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ChemCatChem · 2021 ·Vol. 14 ·期 6 ·e202101539 · IF 5.686

Bandgap Engineering for Photocatalytic Polymerization of 3, 4-Ethylenedioxythiophene (EDOT) over Cs3BixSb(2-x)Br9 Inverse Opals

Siwei Zhao,Shaohua Jin,Huanmin Liu,Youxin Su,Wei Liu,Shengfu Li,Chongchong She,Haonan Li,Kun Chen

Graphical A series of all-inorganic lead-free halide perovskite inverse opals were prepared and furtherly used as the photocatalysts to promote the polymerization of EDOT under the irradiation of visible light. All the samples exhibited the nice replica of the artificial template and high crystallinity. The bandgap of the catalysts was adjusted by screening the ratios of bromide to iodide and antinomy to bismuth. Cs 3 Bi 0.5 Sb 1.5 Br 9 showed the highest performance of the photocatalytic polymerization for EDOT, indicating the dual halide perovskites are more flexible than single halide perovskite in terms of bandgap engineering. A series of all-inorganic lead-free halide perovskite inverse opals were prepared and furtherly used as the photocatalysts to promote the polymerization of 3, 4-ethylenedioxythiophene (EDOT) under the irradiation of visible light. All the samples exhibited the nice replica of the artificial template and high crystallinity. The bandgap of the catalysts was adjusted by screening the ratios of bromide to iodide and antinomy to bismuth, respectively. Among all the samples, Cs 3 Bi 0.5 Sb 1.5 Br 9 inverse opal showed the best catalytic performance and the excellent stability in terms of the morphology and the crystalline phase after four cycles of photocatalytic polymerization. Since EDOT is commercially available, the present observation suggested a convenient protocol of preparing the composited materials or optoelectronic devices based on the lead-free halide perovskites and the conductive poly(3, 4-ethylenedioxythiophene).

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JOURNAL OF CHEMICAL THERMODYNAMICS · 2016 · IF 2.196

Solid-liquid equilibrium and phase diagram for the ternary (2-naphthaldehyde + o-phthalic anhydride + 1,4-dioxane) system

Yi Yu,Fang Zhang,Xiaoqiang Gao,Li Xu,Guoji Liu

In this research, solid-liquid equilibrium for the ternary system (2-naphthaldehyde   +   o -phthalic anhydride   +   1,4-dioxane) was measured at 283.15   K, 293.15   K and 303.15   K, respectively. Three isothermal phase diagrams of the system were plotted using the values of the experimental solubility. Pure 2-naphthaldehyde and o -phthalic anhydride were formed at (283.15, 293.15 and 303.15)   K, and were determined by Schreinemaker’s wet residue method. The crystallization region of o -phthalic anhydride was found to be much larger than that of 2-naphthaldehyde at a certain temperature. The experimental solubility at multiple temperatures was correlated by the NRTL and Wilson models. The NRTL model was more accurate than the Wilson model in this system. The diagram of density versus component was also constructed.

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Journal of Energy Storage · 2022 · IF 8.907

Mg(NO3)2·6H2O-LiNO3 eutectic/expanded graphite composite phase change material for thermal energy storage applications

Hui Wang,Enda Ci,Xiaoqing Li,Ying Zhang,Zhenying Zhang,Jianqiang Li

A new eutectic mixture phase change material containing magnesium nitrate hexahydrate and lithium nitrate has been successfully prepared, which can be applied in the field of residential radiator heating due to the suitable phase change temperature and high latent heat. Further, by physical blending magnesium nitrate hexahydrate/lithium nitrate eutectic mixtures and expanded graphite, the new composites were prepared. The crystalline structure, thermal properties, corrosion performance of eutectic phase change materials were systematically measured. The results showed that the best eutectic mixtures had a phase change temperature of 72.35 °C and latent heat of 170.32 kJ/kg, with a little supercooling degree. The thermal conductivity was effectively improved by adding expanded graphite. Meanwhile, corrosion tests suggested aluminum and stainless steel 304 could be the preferred choices as the container. Overall, the prepared eutectic composite materials with superior performances could be a promising candidate for the residential radiator heating field.

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SENSORS AND ACTUATORS B-CHEMICAL · 2021 · IF 7.46

Layered perovskite oxides Lan+1NinO3n+1 (n = 1, 2, and 3) for detecting ammonia under high temperature

Yuehua Li,Shaoxian Li,Weiwei Meng,Lei Dai,Ling Wang

A series of impedancemetric sensors for ammonia detection were fabricated using yttrium stabilized zirconia (YSZ) electrolyte and La n+1 Ni n O 3n+1 (n = 1, 2, and 3) sensing electrodes. The sensing materials with layered perovskite structure were prepared using in-situ impregnation method and well-dispersed in YSZ porous skeleton after calcination at 900 °C. The sensing performances of the sensors with La n+1 Ni n O 3n+1 sensing electrodes were investigated using the impedancemetric modulus |Z| and phase angle Θ as response signals, respectively. The results show that the sensor with La 2 NiO 4+ δ sensing electrode exhibits the higher response values and sensitivity compared to the sensor using La 3 Ni 2 O 7- δ or La 4 Ni 3 O 10- δ sensing electrodes, which is attributed to the largest NH 3 adsorption capacity of La 2 NiO 4+ δ . The response signals |Z| or Θ of the La 2 NiO 4+ δ based sensor linearly depend on NH 3 concentrations. The sensor hardly is insensitive to co-existing gases such as CO 2 , CH 4 , H 2 and relative humidity, but NO or NO 2 causes a positive error.

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BIOMACROMOLECULES · 2022 · IF 6.978

Synthesis and Post-Functionalization of Poly(conjugated ester)s Based on 3-Methylene-1,5-dioxepan-2-one

Zhaoyue Li,Yilin Qian,Yihuan Lai,Fu-Sheng Du,Zi-Chen Li

Poly(α-methylene ester)s are an attractive type of functional aliphatic polyesters that represent a platform for the fabrication of various biodegradable and biomedical polymers. Herein, we report the controlled ring-opening polymerization (ROP) of a seven-membered α-methylene lactone (3-methylene-1,5-dioxepan-2-one, MDXO) that was synthesized based on the Baylis–Hillman reaction. The chemoselective ROP of MDXO was catalyzed by diphenyl phosphate (DPP) at 60 °C or stannous octoate (Sn(Oct)2) at 130 °C, generating α-methylene-containing polyester (PMDXO) with a linear structure and easily tunable molar mass. The ring-opening copolymerization of MDXO with ε-caprolactone or 1,5-dioxepan-2-one was also performed under the catalysis of DPP or Sn(Oct)2 to afford copolymers with different compositions and sequence structures that are influenced by the kinds of monomers and catalysts. PMDXO is a slowly crystallizable polymer with a glass transition temperature of ca. −33 °C, and its melting temperature and enthalpy are significantly influenced by the thermal history. The thermal properties of the copolymers are dependent on their composition and sequence structure. Finally, the post-modification of PMDXO based on the thiol-Michael addition reaction was briefly explored using triethylamine as a catalyst. Given the optimized condition, PMDXO could be dually modified to afford biodegradable polyesters with different functionalities.

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OPTICAL MATERIALS · 2024 · IF 3.8

Organic pollutant degradation over highly efficient Mn–Mo(O,S)2 oxysulfide photocatalyst under visible light illumination

Worku Lakew Kebede,Kuo Dong-Hau,Chen Xiaoyun

Metal oxide semiconductor photocatalysts have received remarkable consideration as a promising technology for environmental remediation and energy conversion. Oxysulfide semiconductors have narrow band gaps which are appropriate for photocatalytic removal of toxic organic pollutants under visible light illumination. For the elimination purpose of these pollutants, Mo(O,S) 2 , Mn(O,S) 2 , and Mn–Mo(O,S) 2 oxysulfide catalysts containing various Mn contents were synthesized at low temperatures via a simple method. The structural, morphological, electrochemical, compositional, and optical properties of the as-synthesized catalysts were exhaustively characterized. The photocatalytic degradation activity of the bares Mo(O,S) 2 , Mn(O,S) 2 , and other Mn–Mo(O,S) 2 compositions were evaluated over different types of organic pollutants under visible light illumination. The addition of Mn in Mo(O,S) 2 structure improved the photodegradation activity, and Mn–Mo(O,S) 2 -30 was found to be the best composition with superior photodegradation performance towards the four cationic, anionic, and neutral dyes. The degradation efficiency of 10 ppm of MB, and MO dyes reach 99.7 % and 98.6 %, within 30 and 120 min, respectively. Mn–Mo(O,S) 2 -30 catalyst also shows a good photodegradation performance on Rh B and NR organic pollutants. According to the recycling test, the catalyst exhibited excellent performance. The photodegradation follows pseudo-first order kinetics with a rate constant of 0.097 and 0.036 min −1 for MB and MO dyes, respectively. The trapping experiment showed that superoxide anion radicals (O 2 •- ) and holes (h + ) are the responsible active species for the degradation on MO and MB, respectively. The novelty of using Mn–Mo(O,S) 2 -30 for various dyes degradation lies in its remarkable catalytic properties.

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DYES AND PIGMENTS · 2018 · IF 3.767

Pyridone based binary and ternary monomethine dyes derived from 2-amino-4-chloro-5-formylthiophene-3-carbonitrile

Xiao-Lei Zhao,Jiao Geng,Bin Hu,Dan Xu,Wei Huang

New monomethine dyes have been prepared by a simple and highly efficient method in acetic anhydride, in which the common pyridine-2,6-dione moiety and thiophene derivatives occupy each side of the methine unit. Among them, the ternary monomethine-azo dyes were first obtained by the particularly useful post-modification synthetic strategy, in order to further adjust the π -conjugated system and electronic spectra of 2-amino-3-cyano-4-chloro-5-formylthiophene based heterocyclic hydrazone/azo dyes. UV−Vis spectral analyses reveal that the synthesized heterocyclic dyes exhibit a large color gamut because of the extension of the conjugation length of the chromophore , where the maximum absorption wavelength ( λ max ) is significantly red-shifted up to 181 nm from binary monomethine to ternary monomethine-azo dyes.

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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2024 · IF 5.7

De Novo Biosynthesis of L-Azetidine-2-Carboxylic Acid in Escherichia coli Strains for Powdery Mildew Treatment

Jie Zheng,Hongxiang Liu,Jiwen Zhang,Bo Yu

L-Azetidine-2-carboxylic acid (L-Aze), a natural nonproteinogenic amino acid found widely in plants, has recently been identified as an environmentally friendly agent for controlling powdery mildew with low toxicity. In this study, a biological route for L-Aze production via the methionine salvage pathway (Yang Cycle) was first in silico designed for Escherichia coli. Subsequently, systematic engineering strategies were employed to enhance the production efficiency, including the enhancement of the 5-phosphoribosyl 1-pyrophosphate (PRPP) supply, construction of the ATP-adenine cycle, and engineering of the strain’s resistance to L-Aze. The final strain produced L-Aze from glucose with a titer of 568.5 mg/L. The antifungal activity of the produced L-Aze in the fermentation broth was also confirmed for treating powdery mildew in cucurbits. This approach not only provides a sustainable and green route for pesticide production to control powdery mildew but also expands our understanding of the exogenous construction of the Yang Cycle in E. coli.

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JOURNAL OF PHARMACEUTICAL SCIENCES · 2016 · IF 2.641

Crystal Structures, X-Ray Photoelectron Spectroscopy, Thermodynamic Stabilities, and Improved Solubilities of 2-Hydrochloride Salts of Vortioxetine

Jing Li,Li-Yang Li,Sai-Fei He,Shan Li,Chang-Zhi Dong,Lei Zhang

Two vortioxetine (VOT) salts with hydrochloride (VOT-HCl and VOT-0.5HCl) were prepared and structurally characterized. VOT-HCl features 1-dimensional P/M helical chains through N–H···Cl hydrogen bond interactions, whereas VOT-0.5HCl possesses a 1-dimensional zigzag structure in which 2 VOT molecules share a single proton through N···H + ···N interactions. VOT-HCl converts into the monohydrate VOT-HCl·H 2 O after dissolution in water, whereas VOT-0.5HCl remains stable. The N 1s X-ray photoelectron spectroscopy analysis shows a characteristic binding energy peak at approximately 398.0 eV for VOT. The shift to high energy occurs at 400.3 eV for VOT-HCl and VOT-HBr, and at 399.7 eV for VOT-0.5HCl, which supports the salt formation by the degree of proton transfer and is confirmed by single-crystal X-ray analyses. The apparent equilibrium solubilities of VOT in water are significantly improved to 2.90 mg/mL (approximately a 32.0-fold increase over that of the free base) for VOT-HCl and to 0.59 mg/mL (approximately a 5.7-fold increase over that of the free base) for VOT-0.5HCl at 25°C.

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JOURNAL OF MEDICINAL CHEMISTRY · 2024 · IF 6.8

De Novo Discovery of a Noncovalent Cell-Penetrating Bicyclic Peptide Inhibitor Targeting SARS-CoV-2 Main Protease

Yahong Tan,Jinyue Yang,Min Wang,Qi Peng,Yongqi Li,Lifeng Fu,Mengmeng Zhang,Jiang Wu,Guanya Yang,Christopher John Hipolito,Youming Zhang,Jianxun Qi,Yi Shi,Yizhen Yin

Macrocyclic peptides have garnered significant attention as promising drug candidates. However, they typically face challenges in achieving and enhancing cell permeability for access to intracellular targets. In this study, we focused on the de novo screening of macrocyclic peptide inhibitors against the main protease (Mpro) of SARS-CoV-2 and identified novel noncovalently bound macrocyclic peptides that effectively inhibit proteolytic activity. High-resolution crystal structures further revealed molecular interactions between the macrocyclic peptides and Mpro. Subsequently, a specific macrocyclic peptide lacking cell permeability was further optimized and transformed into a low-toxicity, metabolically stable bicyclic peptide with a cell penetration capacity and therapeutic potential against SARS-CoV-2. The bicyclic peptide was achieved using a novel strategy that involved introducing both a bicyclic structure and a bridging perfluorobiphenyl group. Our study not only provides a lead peptide inhibitor for COVID-19 but also offers valuable insights into achieving cell penetration for macrocyclic peptides through strategic modifications.

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ORGANIC & BIOMOLECULAR CHEMISTRY · 2022 ·Vol. 20 ·期 7 ·1510-1517 · IF 3.89

Synthesis of C3-functionalized indole derivatives via Brønsted acid-catalyzed regioselective arylation of 2-indolylmethanols with guaiazulene

Yang Liu,Meng Cao,Shangxi Zhang,Zhenxi Wang,Xin Dai,Xinde Jiang,Yucheng Dong,Jie Fu

A Brønsted acid catalyzed method for the construction of guaiazulenyl C3-functionalized indole derivatives is reported for the first time. The reactions proceeded smoothly at ambient temperature by using (±)-10-camphorsulfonic acid (CSA) as a catalyst, 2-indolylmethanols and guaiazulene as substrates, and the desired products were obtained in high yields with excellent regioselectivities.

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CHIRALITY · 2022 ·Vol. 34 ·期 5 ·701-710 · IF 2.183

Preparation of cellulose derivative bearing bulky 4-(2-benzothienyl)phenylcarbamate substituents as chiral stationary phase for enantioseparation

Fan Wang,Yuqing Wang,Yixuan Min,Junqing Li,Lili Zhang,Ting Zheng,Jun Shen,Yoshio Okamoto

A novel cellulose derivative bearing bulky 4-(2-benzothienyl)phenylcarbamate substituents ( Cel-1 ) was readily synthesized by carbamoylation followed by Suzuki–Miyaura coupling reaction. The corresponding coated-type chiral stationary phase (CSP) was prepared on basis of the derivative, and its chiral recognition ability was then evaluated by high-performance liquid chromatography (HPLC). The chiral recognition ability of the cellulose derivative was greatly influenced by introduction of the bulky benzothienyl pendants on the aromatic moieties of phenylcarbamates, compared with its analog with smaller groups. Many racemates, including the metal tris(acetylacetonate) complexes, chiral drug, and the analyte with axial chirality, were sufficiently separated with good enantioselectivities on Cel-1 . Some of them were even higher than those on the commercially powerful Chiralcel OD, which is also a coated-type CSP derived from cellulose phenylcarbamate derivative containing smaller 3,5-dimethyl pendants. The 1 H NMR and circular dichroism (CD) spectra of Cel-1 indicated that the obtained derivative possessed a regular higher order structure, and a strong cotton effect was observed within the absorption range of π-conjugated pendant at 350–500 nm. Impressively, the cellulose derivative bearing the bulky 4-(2-benzothienyl)phenylcarbamates exhibited good enantioselective fluorescence quenching behavior to the enantiomer pair of 1-phenylethylamine, probably suggesting its potential for the application as a chiral fluorescent sensor with high efficiency. The combination of the arrangement of bulky π-conjugated benzothienyl pendants on the phenylcarbamate moieties surrounding the helical backbone and the regular higher order structure of the polymer itself probably played a key role for this high chiral fluorescent recognition ability of Cel - 1 . The interaction sites of bulky 4-(2-benzothienyl)phenylcarbamate pendants in its excited state can exhibit higher enantioselective discrimination via fluorescent response to the chiral compound Q1 , whereas the chiral recognition ability of Cel-1 to the same compound in the ground state had no clear improvement.

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