Visible-light-induced,autopromoted nickel-catalyzed three-component arylsulfonation of 1,3-enynes and mechanistic insights

Science China Chemistry - A light-induced, nickel-catalyzed three-component arylsulfonation of 1,3-enynes in the absence of photocatalyst is reported. This methodology exhibited mild conditions,...     

How do peace dividends bring about human development and productivity?

Annals of Operations Research - The main purpose of this study was to explore the impact of peace dividends on global changes in national productivity. First, this study assessed changes in...     

白云石制备似立方体状方解石型碳酸钙晶体及其机理研究

以轻烧白云石粉、氯化铵和二氧化碳为原料,在未使用晶型控制剂的情况下,通过蒸氨-沉钙过程制备出了似立方体状碳酸钙。研究了反应温度、溶液中钙离子浓度、通气速率、搅拌速度以及陈化时间对碳酸钙中方解石相含量以及晶体形貌的影响,并探索了沉钙反应的晶型控制机理。结果表明,在反应温度40 ℃、钙离子浓度0.05 mol/L、通碳速率100 mL/min、搅拌速度400 r/min和陈化时间2 h的条件下,制备出形貌规整、粒径分布均匀的似立方体状碳酸钙,平均粒径为5~10 μm。该研究为提升白云石的使用价值、生产高附加价值的碳酸钙产品,以及提高白云石资源的利用率提供理论基础。     

Cu/CuO-Graphene Foam with Laccase-like Activity for Identification of Phenolic Compounds and Detection of Epinephrine

Although great progress has been made in the advancement of nanozymes, most of the studies focus on mimicking peroxidase, oxidase, and catalase, while relatively few studies are used to mimic laccase. However, the use of nanomaterials to mimic laccase activity will have great potential in environmental and industrial catalysis. Herein, Cu/CuO-graphene foam with laccase-like activity was designed for the identification of phenolic compounds and the detection of epinephrine. In a typical experiment, the formation mechanism of Cu/CuO-graphene foam was investigated during the pyrolysis process by thermogravimetric-mass spectrometry. As a laccase mimic, Cu/CuO-graphene foam exhibited excellent catalytic activity with a Michaelis-Menten constant and a maximum initial velocity of 0.17 mmol/L and 0.012 mmol∙L^-1∙s^-1, respectively. Based on this principle, Cu/CuO-graphene foam nanozyme could differentially catalyze phenolic compounds and 4-aminoantipyrine for simultaneous identification of phenolic compounds. Furthermore, a colorimetric sensing platform was fabricated for the quantitative determination of epinephrine, showing linear responses to epinephrine in the range of 3 mg/mL to 20 mg/mL with the detection limit of 0.2 mg/mL. The proposed Cu/CuO-graphene foam nanozyme could be applied for the identification of phenolic compounds and the detection of epinephrine, showing great potential applications for environmental monitoring, biomedical sensing, and food detection fields.     

直接碳燃料电池燃料的研究进展

直接碳燃料电池(DCFC)是一种清洁高效利用碳资源发电的装置。其因能量转换率高,对环境污染小,燃料选择范围广等优点获得了越来越多的关注。DCFC的性能与使用的燃料密切相关,为了探究燃料对DCFC的影响,本文分别阐述了石墨、炭黑、中密度纤维板、生物质、煤、活性炭的特性及改性方法,分析讨论了燃料表面含氧官能团以及燃料中的金属催化剂对阳极电化学反应的促进作用,发现燃料表面化学性质要比比表面积更加重要。同时,本文也提出了对生物质这一优良的可再生资源的期待,为未来DCFC燃料的发展提供参考。     

Mechanistic Investigation and Conductance Modulation of a Metal-Molecule-Metal Junction via Extra Acid Addition

One important prerequisite for the fabrication of molecular functional device strongly relies on the understanding the conducting behaviors of the metal-molecule-metal junction that can respond to an external stimulus. The model Lewis basic molecule 4,4′-(pyridine-3,5-diyl)dibenzonitrile (DBP), which can react with Lewis acid and protic acid, was synthesized. Then, the molecular conducting behavior of DBP, DBP-B(C₆F₅)₃, and DBP-TfOH (DBP-B(C₆F₅)₃, and DBP-TfOH were produced by Lewis acid and protonic acid treatment of DBP) was researched and compared. Given that their identical physical paths for DBP, DBP-B(C₆F₅)₃, and DBP-TfOH to sustain charge transport, our results indicate that modifying the molecular electronic structure, even not directly changing the conductive physical backbone, can tune the charge transporting ability by nearly one order of magnitude. Furthermore, the addition of another Lewis base triethylamine (of stronger alkaline than DBP), to Lewis acid-base pair reverts the electrical properties back to that of a single DBP junction, that is constructive to propose a useful but simple strategy for the design and construction of reversible and controllable molecular device based on pyridine derived molecule.     

An improved LC–MS/MS method for determination of docetaxel and its application to population pharmacokinetic study in Chinese cancer patients

Because of its unpredictable side effects and efficacy, the anticancer drug docetaxel (DTX) requires improved characterisation of its pharmacokinetic profiles through population pharmacokinetic studies. A sensitive and rugged LC–MS/MS method for the detection of DTX in human plasma was developed and optimised using paclitaxel as an internal standard (IS). The plasma samples underwent rapid extraction using hybrid solid-phase extraction-protein precipitation. The analyte and IS were separated with an isocratic system on a Zorbax Eclipse Plus C₁₈ column using water containing 0.05% acetic acid along with 20 μM of sodium acetate and methanol (30/70, v/v) as the mobile phase. Quantification was performed using a triple quadrupole mass spectrometer through multiple reaction monitoring in positive mode, using the m/z 830.3 → 548.8 and m/z 876.3 → 307.7 transitions for DTX and paclitaxel, respectively. The range of the calibration curve was 1–500 ng/mL for DTX, and the linear correlation coefficient was >0.99. The accuracies ranged from −4.6 to 4.2%, and the precision was no higher than 7.0% for the analytes. No significant matrix effect was observed. Both DTX and the IS showed considerable recovery. This method was finally applied to the establishment of a population pharmacokinetic model to optimise the clinical use of DTX.     

Pharmacokinetics of monoester‐diterpenoid alkaloids in myocardial infarction and normal rats after oral administration of Sini decoction by microdialysis combined with liquid chromatography–tandem mass spectrometry

Monoester‐diterpenoid alkaloids are the main bioactive components of Sini decoction, which is a well‐known traditional Chinese medicine formula for the treatment of myocardial infarction (MI) and heart failure in China. In this work, an ultra‐high‐performance liquid chromatography–mass spectrometry combined with microdialysis method was successfully established and applied for investigating for the first time comparative plasma pharmacokinetics of three monoester‐diterpenoid alkaloids (benzoylmesaconitine, benzoylaconitine and benzoylhypacoitine) in normal and MI rats after oral administration of Sini decoction. The statistical results of pharmacokinetic parameters demonstrated that benzoylmesaconitine, benzoylaconitine and benzoylhypacoitine showed lower peak concentration, longer half‐life, smaller area under the concentration–time curve, slower clearance, time to peak concentration and mean residence time in MI rats than in normal rats (p < 0.05), which indicated that monoester‐diterpenoid alkaloids exhibited lower systemic exposure and slower elimination in the MI rats. The results provided the experimental basis for understanding the metabolic fate and therapeutic effects of Sini decoction.     

Miktoarm star‐shaped poly(lactic acid) copolymer: Synthesis and stereocomplex crystallization behavior

The miktoarm star‐shaped poly(lactic acid) (PLA) copolymer, (PLLA)₂‐core‐(PDLA)₂, was synthesized via stepwise ring‐opening polymerization of lactide with dibromoneopentyl glycol as the starting material. ¹H NMR and FTIR spectroscopy proved the feasibility of synthetic route and the successful preparation of star‐shaped PLA copolymers. The results of FTIR spectroscopy and XRD showed that the stereocomplex structure of the copolymer could be more perfect after solvent dissolution treatment. Effect of chain architectures on crystallization was investigated by studying the nonisothermal and isothermal crystallization of the miktoarm star‐shaped PLA copolymer and other stereocomplexes. Nonisothermal differential scanning calorimetry and polarizing optical microscopy tests indicated that (PLLA)₂‐core‐(PDLA)₂ exhibited the fastest formation of a stereocomplex in a dynamic test due to its special structure. In isothermal crystallization tests, the copolymer exhibited the fast crystal growth rate and the most perfect crystal morphology. The results reveal that the unique molecular structure has an important influence on the crystallization of the miktoarm star‐shaped PLA copolymer. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 814–826     

Novel low-dielectric constant and soluble polyimides from diamines containing fluorene and pyridine unit

Polyimides (PI's) with low-dielectric constant and excellent organic solubility have broad application prospects in the electronic field. Herein, this study designed a series of novel, low dielectric, organic soluble PI films by creatively introducing fluorene and pyridine ring into diamine monomers. Because of the noncoplanar structure of fluorenyl and the polarization of pyridine ring, PI films achieved a low-dielectric constant (2.22–3.09 at 10 MHz) and excellent organic solubility. Even in some organic solvents with low-boiling points, these PI films still exhibited outstanding solubility. In addition, all the films possessed high-tensile strength (≈120 MPa) and excellent optical transparency (>70%, 450 nm). It was worth noting that the glass transition temperature of films was all above 280°C and 5% weight loss temperature (T_5%) was at 486–553°C. In general, the novel high-performance low-dielectric PI films are expected to be used in the field of microelectronics.