friedel-Crafts reactions, which were catalyzed by AlCl 3 . The traditional tonalid production was conducted in batch stirring tank reactors, suffering from low production capacity and the safety hazard of temperature runaway. To solve these problems, the continuous-flow technologies were developed for the high-efficiency and intrinsically safe synthesis of tonalid in microreactors. Catalyst AlCl 3 was neatly homogenized in proper solvents by forming complex with reactant, which was a necessary step for the continuous synthesis in microreactors. Several reaction conditions, including reactant molar ratio, catalyst concentration, temperature, and microchannel hydrodynamic diameter, were investigated for the two Friedel-Crafts reactions in microreactors. At optimized conditions, the yields of the two Friedel-Crafts reactions were 44.15% and 97.55%, respectively. In comparison with the batch reactors, the reaction times of these two reactions could both be reduced by nearly two thirds in microreactors at the similar yield.

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PESTICIDE BIOCHEMISTRY AND PHYSIOLOGY · 2019 · IF 2.87

One pot solvothermal synthesis of novel fluorescent phloem-mobile phenylpyrazole amide pesticides fused olefin moieties to enhance insecticidal bioactivities and photodegradation properties

Zhongda Wu,Yanting Du,Quan Zhou,Lianqing Chen

In order to find a novel type of fluorescent phloem-mobile insecticides, a facile one-pot solvothermal strategy via fipronil addition-elimination substitution reaction with the corresponding acyl chloride derivatives has been employed to construct series of phenylpyrazole amide derivatives ( PAs ) fused olefin moieties in high yields. The investigation for insecticidal bioactivities of PAs against 3rd instar larvae of Plutella xylostella exhibited better activities than that of fipronil , which can be elucidated by enhanced phloem mobility and calcium ions' coordination with amide N-C=O, C C double bonds and chloride ions, extended conjugate moieties and decreasing steric hindrance of the stereoscopic structure. The introduction of amide units conferred phloem mobility to PAs , which was evaluated by the hydrophobic parameters determined with reversed-phase HPLC through the chromatographic capacity factor. By introducing conjugate moieties and organic chromophore into phenylpyrazole parent structure to increase their conjugation degree and light absorption abilities, PAs exhibited good photodegradation properties. The relationships between extended conjugate moieties of parent structure, electronegativity of substituted groups and photodegradation properties have been discussed. The olefin units connected to PAs caused electronic absorption and fluorescent wavelengths bathochromic shifted. Under simulated solar irradiation, PAs can be reconverted into fipronil parent fragments by photodegradation, thereby enhancing their insecticidal activity. The fluorescent quantum yields of PAs were almost 4 times that of fipronil, which also laid a foundation for the natural degradation and fluorescence detection of insecticide residues.

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Polymers · 2019 ·Vol. 11 ·期 6 ·1033 · IF 3.164

Acetylated SEBS Enhanced DC Insulation Performances of Polyethylene

Wei Dong,Xuan Wang,Zaixing Jiang,Bo Tian,Yuguang Liu,Jiaming Yang,Wei Zhou

Acetophenone can significantly improve the dielectric properties of polyethylene (PE) insulation materials. However, it easily migrates from the PE due to its poor compatibility with the material, which limits its application. In this paper, the functional units of acetophenone were modified in polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) by an acetylation reaction, and SEBS was used as the carrier to inhibit the migration of acetophenone. The number of functional units in the acetylated SEBS (Ac-SEBS) was measured by1H NMR and the effect of the acetylation degree of SEBS on its compatibility with PE was studied. Meanwhile, the effects of Ac-SEBS on PE’s direct current (DC) breakdown strength and space charge accumulation characteristics were investigated. It is demonstrated that Ac-SEBS can significantly improve the field strength of the DC breakdown and inhibit the accumulation of space charge in the PE matrix. This work provides a new approach for the application of aromatic compounds as voltage stabilizers in DC insulation cable materials.Keywords:polyethylene;voltage stabilizer;insulation material;DC breakdown strength;space charge

CAS / MDL: 7446-70-0 75-36-5
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ANALYTICA CHIMICA ACTA · 2019 · IF 5.256

Quantification of phospholipid fatty acids by chemical isotope labeling coupled with atmospheric pressure gas chromatography quadrupole- time-of-flight mass spectrometry (APGC/Q-TOF MS)

Fangbo Xia,Ruibing Feng,Feng-Guo Xu,Huanxing Su,Chengwei He,Yuan-Jia Hu,Jian-Bo Wan

Phospholipid fatty acids play the crucial role in biophysical properties and the function of cellular membranes. In the present study, an accurate and sensitive method was developed to quantify phospholipid fatty acids in biological samples by using chemical isotope labeling coupled with atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry (APGC/Q-TOF MS). APGC, a soft ionization source, was operated under proton-transfer condition by introducing methanol into the ionization source as a modifier, which provided high quantifiable molecular ion peaks to substantially enhance the sensitivity. Fatty acid standards were methylated with methanol- d 4 to yield FAMEs- d 3 that were used as one-to-one internal standards to ensure accurate quantification. Thirty fatty acids in phospholipids were accurately quantified in wide linear range with limit of quantification ranging from 84.6 to 113.2 pg/mL. The newly developed method was successfully applied to quantify phospholipid fatty acids in brain and liver tissues from both fat-1 and WT mice. This method might be expanded to quantify free fatty acids or other conjugated fatty acids in biological samples or other matrices.

CAS / MDL: 75-36-5 497-19-8
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Frontiers in Oncology · 2019 · IF 4.137

Redox-Responsive Disulfide Bond-Bridged mPEG-PBLA Prodrug Micelles for Enhanced Paclitaxel Biosafety and Antitumor Efficacy

Chang Sheng,Wang Yanfei,Zhang Tianyi,Pu Xiaohui,Zong Lanlan,Zhu Heyun,Zhao Luling,Feng Bo

The toxicity and side effects of traditional chemotherapeutic drugs are the main causes of chemotherapy failure. To improve the specificity and selectivity of chemotherapeutic drugs for tumor cells, a novel redox-sensitive polymer prodrug, polyethylene glycol-poly (β-benzyl-L-aspartate) (PEG-PBLA)-SS-paclitaxel (PPSP), was designed and synthesized in this study. The PPSP micelle was manufactured via high-speed dispersion stirring and dialysis. The particle size and zeta potential of this prodrug micelle were 63.77 ± 0.91 nm and −25.8 ± 3.24 mV, respectively. The micelles were uniformly distributed and presented a spherical morphology under a transmission electron microscope. In the tumor physiological environment, the particle size of the PPSP micelles and the release rate of paclitaxel (PTX) were significantly increased compared with those of mPEG-PBLA-CC-PTX (PPCP) micelles, reflecting the excellent redox-sensitive activity of the PPSP micelles. The inhibitory effect of PPSP on HepG2, MCF-7 and HL-7702 cell proliferation was investigated with MTT assays, and the results demonstrated that PPSP is superior to PTX with respect to the inhibition of two tumor cell types at different experimental concentration. Simultaneously PPSP has lower toxicity against HL-7702 cells then PTX and PPCP. Moreover, the blank micelle from mPEG-PBLA showed no obvious toxicity to the two tumor cells at different experimental concentrations. In summary, the redox-sensitive PPSP micelle significantly improved the biosafety and the anti-tumor activity of PTX.

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Acta Biomaterialia · 2018 · IF 6.383

Rational design of multimodal therapeutic nanosystems for effective inhibition of tumor growth and metastasis

Feihu Wang,Qian Huang,Yun Wang,Wenjun Zhang,Ran Lin,Yanna Yu,Yuanyuan Shen,Honggang Cui,Shengrong Guo

Simultaneous inhibition of both tumor growth and metastasis is the key to treating metastatic cancer, yet the development of effective drug delivery systems represents a great challenge since multimodal therapeutic agents must be rationally combined to overcome the biological mechanisms underpinning tumor cell proliferation and invasion. In this context, we report a hybrid therapeutic nanoscale platform that incorporates an anti-proliferative drug, doxorubicin (DOX), and an anti-NF-κB agent, p65-shRNA, for effective treatment of metastatic breast cancer. In our design, we first conjugated DOX via an acid-labile linker onto gold nanorods that were pre-modified with the tumor targeting peptide RGD and a positively charged, disulfide cross-linked short polyethylenimines (DSPEI), and then incorporated shRNA through electrostatic complexation with DSPEI. We show that this “all in one” nanotherapeutic system (RDG/shRNA@DOX) can be effectively internalized through RGD-mediated endocytosis , followed by stimuli-responsive intracellular co-release of DOX and shRNA. Our in vitro experiments suggest that this multimodal system can significantly inhibit cell proliferation, angiogenesis , and invasion of metastatic MDA-MB-435 cancer cells. Systemic administration of RDG/shRNA@DOX into a metastatic mouse model led to enhanced tumor accumulation, and, most importantly, significant inhibition of in situ tumor growth and almost complete suppression of tumor metastasis. We believe this hybrid multimodal nanotherapeutic system provides important insight into the rational design of therapeutic systems for the effective treatment of metastatic carcinoma. Statement of Significance The key to successfully treat metastatic cancer is the simultaneous inhibition of both tumor growth and metastasis. This represents a great challenge for the design of drug delivery systems since multimodal therapeutic agents must be rationally combined to overcome the respective biological mechanisms underpinning tumor cell proliferation and invasion. Toward this end, we developed a hybrid nanomedicine platform that incorporates an anti-proliferative drug, doxorubicin (DOX), and an anti-NF-κB agent, p65-shRNA, for effective treatment of metastatic breast cancer. We showed that this multimodal system (RDG/shRNA@DOX) enhanced tumor accumulation, led to prolonged circulation, and most importantly, significant inhibition of in situ tumor growth and almost complete suppression of tumor metastasis. We believe this hybrid multimodal nanotherapeutic system provides significant insight into the rational design of therapeutic systems for the effective treatment of metastatic cancer.

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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2018 · IF 3.141

Scalable Preparation of Micro-Meso-Macroporous Polymeric Solid Acids Spheres From Controllable Sulfonation of Commercial XAD-4 Resin

Weiping Kong,Yong Liu,Fujian Liu

Efficient micro-meso-macroporous solid acids spheres with controllable acid strength were successfully synthesized by simultaneous grafting of −SO3H and −SO2CF3 onto the network of commercial XAD-4 resin. The synthesized solid acids are designated as XAD-4-SO3H and XAD-4-SO3H-SO2CF3. Various characterizations show that XAD-4-SO3H and XAD-4-SO3H-SO2CF3 possess high BET surface areas, hierarchical porous structures with combined micro-meso-macropores, high concentrations of acid sites, and strong acid strength. Catalytic tests show that XAD-4-SO3H and XAD-4-SO3H-SO2CF3 exhibit superior activities and good reusability in various acid-catalyzed reactions including esterification of acetic acid with cyclohexanol, acylation of anisole with acetyl chloride, and catalytic synthesis of bisphenol A. Their activities were better than the solid acids of Amberlyst-15, SBA-15-SO3H-0.1, H3PW12O40, and acidic zeolites. This work develops a new method for scalable transformation of commercially macroporous resin into efficient porous solid acids, which promotes their wide use in industrial catalysis.

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SENSORS AND ACTUATORS B-CHEMICAL · 2014 · IF 3.84

Aggregation-enhanced excimer emission (AEEE) based on pyrenylchalcone and 2-to-4 molecular decoder by biothiols and polyanions in aqueous media

Dingyi Tong,Haifeng Duan,Jiajun Wang,Ziqi Yang,Yingjie Lin

An aggregation-enhanced excimer emission (AEEE) fluorophore was successfully synthesized by introducing chalcone into pyrene. Compared with the traditional AIE structure (tetra-phenylethene derivatives), pyrenylchalcone was more available under mild conditions. It exhibited weak emission when molecularly dissolved but strong excimer emission when aggregated. Then we designed a probe with good water solubility based on pyrenylchalcone for polyanion detection in aqueous media. An orange emission could be observed upon simple addition of polyacrylic acid sodium salt. Better than the other “blue-to-green” pyrene probes, this “turn-on” AEEE probe was more likely visible to eyes. Moreover, unlike the double bond in tetra-phenylethene, the unsaturated double bond in chalcone could be easily opened by thiols. It could lead to another different “turn-on” change in fluorescence. Adding biothiol and adding polyanion were two different methods to reduce the intra-molecular rotations and cause different emissions, thus we built a 2-to-4 molecular decoder in aqueous media which could be observed by naked eyes.

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RSC Advances · 2013 ·Vol. 4 ·期 2 ·554-562 · IF 2.562

Synthesis, structure, photo- and electro-luminescence of an iridium(III) complex with a novel carbazole functionalized β-diketone ligand

Tianzhi Yu,Yan Cao,Wenming Su,Chengcheng Zhang,Yuling Zhao,Duowang Fan,Mingjun Huang,Kan Yue,Stephen Z. D. Cheng

A new iridium complex containing coumarin derivative as a cyclometalated ligand (1L) and a carbazole-functionalized β-diketonate (2L) as the ancillary ligand, namely, Ir(III)bis(3-(pyridin-2-yl)coumarinato-N,C4)(1-(9-butyl-9H-carbazol-3-yl)-4,4,4-trifluoro-butane-1,3-dionato-O,O) (Ir(1L)2(2L)), was synthesized. The crystal structure of Ir(1L)2(2L) was determined via combined wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM), which showed π–π the interactions of Ir(1L)2(2L) molecules stacking along the crystal axes. The doped light-emitting diodes using this novel Ir(1L)2(2L) complex as the phosphorescent dopant were fabricated. At a Ir(1L)2(2L) concentration of 6.0 wt%, a green-yellow emitting OLED was achieved with a maximum external quantum efficiency (EQE) of 6.11% and a maximum luminous efficiency of 22.55 cd A−1 at the current density of 6.06 mA cm−2, and a maximum luminance of 6653 cd m−2 at 10.7 V. Furthermore, two reference complexes Ir(1L)2(acac) and Ir(1L)2(TTA) were also used as emitters to fabricate OLED devices with the same device configuration. The maximum luminous efficiency of Ir(1L)2(acac) doped device was measured to be 20.04 cd A−1 at 2.15 mA cm−2 (10.0 wt%), while the doped device of Ir(1L)2(TTA) had a maximum luminous efficiency of 16.59 cd A−1 at 1.36 mA cm−2. The better performances of Ir(1L)2(2L) doped devices could be largely attributed to an improved hole-transporting property due to the introduction of the carbazole moiety.

CAS / MDL: 75-36-5 383-63-1
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CELLULOSE · 2014 ·Vol. 21 ·期 4 ·2369-2378 · IF 3.033

Synthesis, characterization and properties of novel cellulose derivatives containing phosphorus: cellulose diphenyl phosphate and its mixed esters

Xiao Peng,Zhang Jinming,Feng Ye,Wu Jin,He Jiasong,Zhang Jun

Using ionic liquid 1-allyl-3-methylimidazolium chloride as reaction medium, a series of novel cellulose esters containing phosphorus including cellulose diphenyl phosphate (C-Dp) and cellulose acetate (CA)–diphenyl phosphate mixed esters was synthesized homogeneously. The degree of substitution was well controlled by altering reaction conditions, such as the molar ratio of the acylating reagents/anhydroglucose unit and reaction time. The structure and thermal properties of cellulose esters were characterized by FTIR, NMR, wide-angle X-ray powder diffraction and differential scanning calorimetry. All the products possessed excellent solubility in some common organic solvents, and transparent films of cellulose esters were obtained by solution casting. In contrast to C-Dp, CA–diphenyl phosphate mixed esters showed clear glass transitions. More interestingly, these cellulose mixed esters exhibited thermoplastic behavior and could be processed by traditional melt processing methods.

CAS / MDL: 75-36-5
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Advanced Healthcare Materials · 2017 ·Vol. 6 ·期 24 ·1700829 · IF 5.11

Rational Design of a New Self-Codelivery System from Redox-Sensitive Camptothecin–Cytarabine Conjugate Assembly for Effectively Synergistic Anticancer Therapy

Wenxiu He,Xu Hu,Wei Jiang,Ruiling Liu,Di Zhang,Jing Zhang,Zhonghao Li,Yuxia Luan

Herein, two careful selected anticancer drugs camptothecin (CPT) and cytarabine (Ara-C) with different biological action mechanisms and different water solubility are conjugated together through a glutathione (GSH) cleavable disulfide bond to construct a redox-sensitive drug–drug conjugate, which can self-assemble into nanoparticles, thus notably improving the water solubility of CPT and the cell membrane permeability of Ara-C. Compared with free drugs, the self-assembled CPT-ss-Ara nanoparticles can concentrate in tumor tissues through the enhanced permeability and retention (EPR) effect, then they can be rapidly internalized by tumor cells and degrade into free drugs for killing the tumor cells when exposed to the reductive environment (GSH) of tumor cells, thereby reducing the injury to normal cells. Meanwhile, the CPT-ss-Ara nanoparticles can effectively protect CPT and Ara-C molecules from biological inactivation before their arrival in tumor microenvironment since free CPT and Ara-C are easy to partly lose their therapy efficacy due to their structure degradation in blood circulation. The in vitro and in vivo anticancer experimental results indicate that simultaneous release of free CPT and Ara-C can realize synergistic chemotherapy effects, thus markedly improve their anticancer activity. Therefore, our designed carrier-free, redox-sensitive CPT-ss-Ara nanoparticles might have promising clinical application to combat cancers.

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BIOMEDICAL CHROMATOGRAPHY · 2016 ·Vol. 30 ·期 11 ·1796-1806 · IF 1.729

Simultaneous determination of thirteen kinds of amino acid and eight kinds of acylcarnitine in human serum by LC–MS/MS and its application to measure the serum concentration of lung cancer patients

Junjun Ni,Li Xu,Wei Li,Lijun Wu

Easy-to-use early cancer detection methods based on metabolomics using serum samples have been developed recently. Among metabolites, amino acids and acylcarnitine are two of the most suitable candidates for diagnosing lung cancer. The purpose of the present study was to develop a novel, sensitive and specific liquid chromatography–tandem mass spectrometry (LC–MS/MS) method to simultaneously determine 13 amino acids and 8 acylcarnitines in lung cancer patients in serum. After derivatization, the 21 analytes were separated using a C 18 column with gradient elution program in 14 min, obtaining recovery within 90.4–113.8% and precision within 0.3–14.8%. The method was successfully applied in concentration determination of lung cancer patients and healthy controls. The results showed that the serum concentration of lung cancer patients were significant from those of healthy controls.

CAS / MDL: 75-36-5 71-36-3 123-86-4
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