Synthesis,Crystal Structure,Fluorescent and Antioxidation Properties of Cerium(III) and Europium(III) Complexes with Bis(3‐methoxysalicylidene)‐3‐oxapentane‐1,5‐diamine

Two aliphatic ether Schiff base lanthanide complexes (Ln = Eu, Ce) with bis(3‐methoxysalicylidene)‐3‐oxapentane‐1,5‐diamine (Bod), were synthesized and characterized by physicochemical and spectroscopic methods. [Eu(Bod)(NO₃)₃] ( 1 ) is a discrete mononuclear species and [Ce(Bod)(NO₃)₃DMF]_∞ ( 2 ) exhibits an inorganic coordination polymer. In the two complexes, the metal ions both are ten‐coordinated and the geometric structure around the Ln^III atom can be described as distorted hexadecahedron. Under excitation at room temperature, the red shift in the fluorescence band of the ligand in the complexes compared with that of the free ligand can be attributed to coordination of the rare earth ions to the ligand. Moreover, the antioxidant activities of the two complexes were investigated. The results demonstrated that the complexes have better scavenging activity than both the ligand and the usual antioxidants on the hydroxyl and superoxide radicals.     

Review: recent advances and future development of metal complexes as anticancer agents

Since the initial discovery of applications of platinum complexes in the clinical treatment of many kinds of cancers, the efficiency of platinum complexes in inhibiting the proliferation of various types of tumors surprised researchers working on the development of anticancer drugs. Meanwhile, despite the potent clinical treatment patients get from platinum complexes, there are also disadvantages including limited solubility in aqueous media and side effects like ototoxicity, myelosuppression, nephrotoxicity, and poor selectivity toward healthy cells. For this reason, efforts have been made to search for novel solutions. Non-platinum complexes (like Fe, Pd, Ru, Cu, Bi, Zn, etc.) were found with potential anticancer activities. We here review the properties of five metal complexes as anticancer agents and make comparisons among them in biological features and cytotoxic activity. Seeking the interrelation between microstructure and mechanism of anticancer, we hope this review provides distinct insights into future study of anticancer agents.     

NMR and theoretical study on the linking properties of peroxovanadium(V) complexes with the 3-aminomethyl-pyridine derivatives

To understand the substitution effects of 3-aminomethyl-pyridine on the reaction equilibrium, the interactions between a series of 3-aminomethyl-pyridine derivatives and peroxovanadium(V) complex [OV(O₂)₂(D₂O)]^?/[OV(O₂)₂(HOD)]^? in solution were explored by the combined use of multinuclear (¹H, ¹³C, and ⁵¹V) magnetic resonance spectroscopy together with HSQC in 0.15 M NaCl ionic medium for mimicking the physiological conditions. Some direct NMR data are given for the first time. The relative reactivity among the 3-aminomethyl-pyridine derivative ligands are N-(pyridin-3-ylmethyl)acetamide (1) ≈ N-(pyridin-3-ylmethyl)propionamide (2) > N-(pyridin-3-ylmethyl)pivalamide (3) > t-butyl(pyridin-3-ylmethyl)carbamate (4). The competitive coordination results in the formation of a series of new six-coordinate peroxovanadium species [OV(O₂)₂L]^? (L = 1–4). The results of density functional calculations indicated that the solvation effects play an important role in these reactions, providing a reasonable explanation on the relative reactivity of the 3-aminomethyl-pyridine derivatives.     

Highly fluorescent carbon polymer dots prepared at room temperature,and their application as a fluorescent probe for determination and intracellular imaging of ferric ion

Carbon polymer dots (CPDs) were prepared by a one-pot aqueous synthetic route from ascorbic acid and diethylenetriamine at room-temperature. The CPDs under 350-nm excitation exhibit blue fluorescence peaking at 430 nm with a quantum yield of 47%. Other features include an average diameter of 5 nm, a fluorescence that is independent of the excitation wavelength, good water dispersibility and photostability, and excellent biocompatibility. The CPDs are shown to be viable fluorescent probes for ferric ion which acts as a strong quencher. The response to Fe(III) is linear in the 0.2 to 10 μM concentration range, and the detection limit is 0.1 μM. The probe was applied to the determination of Fe(III) in environmental waters and to intracellular imaging of ferric ions in HeLa cells.

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Graphical abstract Carbon polymer dots (CPDs) are prepared from ascorbic acid and diethylenetriamine (DETA) at room-temperature (RT). The RT-CPDs exhibit excellent optical performance, biocompatibility and selectivity of quenching by ferric ions. This can be applied for determination and intracellular imaging of ferric ion.

     

Transition-metal-free trifluoromethylthiolation and difluoromethylthiolation of thiols with trifluoromethanesulfonyl chloride and difluoromethanesulfonyl chloride

Triphenylphosphine-mediated metal-free trifluoromethylthiolation and difluoromethylthiolation of thiols by CF₃SO₂Cl and CHF₂SO₂Cl to synthesize trifluoromethyl disulfides and difluoromethyl disulfides, respectively, was achieved at room temperature. Iodine generated in situ from iodide facilitated this reaction via the formation of iodotriphenylphosphonium iodide which could serve as a reducing agent in this transformation. Readily available reagents and mild reaction conditions without transition-metals allow this protocol to be more practical than traditional methods.     

山西典型高铝煤灰熔融及黏温特性改性实验研究

以山西典型高铝煤为研究对象,研究了工业助熔剂石灰石、黏土以及两者的复合助熔剂对其灰熔融特性及黏温特性的影响。结果表明,随着助熔剂含量的增加,煤灰熔融流动温度下降;石灰石的助熔效果优于黏土,复合助熔剂效果优于单一助熔剂。添加石灰石使灰渣临界黏度温度tcv显著降低,添加黏土使其渣型向玻璃渣转变,复合助熔剂较单一助熔剂存在显著协同作用,即能同时实现tcv的降低和渣型的有利转变。对山西典型高铝煤两渡煤,在复合助熔剂添加量为4%(2%石灰石+2%黏土)时,不仅其渣型向玻璃渣转变,且tcv较单独添加石灰石(2%)降低133℃,较单独添加黏土(6%)降低222℃。矿物质分析结果证实了助熔剂的助熔原理。添加复合助熔剂改性的山西高铝煤可达到工业气流床气化对煤种的要求。     

金属-有机纳米管分散固相萃取-气相色谱-串联质谱高灵敏分析环境水样中痕量多氯联苯

采用含铅金属-有机纳米管为吸附剂,基于分散固相萃取和气相色谱-串联质谱建立了一种高灵敏分析环境水样中痕量多氯联苯的方法.采用正交设计响应面法对影响萃取效果的重要因素(如离子强度、萃取时间和吸附剂用量等)进行了优化.获得的最优条件为:离子强度4.92 %(w/V)NaCl,萃取时间4.5 min,正己烷为解吸剂,吸附剂用量62.5 mg.在优化条件下,方法的线性范围为2~1000 ng/L,检出限为0.26~0.82 ng/L. 日内和日间相对标准偏差分别为0.8%~5.5% (200 ng/L, n=6)和2.7%~7.4% (200 ng/L, n=6).将本方法应用于实际环境水样中多氯联苯的分析,回收率为78.9%~113.3%,结果满意.     

Transport Coefficients of Two-temperature Lithium Plasma for Space Propulsion Applications

Lithium has been proposed as an attractive metal propellant for advanced electric propulsion. In our current work, transport coefficients including the viscosity, thermal conductivity, and electrical conductivity of lithium plasma under both the equilibrium and non-equilibrium conditions are calculated based on a two-temperature model. The collision integrals used in calculating the transport coefficients are significantly more accurate than values used in previous theoretical studies, resulting in more reliable values of the transport coefficients. Results are computed for different degrees of thermal non-equilibrium, i.e. the ratio of electron to heavy particle temperatures, from 1 to 15, with the electron temperature ranging from 300 to 60,000 K in a wide pressure range from 0.0001 to 100 atm. We compare our calculated results with existing published results and discrepancies are found and explained.     

APPLICATION OF VARIABLE-FIDELITY MODELS TO AERODYNAMIC OPTIMIZATION

For aerodynamic shape optimization, the approximation management framework (AMF) method is used to organize and manage the variable-fidelity models. The method can take full advantage of the low-fidelity, cheaper models to concentrate the main workload on the low-fidelity models in optimization iterative procedure. Furthermore, it can take high-fidelity, more expensive models to monitor the procedure to make the method globally convergent to a solution of high-fidelity problem. Finally, zero order variable-fidelity aerodynamic optimization management framework and search algorithm are demonstrated on an airfoil optimization of UAV with a flying wing. Compared to the original shape, the aerodynamic performance of the optimal shape is improved. The results show the method has good feasibility and applicability.     

心电激励下的人体左心室力学响应分析

人体心脏通过电兴奋引起的心肌收缩实现泵血功能 ,而心肌的力学特性高度依赖于肌纤维结构。本文根据肌纤维旋向和复合材料理论以及电生理心脏模型建立了左心室的有限元机械模型 ,仿真研究了左心室在心电兴奋力作用下的力学响应。结果表明左心室的收缩过程是十分复杂的 ,包括轴向和径向的收缩及绕长轴的不同程度的旋转扭曲。从总体趋势上看 ,心尖处变形最为严重。此外 ,仿真结果还表明 ,心壁应力分布不均匀 ,从内壁到外壁有所减少 ;在心尖和心底部应力较大 ,其中内壁心尖处应力最大。这些结果说明了心脏的力学特性与心肌纤维结构、左心室的几何形状以及电兴奋刺激密切相关。作者将本文的仿真结果与医学图像及其它模型进行了对比分析 ,结果表明了该模型用于分析心肌力学功能特性的可行性