原位溶剂热聚合法制备金属有机骨架/碳化氮纳米片涂覆的固相微萃取纤维用于红茶中农药残留的高灵敏检测

有机氯（OCPs）和拟除虫菊酯（PYs）是两类广泛使用的农药,对自然环境和人类健康具有极大危害。在本研究中,通过原位溶剂热聚合法制备了金属有机骨架/碳化氮纳米片（UiO-66/HOCN）复合材料涂覆的固相微萃取（SPME）纤维,该纤维拥有良好的稳定性,并对OCPs和PYs具有高效的萃取性能。将其与气相色谱-质谱（GC-MS）相结合,建立了用于OCPs和PYs检测的高灵敏分析方法。该方法对9种农药目标物表现出了令人满意的回收率和重现性,具有检出限低（0.03~0.30 ng/L）、线性范围宽（0.1~800.0 ng/L）和线性相关系数良好（≥ 0.9978）等优点。将所建立的方法用于实际红茶样品中农药残留的检测,成功地在实际样品中检测出了艾试剂（6.6 ng/L）、α-硫丹（54.7 ng/L）和联苯菊酯（185.8 ng/L）。实验结果表明,所建立的分析方法适用于复杂基质中农药残留的分析和监测。     

Autocatalytic polymerization of selenium/polypyrrole nanocomposites as functional theranostic agents for multi-spectral photoacoustic imaging and photothermal therapy of tumor

The synchronization of diagnosis and treatment is a new trend in cancer treatment. Photoacoustic imaging (PAI) and photothermal therapy (PTT) are recognized as one of the perfect combinations. The autocatalytic polymerization of selenium/polypyrrole (Se@PPy) nanocomposites with a wide-absorption band at near-infrared region (NIR, 800 nm) has been developed in this paper. The wide optical absorption characteristics enable Se@PPy nanocomposites to achieve multi-spectral PAI. Ex vivo experiments show desirable photoacoustic ability of the Se@PPy nanocomposites at wavelengths ranging from 700 nm to 900 nm, which is better than that of commercial indocyanine green (ICG). Se@PPy nanocomposites have high photothermal conversion efficiency up to 36.3% as well as excellent photo-thermal stability. In vitro cytotoxicity test demonstrates that the Se@PPy nanocomposites have good bio-safety. Furthermore, the feasibility of Se@PPy nanocomposites for enhancing multi-spectral PAI guided PTT was verified on 4T1 tumor-bearing nude mice. Our results indicate that Se@PPy nanocomposites could be used as an effective theranostic agent for near-infrared light-mediated PAI and PTT of tumor.     

Rhodium(III)‐Catalyzed Asymmetric Access to Spirocycles through C−H Activation and Axial‐to‐Central Chirality Transfer

Axial‐to‐central chirality transfer is an important strategy to construct chiral centers, where the axially chiral reagents are mostly limited to atropomerically stable ones. Reported herein is a Rh^III‐catalyzed enantioselective spiroannulative synthesis of nitrones. The coupling proceeds via C?H arylation to give an atropomerically metastable biaryl, followed by intramolecular dearomative trapping under oxidative conditions with high degree of chirality transfer.     

Palladium‐Catalyzed Asymmetric [8+2] Dipolar Cycloadditions of Vinyl Carbamates and Photogenerated Ketenes

Higher‐order cycloadditions, particularly [8+2] cycloadditions, are a straightforward and efficient strategy for constructing significant medium‐sized architectures. Typically, configuration‐restrained conjugated systems are utilized as 8π‐components for higher‐order concerted cycloadditions. However, for this reason, 10‐membered monocyclic skeletons have never been constructed via catalytic asymmetric [8+2] cycloaddition with high peri‐ and stereoselectivity. Here, we accomplished an enantioselective [8+2] dipolar cycloaddition via the merger of visible‐light activation and asymmetric palladium catalysis. This protocol provides a new route to 10‐membered monocyclic architectures bearing chiral quaternary stereocenters with high chemo‐, peri‐, and enantioselectivity. The success of this strategy relied on the facile in situ generation of Pd‐containing 1,8‐dipoles and their enantioselective trapping by ketene dipolarophiles, which were formed in situ via a photo‐Wolff rearrangement.     

Iterative Suzuki‐Miyaura Cross‐coupling/Bromo‐desilylation Reaction Sequences for the Assembly of Chemically Well‐defined,Acyclic Oligopyrrole/Benzenoid Hybrids Embodying Mixed Modes of Connectivity

Syntheses of a range of chemically well‐defined oligopyrrole/benzenoid hybrids are described using tandem Suzuki‐Miyaura cross‐coupling/bromo‐desilyation reaction sequences for linking borylated pyrroles, halogenated pyrroles and/or dibromobenzenes to one another. By such means, including iterative variants, a range of all α‐linked, all β‐linked oligopyrroles as well as certain combinations thereof have been assembled, some of them for the first time. The conductivities of iodine‐treated thin films formed from certain such systems have been determined.     

低聚水溶性壳聚糖修饰阿魏酸及细胞毒活性研究

阿魏酸（Ferulic acid,FA）,化学学名为4-羟基3-甲氧基苯丙烯酸,是当归、川芎、木贼、升麻、樟白皮等中药材水溶性提取物中主要的单体活性成份,属天然酚酸类化合物,由于其优良的抗氧化性,故对一些肿瘤表现出抑制作用,但活性不是很好。另外,由于FA的稳定性差,在人体内不参与肝肠循环等缺陷也影响其药效的发挥。     

Synthesis and Structural Characterization of a Di-nuclear Uranyl Complex with Quinoline-6-carboxylate

Crystallography Reports - A di-nuclear uranyl complex with the formula of [(UO2)2(L)4(H2O)2]?4H2O (1) (HL = quinoline-6-carboxylic acid) was synthesized hydrothermally and characterized by...     

卡维地洛印迹聚合物的合成及其识别性能的研究

以卡维地洛药物分子为模板,甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,采用紫外光引发聚合的分子印迹技术,成功制备出卡维地洛分子印迹聚合物。用热重分析、扫描电镜对聚合物进行了表征,通过Scatchard方程研究了印迹聚合物对模板分子的结合特性。结果表明,在所研究的浓度范围内,印迹聚合物存在一类等价的结合位点,并计算出印迹聚合物与模板分子的平衡离解常数为0.5642 mmol/L,最大表观吸附量为97.44μmol/g,为理论值的63.53%。对不同底物的结合实验表明,该聚合物对卡维地洛具有优良的吸附选择性。     

Plasma assisted synthesis of LiNi0.6Co0.2Mn0.2O2 cathode materials with good cyclic stability at subzero temperatures

Layered Ni-rich cathode materials,LiNi_0.6Co_0.2Mn_0.2O₂(NCM622),are synthesized via solid reaction assisted with a plasma milling pretreatment,which is resulted in lowering sintering temperatures for solid precursors.The plasma milling pretreated NCM622 cathode material sintered at 780℃(named as PM-780)demonstrates good cycling stability at both room and subzero temperatures.Specifically,the PM-780 cathode delivers an initial discharge capacity of 171.2 mAh g^-1 and a high capacity retention of 99.7%after 300 cycles with current rate of 90 mA g^-1 at 30℃,while stable capacities of 120.3 and 94.0 m Ah g^-1 can be remained at-10℃and-20℃in propylene carbonate contained electrolyte,respectively.In-situ XRD together with XPS and SEM reveal that the NCM622 cycled at-10℃presented better structural stability and more intact interface than that of cathodes cycled at 30℃.It is also found that subzero temperatures only limit the discharge potential of NCM622 without destroying its structure during cycling since it still exhibits high discharge capacity at 30℃after cycled at subzero temperatures.This work may expand the knowledge about the low-temperature characteristics of layered cathode materials for Li-ion batteries and lay the foundation for its further applications.     

Optimizing the quasi-equilibrium state of hot carriers in all-inorganic lead halide perovskite nanocrystals through Mn doping: fundamental dynamics and device perspectives

Hot carrier (HC) cooling accounts for the significant energy loss in lead halide perovskite (LHP) solar cells. Here, we study HC relaxation dynamics in Mn-doped LHP CsPbI₃ nanocrystals (NCs), combining transient absorption spectroscopy and density functional theory (DFT) calculations. We demonstrate that Mn²⁺ doping (1) enlarges the longitudinal optical (LO)–acoustic phonon bandgap, (2) enhances the electron–LO phonon coupling strength, and (3) adds HC relaxation pathways via Mn orbitals within the bands. The spectroscopic study shows that the HC cooling process is decelerated after doping under band-edge excitation due to the dominant phonon bandgap enlargement. When the excitation photon energy is larger than the optical bandgap and the Mn²⁺ transition gap, the doping accelerates the cooling rate owing to the dominant effect of enhanced carrier–phonon coupling and relaxation pathways. We demonstrate that such a phenomenon is optimal for the application of hot carrier solar cells. The enhanced electron–LO phonon coupling and accelerated cooling of high-temperature hot carriers efficiently establish a high-temperature thermal quasi-equilibrium where the excessive energy of the hot carriers is transferred to heat the cold carriers. On the other hand, the enlarged phononic band-gap prevents further cooling of such a quasi-equilibrium, which facilitates the energy conversion process. Our results manifest a straightforward methodology to optimize the HC dynamics for hot carrier solar cells by element doping.

Mn doping modulates the hot carrier dynamics in all-inorganic lead halide perovskite nanocrystals according to the excitation energy.