槲皮素-3-O-丙基衍生物的合成及生物活性研究

槲皮素是具有丰富生物活性的黄酮类化合物,药理活性显著。本文以槲皮素为先导物,选择性对C环3位羟基进行修饰,以廉价的芦丁为原料,经苄基保护、Williamson成醚反应,再经Pd/C催化加氢脱苄基得到28个未见文献报道的槲皮素-3-O-丙基衍生物,其结构经¹H NMR、¹³C NMR、ESI-MS进行确证。采用MTT法考察了所合成化合物对人食管鳞癌（EC109）、人胃癌（HGC27）、人乳腺癌（MCF-7）、小鼠黑色素瘤（B16-F10）的增殖抑制作用。结果显示,通过化学方法对槲皮素结构进行修饰后,其体外抗肿瘤活性增强。其中,化合物F3(IC₅₀=5.23±0.37μmol/L)、F5(IC₅₀=2.63±0.09μmol/L)对小鼠黑色素瘤（B16-F10）抑制作用比5-氟尿嘧啶(IC₅₀=14.38±0.27μmol/L)好,值得进一步研究。     

Electrochemical strategy for ultrasensitive detection of microRNA based on MNAzyme-mediated rolling circle amplification on a gold electrode

Microchimica Acta - The authors describe an electrochemical strategy for ultrasensitive and specific detection of microRNA (miRNA). It is based on both multicomponent nucleic acid enzyme (MNAzyme)...     

Visible light induced decomposition of sulfonyl hydrazides using Pd/ZrO2 nanocomposite photocatalyst

A new approach to synthesis of thiosulfonates has been developed under mild conditions without any oxidants and promoting reagents through a Pd/ZrO₂ nanocomposite photocatalyst catalyzed decomposition of sulfonyl hydrazides. This protocol gave the products in moderate yields, comparable to the best results reported so far. Finally, a plausible reaction mechanism was proposed.     

Magnetic Multi-Walled Carbon Nanotubes Matrix Solid-Phase Dispersion with Dispersive Liquid–Liquid Microextraction for the Determination of Ultra Trace Bisphenol A in Water Samples

Magnetic nanoparticle-assisted solid-phase dispersion (MMSPD) combined with dispersive liquid–liquid microextraction (DLLME) prior to high performance liquid chromatography with fluorescence detector (HPLC–FLU) is presented for determination of ultra trace Bisphenol A (BPA) in water. Magnetic multi-walled carbon nanotubes (MMWCNTs) were synthesized for the adsorption of BPA in water. Ultra trace BPA in water was transferred into the elute solvent by the MMSPD and further concentrated into trace volume extraction solvent by the DLLME. The limit of detection and limit of quantitation were 0.003 and 0.01 µg L^?1, respectively. Good linearity of BPA was found, ranging from 0.01 to 10 µg L^?1, with good squared regression coefficient (R ²) of 0.9999. Additionally, relative recoveries were 83.1 and 95.9% for two environmental water samples spiked with 0.20 µg L^?1 BPA, respectively. All results showed that the MMWCNTs nanoparticle-assisted MMSPD–DLLME–HPLC–FLU method was simple and reliable for the determination of ultra trace BPA in environmental water.     

Mixing of Racemic Poly(L-lactide)/Poly(D-lactide) Blend with Miscible Poly(D,L-lactide):Toward All Stereocomplex-type Polylactide with Strikingly Enhanced SC Crystallizability

Stereocomplex-type polylactide (SC-PLA) consisting of alternatively arranged poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) chains has gained a good reputation as a sustainable engineering plastic with outstanding heat resistance and durability,however its practical applications have been considerably hindered by the weak SC crystallizability.Current methods used to enhance the SC crystallizability are generally achieved at the expense of the precious bio-renewability and/or bio-degradability of PLAs.Herein,we demonstrate a feasible method to address these challenges by incorporating small amounts of poly(D,L-lactide) (PDLLA) into linear high-molecular-weight PLLA/PDLA blends.The results show that the incorporation of the atactic PDLLA leads to a significant enhancement in the SC crystallizability because its good miscibility with the isotactic PLAs makes it possible to greatly improve the chain mixing between PLLA and PDLA as an effective compatibilizer.Meanwhile,the melt stability (i.e.,the stability of PLLA/PDLA chain assemblies upon melting) could also be improved substantially.Very intriguingly,SC crystallites are predominantly formed with increasing content and molecular weight of PDLLA.More notably,exclusive SC crystallization can be obtained in the racemic blends with 20 wt％ PDLLA having weight-average molecular weight of above 1 ×10s g/mol,where the chain mixing level and intermolecular interactions between the PLA enantiomers could be strikingly enhanced.Overall,our work could not only open a promising horizon for the development of all SC-PLA-based engineering plastic with exceptional SC crystallizability but also give a fundamental insight into the crucial role of PDLLA in improving the SC crystallizability of PLLA/PDLA blends.     

Sustainable and Robust Graphene Cellulose Paper Decorated with Lithiophilic Au Nanoparticles to Enable Dendrite-free and High-Power Lithium Metal Anode

Lithium metal anodes (LMAs) with high energy density have recently captured increasing attention for development of next-generation batteries. However, practical viability of LMAs is hindered by the uncontrolled Li dendrite growth and infinite dimension change. Even though constructing 3D conductive skeleton has been regarded as a reliable strategy to prepare stable and low volume stress LMAs, engineering the renewable and lithiophilic conductive scaffold is still a challenge. Herein, a robust conductive scaffold derived from renewable cellulose paper, which is coated with reduced graphene oxide and decorated with lithiophilic Au nanoparticles, is engineered for LMAs. The graphene cellulose fibres with high surface area can reduce the local current density, while the well-dispersed Au nanoparticles can serve as lithiophilic nanoseeds to lower the nucleation overpotential of Li plating. The coupled relationship can guarantee uniform Li nucleation and unique spherical Li growth into 3D carbon matrix. Moreover, the natural cellulose paper possesses outstanding mechanical strength to tolerate the volume stress. In virtue of the modulated deposition behaviour and near-zero volume change, the hybrid LMAs can achieve reversible Li plating/stripping even at an ultrahigh current density of 10 mA cm⁻² as evidenced by high Coulombic efficiency (97.2 % after 60 cycles) and ultralong lifespan (1000 cycles) together with ultralow overpotential (25 mV). Therefore, this strategy sheds light on a scalable approach to multiscale design versatile Li host, promising highly stable Li metal batteries to be feasible and practical.     

Fabrication of liquid crystal Fe3O4 composites and their magnetorheological properties

Some supramolecular polyacrylate-based liquid crystal polymers (PLCPs) were prepared by polyacrylic acid, a liquid crystal monomer and 3,5-pyridinedicarboxylic acid. Series of magnetic liquid crystal particles (Fe₃O₄@PLCPs) with core-shell structure were prepared by modifying surface of magnetic nanoparticles Fe₃O₄ by the PLCPs. The Fe₃O₄@PLCPs showed a saturation magnetization strength above 51.17 emu/g, which is similar to pure magnetic Fe₃O₄, indicating good magnetism and magnetic field dependence. Series of magnetorheological fluids were fabricated by Fe₃O₄@PLCPs (using as dispersed phase) and silicone oil (using as carrier liquid). The effects of mesogen, magnetic particle, and the polymer matrix on magnetorheological performance and settling stability were investigated. The magnetorheological fluid based on 10% Fe₃O₄@PLCP-1 showed the best performance at an applied magnetic field of 100 mT in this study. Furthermore, the magnetorheological fluids showed excellent settling stability because the density of Fe₃O₄@PLCPs was lower than that of Fe₃O₄. The Fe₃O₄@PLCPs-based fluids presented certain application potential in the field of magnetic fluid due to the excellent magnetorheological effect and settling stability.     

3一致 C-超图的最小边数

混合超图是含有两类超边的超图,一类称为C-超边,一类称为D-超边,它们的区别主要体现在染色要求上．混合超图的染色,要求每一C-超边至少有两个点染相同的颜色,而每一D-超边至少有两个点染不同的颜色．所用的最大颜色数称为对应混合超图的上色数,所用的最小颜色数称为对应混合超图的下色数．上、下色数与边数有密切关系．作者在文献[2]中证明了具有最小上色数的3一致C-超图边数的一个下界为‘n(n-2)/3’,其中n为对应混合超图的顶点数．该文证明当n=2k 1时,该下界是可以达到的．     

4一致反超图的最小边数问题

混合超图是在超图的基础上添加一个反超边得到的图．超边和反超边的区别主要体现在着色要求上．在着色中,要求每一超边至少要有两个点着不同的颜色,而每一反超边至少有两个点着相同的颜色．最大最小颜色数分别称为混合超图的上色数和下色数。本文主要研究反超图,即只含反超边的超图。讨论了上色数为3的4一致超图的最小边数问题．给出了上色数为3的4一致反超图的最小边数的一个上界和一个下界．     

A general transformation class of semiparametric cure rate frailty models

We consider a class of cure rate frailty models for multivariate failure time data with a survival fraction. This class is formulated through a transformation on the unknown population survival function. It incorporates random effects to account for the underlying correlation, and includes the mixture cure model and the proportional hazards cure model as two special cases. We develop efficient likelihood-based estimation and inference procedures. We show that the nonparametric maximum likelihood estimators for the parameters of these models are consistent and asymptotically normal, and that the limiting variances achieve the semiparametric efficiency bounds. Simulation studies demonstrate that the proposed methods perform well in finite samples. We provide an application of the proposed methods to the data of the age at onset of alcohol dependence, from the Collaborative Study on the Genetics of Alcoholism.