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ACS Sustainable Chemistry & Engineering · 2020 · IF 7.632

Ferromagnetic Lignin-Derived Ordered Mesoporous Carbon for Catalytic Hydrogenation of Furfural to Furfuryl Alcohol

Xiaoqi Wang,Mo Qiu,Richard Lee Smith Jr.,Jirui Yang,Feng Shen,Xinhua Qi

Ferromagnetic Ni-doped lignin-derived ordered mesoporous carbon (Ni@OMC) was synthesized in one pot by evaporation-induced self-assembly (EISA) for use as catalysts. Lignin was used to partially replace phloroglucinol (up to 80%) as the carbon precursor under conditions that allowed ordered mesoporous structures to be perfectly retained and Ni particles to be uniformly dispersed within the material. The as-synthesized Ni@OMC catalysts promoted hydrogenation of furfural, affording furfuryl alcohol (FAL) yields and selectivities as high as 91.0 and 98.6% at 180 °C for a 12 h reaction time in the presence of H2 gas. The Ni@OMC catalyst could be simply separated through application of a magnetic field and was recyclable for at least five cycles. The stability of the Ni@OMC catalyst is attributed to space confinement effects of the carbon skeleton on the doped Ni particles through coordinated interactions between lignin and metal ions (Ni2+). The proposed method allows the synthesis of metal-doped ordered porous carbons from lignin and is green and sustainable.

CAS / MDL: 98-01-1 71-23-8 108-73-6
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BIORESOURCE TECHNOLOGY · 2020 · IF 7.539

Oxidation of organosolv lignin in a novel surfactant-free microemulsion reactor

Juanhua Kong,Lixia Li,Qiang Zeng,Zhenping Cai,Yingying Wang,Hongyan He,Sijie Liu,Xuehui Li

Lignin is considered as a promising substitute for fossil resources, but its efficient conversion remains a huge challenge due to the structural complexity and immiscibility with typical solvents. Herein, a series of surfactant-free microemulsion reactors comprised of n -octane, water and n -propanol were designed and their corresponding phase behaviors alongside their ability to intensify oxidative depolymerization of lignin were explored. Experimental results show that the phenolic monomer yield improves substantially (40–500 wt%) by comparison with processes performed in a single solvent. Detailed characterizations also suggest that the above intensification is rationalized by the solubilization effect of microemulsion system and directional aggregation of lignin at the microemulsion interface.

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JOURNAL OF SOLUTION CHEMISTRY · 2020 ·Vol. 49 ·期 9 ·1237-1249 · IF 1.273

Investigations on the Thermophysical Properties of the Binary Mixtures of Ethyl Laurate with Four n-Alkanols

Li Dan,Guo Meng,Wu Qian,Li Menglei,Ruan Nannan,Gao Lijun

The density, viscosity and excess properties of biodiesel–alcohol fuel blends are investigated for research into the blending of fuels. Four n -alkanols (1-propanol, 1-butanol, 1-pentanol and 1-hexanol) as additives were mixed with ethyl laurate to form binary systems for density and viscosity measurement. Excess molar volumes and viscosity deviations of the four binary systems (1-propanol + ethyl laurate), (1-butanol + ethyl laurate), (1-pentanol + ethyl laurate), and (1-hexanol + ethyl laurate) were calculated from the experimental density and viscosity data and fitted with the Redlich–Kister equation. Grunberg–Nissan and McAllister equations were used to correlate viscosities and the correlated values from McAllister equation are in good agreement with the experimental data. The results may be useful for the research and development of biodiesel–alcohol fuel blends.

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JOURNAL OF CHROMATOGRAPHY A · 2020 · IF 4.049

Development of histidine-tagged cyclic peptide functionalized monolithic material for the affinity purification of antibodies in biological matrices

Rongrong Xu,Li Lu,Lingjue Sun,Xiao Liu,Yutian Lei,Shengfeng Huang,Hao Huang,Jacques Crommen,Hai Han,Qiqin Wang,Zhengjin Jiang

The rapidly increasing applications of monoclonal antibodies (mAbs) in therapy have necessitated the development of mAb production and purification technologies for both academic and industrial usage. Herein, a histidine-tagged cyclic peptide (HHHHHHGSGSGSDC*AWHLGELVWC*T, the disulfide-bonded cysteines of which are indicated by asterisks, named HT25-cyclopeptide) functionalized monolithic material was developed by the metal ion chelation-based approach. The resulting material possessed suitable affinity and peptide ligand density (13.8 mg peptide ligand per mL of material), good porosity (67.1 %), acceptable specific surface area (52.95 m 2 /g), and lots of macropores (4.13 μm). Moreover, excellent antibody-specific selectivity, comparable or even better binding capacity (for dried material, maximum static binding capacity and dynamic binding capacity are about 119.3 mg/g and 17.05 mg/g, respectively) for antibody compared to previously developed affinity materials, acceptable resistance to trypsin digestion, and negligible nonspecific protein adsorption, were also achieved on this novel monolithic material. Compared with the corresponding cyclic peptide-based sepharose material, milder elution conditions were employed for the HT25-cyclopeptide-based monolithic material, which could effectively prevent the aggregation and denaturation of the enriched antibodies. This novel material was then successfully applied to the affinity enrichment and purification of mAbs (including infliximab and rituximab) in different cell culture media or IgG in human serum.

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JOURNAL OF MOLECULAR LIQUIDS · 2020 · IF 5.065

Solid-liquid phase equilibrium of naphazoline hydrochloride in eleven neat solvents: Determination, solvent effect, molecular simulation and thermodynamic analysis

Haixia He,Jiao Sha,Yameng Wan,Renren Sun,Gaoliang Jiang,Yu Li,Tao Li,Baozeng Ren

The purpose of this work was to measure the equilibrium solubility of naphazoline hydrochloride (NPZ) in different mono-solvents ranged from 278.15 K to 323.15 K by a laser monitoring method. In this research, N -methyl pyrrolidone (NMP), n -propanol, 2-butoxyethanol, ethanol, 2-methoxyethanol, N , N -dimethylformamide (DMF), methanol, ethylene glycol (EG), isopropanol, 2-propoxyethanol and 2-ethoxyethanol were selected as the experimental solvents. The results indicated that solubility data of NPZ in 11 neat solvents increased with the increase of temperature. At 298.15 K, the maximum solubility was observed in EG (5.028e-2), followed by 2-methoxyethanol (2.460e-2), methanol (2.429e-2), 2-ethoxyethanol (7.788e-3), ethanol (6.391e-3), 2-propoxyethanol (4.216e-3), n -propanol (3.373e-3), 2-butoxyethanol (3.144e-3), DMF (2.348e-3), NMP (2.002e-3) and isopropanol (1.689e-3). Moreover, the solvent polarity, radial distribution function (RDF) and solvent effect (KAT-LSER model) were implemented to investigate the impact of solute-solvent interactions on solubility behavior of NPZ. The results demonstrated that the whole dissolution behavior of NPZ in organic solvents was a complicated process, and the solvent-solute interactions were associated with hydrogen bond acidity and dipolarity/polarizability of solvent. Besides, the NRTL-SAC, Two-Suffix Margules, Wilson, NRTL and UNIQUAC models were employed to fit experimental solubility data. Deviation analysis revealed that the Wilson model reflected the best agreement between measured data and calculated values with the minimum mean values of average relative deviation (100ARD, 0.9144) and root-mean square deviation (10 4 RMSD, 1.062). Furthermore, the positive entropy changes and negative values of Gibbs energy changes showed that mixing and dissolution process of NPZ in 11 neat solvents were confirmed to entropy-driven and spontaneous.

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JOURNAL OF CHROMATOGRAPHY A · 2020 · IF 4.049

Rapid preparation of 1-vinylimidazole based non-affinity polymers for the highly-selective purification of antibodies from multiple biological sources

Yutian Lei,Xiao Liu,Li Lu,Cuihua Liu,Rongrong Xu,Shengfeng Huang,Yuan Shen,Chunping Deng,Jinchen Yu,Tingting Zhang,Jacques Crommen,Qiqin Wang,Zhengjin Jiang

There is an urgent need for developing advanced purification techniques with the merits of low cost and satisfactory capacity in order to meet the challenges in the current downstream purification of monoclonal antibodies (mAbs). Herein, a simple and inexpensive nitrogen heterocycle molecule, 1-vinylimidazole (VIM), was proposed as the capture ligand of antibodies for the first time. The corresponding VIM-based non-affinity polymeric material (polyVIM) was then fabricated via a one-step polymerization for use in the highly selective purification of antibodies. Compared to the previously reported materials, this novel material exhibited many advantages without clearly sacrificing selectivity , such as a simpler and faster fabrication (within 1.5 h), comparable or even higher binding capacity (saturated static adsorption capacity > 190 mg/g polymer, dynamic binding capacity about 31.62 mg/g polymer), lower non-specific protein adsorption, and much lower cost. Notably, the polyVIM can effectively purify the antibodies from multiple biological sources with high purity (95.4% for mAbs in the cell culture medium, 93.3% for hIgG in the human serum), with an acceptable recovery (91.6% for mAbs, 77.0% for hIgG), and good reusability (> 10 times). Moreover, the target ELISA binding assay and NFAT-luc reporter gene assay demonstrated that the enriched antibodies can well maintain their binding activity and bioactivity during the whole purification process. The excellent performance of the polyVIM material may be attributed to the high recognition ability of VIM for antibodies, as well as the biocompatible and antifouling properties of the porous polymer . This study provides a promising alternative material for the purification of mAbs in downstream processes and the enrichment of hIgG in human serum.

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JOURNAL OF MOLECULAR LIQUIDS · 2020 · IF 5.065

Microstructures of the Gemini surfactant microemulsion system 14-4-14/1-propanol/n-heptane/water

Xiaoxing Lu,Shaoxia Xie,Jian Kuang,Hujun Xie

A comprehensive experimental investigation on the microstructures of microemulsion constructed with Gemini surfactant has been carried out. The structural transition of the microemulsion system, 14-4-14/1-propanol/ n -heptane/water, from water-in-oil (W/O) to bi-continuous (B.C.) has been characterized by electrical conductivity and cyclic voltammetry . Being a typically percolative system, spherical nanodroplets are observed in the W/O system, while interlinks of water and oil continuous phases are observed in the middle phase, as confirmed by cryo-TEM. Most importantly, the role of water is clearly revealed. Increasing the water content results in size enhancement as well as improvement of micropolarity and diffusion behavior. Results of DSC measurements suggest that free water dominates only at high total water content. The unfrozen water which is not detected by DSC takes a considerable amount in the W/O system at low total water content, while the interphasal water reaches over 50% of total water in the middle phase system.

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JOURNAL OF SOLUTION CHEMISTRY · 2020 ·Vol. 49 ·期 11 ·1402-1418 · IF 1.273

Investigation of the Effect of Alkyl Chain Length on Molecular Interactions Between Methyl Benzoate with Alcohols: A Study of Physicochemical Properties

Chen Tingting,Feng Xiao,Yin Yuqiao,Xu Yingjie

Densities, speeds of sound, and viscosities of binary mixtures of methyl benzoate (MB) with ethanol, 1-propanol, and 1-butanol were measured at temperature ranging from T  = 293.2 to 313.2 K and refractive indices were determined at T  = 303.2 K. Excess molar volumes, V E , isentropic compressibility deviations ∆ κ s and viscosity deviations, Δ η , were obtained and fitted with the Redlich–Kister equation with satisfactory results. Based on the measured and derived physicochemical properties, the influence of the alkyl chain length of the alcohol on the molecular interactions of the studied mixtures was explored. The results show that both hydrogen bond interaction between carbonyl group of MB and hydroxyl group of alcohol and the packing efficiency, such as accommodation of alcohol in the interstice of MB, play an important role in the microstructure of the mixtures, which leads to the disruption of alcohol with the addition of MB. Moreover, by comparing V E , ∆ κ s and Δ η values of MB (1) + alcohol (2) systems at T  = 303.2 K, it is found that the strength of hydrogen bond interaction and the packing efficiency significantly weakens with increasing alkyl chain length of alcohol in going from ethanol to 1-butanol, resulting in the V E values of the studied systems gradually changing from a negative deviation to an S shape, the ∆ κ s and Δ η values have negative deviations, and the ∆ n D values have positive deviations. The obtained results will provide thermodynamic guidance for the industrial purification of methyl benzoate.

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COMPUTERS AND ELECTRONICS IN AGRICULTURE · 2020 · IF 3.858

Discrimination of wood-boring beetles infested Platycladus orientalis plants by using gas chromatography-ion mobility spectrometry

Chengyu Zheng,Zhenhe Wang,Jing Zhang,Jun Wang,Jianli Zhong,Yongwei Wang

Platycladus orientalis plants in China are experiencing a serious problem with wood-boring beetles, but conventional physical detection methods cannot perform well due to hidden larvae and less obvious symptoms in the early infestation. In this study, the volatile organic compounds (VOCs) of P. orientalis were investigated using gas chromatography-ion mobility spectrometry (GC-IMS) to identify its internal infestation. An image-based evaluation method of the degree of internal wood damage was proposed, the principal component analysis (PCA) based on specific markers was applied for natural clustering of samples, and unsupervised learning approaches based on specific markers and automatically located peaks were used to create predictive models for sample classification. The results showed that the herbivore-induced plant volatiles (HIPVs) of P. orientalis samples had two main characteristics compared with undamaged plants. One was the emergence of several compounds such as C 3 -C 6 ketones, aldehydes, and alcohols, while the other was the obvious content variation of several monoterpenes and their derivatives. The classification models based on specific markers and automatically located peaks could correctly classify at least 89.5% and 87.9% of the samples, respectively. In a word, these results proved that GC-IMS based approaches combined with different feature extraction methods have the potential to identify the internal infestation of wood-boring beetles in P. orientalis .

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POLYMERS FOR ADVANCED TECHNOLOGIES · 2020 ·Vol. 32 ·期 3 ·1126-1134 · IF 2.578

Structure and properties of polycarboxylic acid dispersants synthesized by RAFT method

Xiangyun Mi,Xiuzhi Zhang,Mei Ding,Ming Zhang,Meishan Pei

Polycarboxylic acid dispersants (PCs) with comb-like molecular structure have become the focus of dispersants. However, there are many contradictions in the study of molecular structure of polycarboxylic acids. In this article, a series of PCs with different molecular structures were prepared from acrylic acid (AA) and methyl allyl alcohol polyoxyethylene ether (TPEG) by reversible addition fragmentation chain transfer (RAFT) polymerization. The structural characteristics of PCs were characterized by flourier transform infrared spectrometer (FT-IR), 1 H nuclear magnetic resonance (NMR) spectroscopy and gel permeation chromatography (GPC). The dispersion performance of PCs to cement was measured by the fluidity and adsorbing capacity. The results show that the dispersion performance and adsorbing capacity of PCs are significantly related to its structure. The adsorption and dispersion properties increase with the increase of carboxyl content and molecular weight. However, this phenomenon is limited to a certain range that the acid ether ratio in this range is no greater than 5:1, and the molecular weight is no greater than PC-4 ( Mw = 82 125, Mn = 63 889).

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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2020 · IF 3.99

Janus lamellar nanosheets fabricated at the air/liquid interface

Ming Han,Hong-Guo Liu

Two-dimensional (2D) Janus nanostructures have attracted much interest due to their unique structure and properties, and researchers are making great efforts continuously to explore new preparation methods. Herein, we reported a facile method to fabricate Janus nanosheets with lamellar structures at the air/liquid interface of a water-miscible organic solution of fatty acids and an aqueous solution of metal ions . The organic solution spread on the subphase surface and diffuse into the subphase simultaneously, and the aqueous solution diffused into the organic solution at the same time. Thus, the fatty acid molecules and metal ions self-assembled into layered nanosheets with the aid of hydrophobic interaction of alkyl chains and coordination between carboxylic groups and metal ions in the mixed solution. The sides facing to air and the subphase are composed of alkyl chains and carboxylates, respectively, indicating that the nanosheets are Janus ones. Various organic solvents , metal ions and fatty acid molecules have been tried to fabricate such layered Janus nanosheets. This method is expected to be a useful way to assemble Janus nanostructures.

CAS / MDL: 71-23-8
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RENEWABLE ENERGY · 2021 · IF 8.001

Selective hydrogenation of furfural and its derivative over bimetallic NiFe-based catalysts: Understanding the synergy between Ni sites and Ni–Fe alloy

Yuewen Shao,Junzhe Wang,Kai Sun,Guoming Gao,Chao Li,Lijun Zhang,Shu Zhang,Leilei Xu,Guangzhi Hu,Xun Hu

Pentanediols (1,2-pentanediol and 1,5-pentanediol) are important feedstock for synthesis of fine chemicals, production of which from the biomass-derived furfural or furfuryl alcohol (FA) has been considered as a sustainable route and attracted much interest. In this study, the catalysts with Ni–Fe as the metal sites and Mg–Al layered double hydroxides (LDH) as precursor of support were synthesized. The results showed that the presence of Fe in catalyst affected both the development of the pores of the catalyst and the catalytic behaviors of nickel species. A low Fe content facilitated formation of mesoporous structure, but the higher content destroyed the LDH structure, resulting in a decreased surface area. Fe could also react with metallic Ni to form NiFe alloy. This decreased the catalytic activity for the further hydrogenation of the furan ring in FA, and FA would thus have the chance to produce pentanediols via hydrogenolysis . The In-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy characterization of hydrogenation of FA indicated that the alloying between Fe and Ni resulted in a weak adsorption of C C group in furan ring and moderate adsorption of C–O–C group, which suppressed the complete hydrogenation of FA while facilitated the ring-opening of FA to form the pentanediols.

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