Biological and catalytic evaluation of Ru(II)‐p‐cymene complexes of Schiff base ligands: Impact of ligand appended moiety on photo‐induced DNA and protein cleavage,cytotoxicity and C‐H activation

Two organometallic Ru(II)‐p‐cymene complexes of the type [Ru(η⁶‐p‐cymene)(L)Cl]PF₆ 1 and 2 , where L is N,N‐bis(4‐isopropylbenzylidene)ethane‐1,2‐diamine (bien, L1 ) or N,N‐bis (pyren‐2‐ylmethylene)ethane‐1,2‐diamine (bpen, L2 ) have been prepared and characterized well. Because of appended pyrenyl groups in coordinated bpen ligand, the complex 2 exhibits higher DNA and protein binding than complex 1 in which isopropylbenzyl groups are incorporated. Interestingly, the luminescent characteristic complex 2 is unique in displaying DNA cleavage after light activation by UVA light at 365 nm through oxygen dependent mechanism. AFM analysis attests the photo‐induced DNA fragmentation ability of complex 2 . Also, the complex 2 cleaves the protein after light exposure in a non‐specific manner suggesting that it can act as a protein photo cleaving agent. In contrast to the trend of DNA and protein interaction of complexes, the complex 1 exhibits cytotoxic activity against human breast carcinoma ( MCF‐7 ) and liver carcinoma ( HepG2 ) with potency higher than that of complex 2 due to enhanced hydrophobicity of isopropyl groups present in p‐cymene and bien ligands. Indeed, complex 2 is inactive against MCF‐7 and HepG2 cancer cell lines even up to 200 μM concentration. The AO/EB staining assay reveals that the complex 1 is able to induce late apoptotic mode of cell death in breast cancer cells, which is further confirmed by inter‐nucleosomal DNA cleavage. Furthermore, the complexes 1 and 2 are evaluated for their catalytic activities and found to be working well for the β‐carboline directed C–H arylation to afford the desired products in good yield (40–47%).     

Pattern transition and regulation in a subthalamopallidal network under electromagnetic effect

Although the significant roles of magnetic induction and electromagnetic radiation in the neural system have been widely studied, their influence on Parkinson's disease (PD) has yet to be well explored. By virtue of the magnetic flux variable, this paper studies the transition of firing patterns induced by magnetic induction and the regulation effect of external magnetic radiation on the firing activities of the subthalamopallidal network in basal ganglia. We find: (i) The network reproduces five typical waveforms corresponding to the severity of symptoms: weak cluster, episodic, continuous cluster, episodic, and continuous wave. (ii) Magnetic induction is a double-edged sword for the treatment of PD. Although the increase of magnetic coefficient may lead the physiological firing activity to transfer to pathological firing activity, it also can regulate the pathological intensity firing activity with excessive β-band power transferring to the physiological firing pattern with weak β-band power. (iii) External magnetic radiation could inhibit continuous tremulous firing and β-band power of subthalamic nucleus (STN), which means the severity of symptoms weakened. Especially, the bi-parameter plane of the regulation region shows that a short pulse period of magnetic radiation and a medium level of pulse percentage can well regulate pathological oscillation. This work helps to understand the firing activity of the subthalamopallidal network under electromagnetic effect. It may also provide insights into the mechanisms behind the electromagnetic therapy of PD-related firing activity.     

绝缘环打火研究

绝缘问题是高电压、高场强器件和设备中不可回避的问题,是决定器件、设备运行参数和稳定性的重要因素。针对一台直线感应加速器调试中出现的加速腔绝缘环在带束负载情况下的真空沿面闪络现象,进行了分析和研究。分析表明,在排除设计、材料、加工、洁净和真空度等常规异常因素后,导致绝缘环真空沿面闪络的可能因素是电子在绝缘环表面的吸附和累积,绝缘环上累积的电子来源和加速器中加速、传输的电子束的丢失有关。从加速腔工作状态出发,分析绝缘环表面积累电荷和丢失电子束的相关途径,进而提出相应的技术措施,以提高加速腔运行稳定性。     

Second harmonic magnetoacoustic responses of magnetic nanoparticles in magnetoacoustic tomography with magnetic induction

Due to the unique magnetic, mechanical and thermal properties, magnetic nanoparticles(MNPs) have comprehensive applications as the contrast and therapeutic agents in biomedical imaging and magnetic hyperthermia. The linear and nonlinear magnetoacoustic responses determined by the magnetic properties of MNPs have attracted more and more attention in biomedical engineering. By considering the relaxation time of MNPs, we derive the formulae of second harmonic magnetoacoustic responses(2H-MARs) for a cylindrical MNP solution model based on the mechanical oscillations of MNPs in magnetoacoustic tomography with magnetic induction(MAT-MI). It is proved that only the second harmonic magnetoacoustic oscillations can be generated by MNPs under an alternating magnetic excitation. The acoustic pressure of the 2H-MAR is proportional to the square of the magnetic field intensity and exhibits a linear increase with the concentration of MNPs. Numerical simulations of the 2H-MAR are confirmed by the experimental measurements for various magnetic field intensities and solution concentrations using a laser vibrometer. The favorable results demonstrate the feasibility of the harmonic measurements without the fundamental interference of the electromagnetic excitation, and suggest a new harmonic imaging strategy of MAT-MI for MNPs with enhanced spatial resolution and improved signal-to-noise ratio in biomedical applications.     

Performance analysis and design of quasi-cyclic LDPC codes for underwater magnetic induction communications

Magnetic induction (MI) communication is an effective scheme for underwater wireless communication. In this paper, we aim to design an underwater MI communication system based on Quasi-cyclic LDPC (QC-LDPC) codes. Firstly, for a given QC-LDPC code used in underwater MI communication, we propose a novel algorithm to evaluate its performance, which is named as underwater magnetic induction protograph (UWMIP) extrinsic information transfer algorithm. Furthermore, we present a differential evolution UWMIP (DE-UWMIP) algorithm, which incorporates the differential evolution method and the UWMIP algorithm. By this algorithm, we search the optimized QC-LDPC codes with best distance threshold. Simulation results show that the proposed algorithm is effective and provide a good guidance to design the underwater MI communication system.     

高频感应炉燃烧–红外吸收法测定银杏及银杏叶中的硫含量

采用高频感应炉燃烧–红外吸收法测定银杏叶、银杏果肉、银杏壳和银杏仁中的硫含量。样品以艾士卡试剂为熔融剂,在800℃马弗炉内熔融1 h,冷却后测定硫含量。硫的质量分数在0.40%~4.00%范围内与吸收峰面积呈良好的线性关系,线性相关系数为0.990 4,检出限为0.000 9%。测定结果的相对标准偏差为4.04%(n=11),平均加标回收率为101.03%。将红外吸收法与电感耦合等离子体原子发射光谱法及硫酸钡重量法进行比对试验,3种方法测定结果相一致。利用该方法测定了不同区域银杏叶中硫的含量,结果表明,风景区和居民区银杏叶干燥基全硫的含量较低,重工业区硫含量较高。对同一地区的银杏果肉、银杏壳、银杏仁中干燥基全硫的含量进行比较,结果表明银杏果肉硫含量最高,银杏壳次之,银杏仁最低。该方法灵敏度高,重现性好,可用于银杏及银杏叶中硫含量的准确测定。     

Kinetic Behavior of Quaternary Ammonium Hydroxides in Mixed Methane and Carbon Dioxide Hydrates

This study evaluates the kinetic hydrate inhibition (KHI) performance of four quaternary ammonium hydroxides (QAH) on mixed CH₄ + CO₂ hydrate systems. The studied QAHs are; tetraethylammonium hydroxide (TEAOH), tetrabutylammonium hydroxide (TBAOH), tetramethylammonium hydroxide (TMAOH), and tetrapropylammonium hydroxide (TPrAOH). The test was performed in a high-pressure hydrate reactor at temperatures of 274.0 K and 277.0 K, and a concentration of 1 wt.% using the isochoric cooling method. The kinetics results suggest that all the QAHs potentially delayed mixed CH₄ + CO₂ hydrates formation due to their steric hindrance abilities. The presence of QAHs reduced hydrate formation risk than the conventional hydrate inhibitor, PVP, at higher subcooling conditions. The findings indicate that increasing QAHs alkyl chain lengths increase their kinetic hydrate inhibition efficacies due to better surface adsorption abilities. QAHs with longer chain lengths have lesser amounts of solute particles to prevent hydrate formation. The outcomes of this study contribute significantly to current efforts to control gas hydrate formation in offshore petroleum pipelines.     

Synthesis and Reaction of Some Indenopyridine and Thieno[2,3-b]Indeno[2,1-e]Pyridine Derivatives

Synthesis of indenopyridine-2-thione derivatives 6a-e via reaction of compound 1 with thioamides 2a-e in good yields. Several thieno[2,3-b]indeno[2,1-e]pyridine 9a-e have been synthesized. Some of them was used as a key intermediate in synthesis of 10-12. On the other hand, compound 1 reacted with various reagents to yield 16, 19, 21-24.     

Ionic Copolymerizations

It is shown that for the reported instances of “random” copolymerization in cationic systems, N values related to relative reactivity may be derived for monomers. The N values approximate reasonably well the values of the function, exp (-e) - 1.23, where e is the polarity e of the Q-e scheme for free-radical copolymerizations.

In a recent paper [1] it was shown that for the reported instances [2-4] of “random” copolymerization (r₁,r₂ = 1) in cationic systems, N values, related to relative reactivity, might be derived for monomers, employing styrene as a base monomer (N = 1). Thus d[M₁]/d[M₂] =N₁[M₁]/N₂[M₂] (1)

where d[M₁]/d[M₂] is the instantaneous copolymer composition, [M₁]/[M₂] is the ratio of unreacted monomers, and N₁ and N₂ are parameters related to general monomer reactivity of monomers 1 and 2, respectively, in cationic copolymerization.     

Oxidative Stabilization of Poly(norbornene) Polymers Prepared by Ring Opening Metathesis Polymerization

Polymers prepared by ring opening methathesis polymerization contain double bonds along the backbone and are susceptible to oxidation during high temperature processing or device operation. To overcome this, we report a simple method to improve the oxidative stability of ROMP based polymers by inclusion of a small percentage of monomer functionalized with a radical scavenger in the feedstock. The oxidation induction temperature was improved from 111°C up to 262°C when 8 mol% of the functionalized comonomer was included in the feedstock. Modest improvements in the thermal decomposition temperature were also observed.