Pincer‐Type Platinum(II) Complexes Containing N‐Heterocyclic Carbene (NHC) Ligand: Structures,Photophysical and Anion‐Binding Properties,and Anticancer Activities

Two classes of pincer‐type Pt^II complexes containing tridentate N‐donor ligands ( 1 – 8 ) or C‐deprotonated N^C^N ligands derived from 1,3‐di(2‐pyridyl)benzene ( 10 – 13 ) and auxiliary N‐heterocyclic carbene (NHC) ligand were synthesized. [Pt(trpy)(NHC)]²⁺ complexes 1 – 5 display green phosphorescence in CH₂Cl₂ (Φ: 1.1–5.3 %; τ: 0.3–1.0 μs) at room temperature. Moderate‐to‐intense emissions are observed for 1 – 7 in glassy solutions at 77 K and for 1 – 6 in the solid state. The [Pt(N^C^N)(NHC)]⁺ complexes 10 – 13 display strong green phosphorescence with quantum yields up to 65 % in CHCl₃. The reactions of 1 with a wide variety of anions were examined in various solvents. The tridentate N‐donor ligand of 1 undergoes displacement reaction with CN^? in protic solvents. Similar displacement of the N^C^N ligand by CN^? has been observed for 10 , leading to a luminescence “switch‐off” response. The water‐soluble 7 containing anthracenyl‐functionalized NHC ligand acts as a light “switch‐on” sensor for the detection of CN^? ion with high selectivity. The in vitro cytotoxicity of the Pt^II complexes towards HeLa cells has been evaluated. Complex 12 showed high cytotoxicity with IC₅₀ value of 0.46 μM , whereas 1 – 4 and 6 – 8 are less cytotoxic. The cellular localization of the strongly luminescent complex 12 traced by using emission microscopy revealed that it mainly localizes in the cytoplasmic structures rather than in the nucleus. This complex can induce mitochondria dysfunction and subsequent cell death.     

Small molecule‐mediated glass transition of acrylic copolymers: Effect of hydrogen bonding strength on glass transition temperature

Poly(styrene‐co‐ethyl acrylate) [P(St‐co‐EA)] with different ratios of St/EA was mixed with the small molecule 4,4′‐thio‐bis(6‐tert‐butyl‐m‐methyl phenol) (AO300) to investigate the influence of hydrogen bonding strength on the glass transition behavior. The glass transition temperature (T_g) linearly increased after adding AO300, and the slope value decreased with increased St/EA ratio. All lines could be extended to 62 °C, demonstrating that T_g of the small molecule in situ detected by the polymer chain was much higher than that by small molecule itself (29 °C). Fourier transform infrared spectroscopy analysis showed that the small molecules began to be self‐associated at a concentration where the hydrogen bonded carbonyl ratio of the bulk polymer was approximately 0.5 and irrespective of the St/EA ratio. Above the critical loading, the mixture's T_g negatively deviated from the linearly extended lines because of self‐association of the small molecules. The apparent T_g of AO300 was found to strongly depend on intermolecular hydrogen bonding number and strength. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 400–408     

负反馈诱发神经电振荡的反常现象的复杂动力学

传统观念认为,负反馈容易使系统达到稳定平衡点而正反馈容易引起振荡.本研究基于神经元理论模型,提出了负反馈可以诱发稳定平衡点、也就是静息、变为振荡、也就是放电的新观点.在Hopf分岔点附近,作用在静息上的一次足够大的负向脉冲电流的抑制性刺激,能够引起一个动作电位及随后的衰减振荡的后电位;而能够在后电位上诱发出动作电位的负脉冲电流强度阈值也是衰减振荡的.在模型中,引入具有时滞($\tau$)的负反馈来模拟抑制性自突触,一个动作电位诱发的负反馈自突触电流会作用到比动作电位延迟$\tau$的后电位上.随时滞增加,能够诱发出放电的负反馈增益强度阈值呈现出具有衰减振荡特点的类似多重相干共振的特性,衰减振荡的周期与电流阈值曲线的周期以及分岔点附近的放电周期相关.另外,负反馈还能诱发出放电与静息共存的复杂行为.本研究的结果不仅揭示了负反馈的新的反常调控作用,还有助于理解在现实神经系统中存在的慢抑制性自突触的潜在功能.      

Fractional-order sliding mode control of uncertain QUAVs with time-varying state constraints

Nonlinear Dynamics - In this paper, a novel robust fractional-order sliding mode (FOSM)-based state constrained control scheme is designed for uncertain quadrotor UAVs (QUAVs). Model uncertainties...     

时滞Rucklidge系统Hopf分岔分析与电路实现

以一类新的单时滞Rucklidge系统为分析对象，通过计算时滞系统的平衡点，分析该系统在各平衡点的稳定性和Hopf分岔的存在性，得到其发生Hopf分岔的条件。Matlab多组数值仿真验证了理论分析的正确性。基于此设计了一种可切换时滞与非时滞的混沌电路，并运用Multisim14.0进行仿真，实验结果表明，该电路可行且有效。     

Dose‐dependent exposure profile and metabolic characterization of notoginsenoside R1 in rat plasma by ultra‐fast liquid chromatography–electrospray ionization–tandem mass spectrometry

Notoginsenoside R₁ (NGR₁), a diagnostic protopanaxatriol‐type (ppt‐type) saponin in Panax notoginseng, possesses potent biological activities including antithrombotic, anti‐inflammatory, neuron protection and improvement of microcirculation, yet its pharmacokinetics and metabolic characterization as an individual compound remain unclear. The aim of this study was to investigate the exposure profile of NGR₁ in rats after oral and intravenous administration and to explore the metabolic characterization of NGR₁. A simple and sensitive ultra‐fast liquid chromatographic–tandem mass spectrometric method was developed and validated for the quantitative determination of NGR₁ and its major metabolites, and for characterization of its metabolic profile in rat plasma. The blood samples were precipitated with methanol, quantified in a negative multiple reaction monitoring mode and analyzed within 6.0 min. Validation parameters (linearity, precision and accuracy, recovery and matrix effect, stability) were within acceptable ranges. After oral administration, NGR₁ exhibited dose‐independent exposure behaviors with t_1/2 over 8.0 h and oral bioavailability of 0.25–0.29%. A total of seven metabolites were characterized, including two pairs of epimers, 20(R)‐notoginsenoside R₂/20(S)‐notoginsenoside R₂ and 20(R)‐ginsenoside Rh₁/20(S)‐ginsenoside Rh₁, with the 20(R) form of saponins identified for the first time in rat plasma. Five deglycometabolites were quantitatively determined, among which 20(S)‐notoginsenoside R₂, ginsenoside Rg₁, ginsenoside F₁ and protopanaxatriol displayed relatively high exploration, which may partly explain the pharmacodynamic diversity of ginsenosides after oral dose.