Online high‐pH reversed‐phase liquid chromatography × low‐pH reversed‐phase liquid chromatography tandem electrospray ionization mass spectrometry combined with pulse elution gradient in the first dimension for the analysis of alkaloids in Macleaya cordata (willd.) R. Br

An online high‐pH reversed‐phase liquid chromatography× low‐pH reversed‐phase liquid chromatography tandem electrospray ionization mass spectrometry combined with pulse elution gradient in the first dimension was constructed to separate and identify alkaloids from Macleaya cordata (willd.) R. Br. The modulation was performed by using a dual second dimensional columns interface combined with a make‐up dilution pump, which is responsible for dilution and neutralization of the first dimensional effluent, and the dual second dimensional columns integrated the trapping and the separation function to reduce the second dimension system dead volume. Taking advantage of the dissociable characteristics of alkaloids, mobile phases with different pH values were applied in the first dimension (pH 9.0) and the second dimension (pH 2.6) to improve the orthogonality of two‐dimension separation. Besides, the pulse elution gradient in first dimension and second dimensional gradient were carefully optimized and much better separation was achieved compared to the separation with the traditional two‐dimensional liquid chromatography approach. Finally, mass measurement was performed for alkaloids in M. cordata (willd.) R. Br. by coupling proposed two‐dimensional liquid chromatography system with triple quadrupole mass spectrometry, and 39 alkaloids were successfully identified by comparing the obtained result with the former reported results.     

Kinetics and thermodynamics of rebaudioside A adsorption on a strongly acidic cation exchange resin

To explain the mechanism underlying the adsorption of stevia's polar component rebaudioside A in hydrophilic interaction liquid chromatography mode, the characteristics of rebaudioside A adsorption on various resins in an organic‐solvent‐rich system were studied. Among the tested resins, the strongly acidic cation resin FPC11 showed the best adsorption behavior for rebaudioside A. The factors affecting the adsorption kinetics of the resin for rebaudioside A are discussed. The results showed that the pseudo‐second‐order reaction model and intra‐particle diffusion model best described the adsorption kinetics of rebaudioside A on the resin. The adsorption rate was controlled by physical sorption, mainly via electron sharing or electron transfer between the adsorbent and the adsorbate. The adsorption process with multiple stages involved weak initial adsorption behavior. Thermodynamic studies showed that the adsorption of rebaudioside A on the resin was not an ideal monolayer adsorption, but mutual adsorption effects between the adsorbates. The adsorption was a spontaneous, entropy‐increasing endothermic process. The synergistic effect of hydrogen bonding and ion–dipole was a possible driving force.     

CuO/Cu2O nanowire array photoelectrochemical biosensor for ultrasensitive detection of tyrosinase

Photoelectrochemical(PEC) biosensors have shown great promise in bioanalysis and diagnostic applications in recent years. In this work, the CuO/Cu_2O nanowire array(CuO/Cu_2O Nanowire) supported on copper foam was prepared as a photocathode for detection of tyrosinase though quinone-chitosan conjugation chemistry method. The in-situ generated quinones that were the catalytic product of tyrosinase acted as electron acceptors, which were captured by the chitosan deposited on the surface of the electrode. Direct immobilization of electron acceptor on the electrode surface improved the photocurrent conversion efficiency and thus sensitivity. The as-prepared biosensor can realize a rapid response in a wide linear range of 0.05 U/mL to 10 U/mL with the detection limit as low as 0.016 U/mL of tyrosinase. The current work provides a new perspective to design and develop highly sensitive and selective PEC biosensor.     

多层CT与DSA对急性冠状动脉综合征患者冠状动脉支架置入术后通畅性及狭窄程度的影响

研究多层CT与DSA对急性冠状动脉综合征患者冠状动脉支架置入术后通畅性及狭窄程度的影响。以我院2017年8月-2018年11月在我院诊断治疗的急性冠脉综合征患者80例作为研究对象,对所有患者进行经皮冠状动脉介入治疗(percutaneous coronary intervention,PCI)手术后,分别进行DSA检查以及64排螺旋CT检查。分析不同检查的冠状动脉狭窄、通畅性之间的差异以及不同检查的一致性。通过对CT检查结果以及DSA检查结果的配对卡方检验,两组患者的检查结果之间的差异不存在统计学意义,两种检查对患者的冠状动脉的狭窄情况诊断一致性较好;两种检查方法对患者的管壁厚度以及管径直径诊断之间的差异不存在统计学意义,两种检验方法对患者的管壁厚度以及管径直径诊断一致性较好。总之,多层CT与DSA对急性冠状动脉综合征患者冠状动脉支架置入术后通畅性及狭窄程度的诊断具有较高的一致性,建议临床推广。     

Core‐Shell Structured Layered Lanthanide‐Organic Complexes with Stilbazolium‐type Dye Encapsulation for Multifunctional Performances

Host‐guest encapsulation of functional organic dye into a porous metal‐organic framework can give rise to the development of new functional materials. In this work, by intercalating the stilbazolium‐type dye (DEAST)I (4′‐diethylamino‐N‐methyl stilbazolium) into four lanthanide layered metal‐organic complexes (Ln‐LMOCs), i. e. {[Ln(BTB)(H₂O)₂]?3(DMF)?2(H₂O)}_n (Ln=La (1), Nd (2), Sm (3), Er (4)), four responsive (DEAST)I@Ln‐LMOC composites have been prepared, serving as multifunctional performance platform. The core–shell structures of (DEAST)I@Ln‐LMOC composites have been fully characterized by IR, UV/Vis, PXRD, SEM, TEM, TGA and ESR. Significantly, after intercalation of dyes, the (DEAST)I@Ln‐LMOC composites exhibit enhanced luminescent sensing properties in detecting Fe³⁺ with much higher water stabilities. The luminescent sensing behavior stems from the fluorescence resonance energy transfer (FRET) from the π‐electron‐rich BTB ligands to the Fe³⁺, and their higher water stabilities are induced by electrostatic interactions and lower porosity. Specially, the characteristic emissions of Sm³⁺ will not be affected after the encapsulation guest dyes, which provide a theoretical guide for the modulation of luminescence devices. Finally, better ion conductivities and diminished photocurrents can be achieved after the embedding of the functional organic dye. In all, the formation of (DEAST)I@Ln‐LMOC composites with core–shell structures can be utilized as a multifunctional platform with good stability.     

Tuning Magnetic Anisotropy in a Class of Co(II) Bis(hexafluoroacetylacetonate) Complexes

Tuning the magnetic anisotropy of metal ions remains highly interesting in the design of improved single‐molecule magnets (SMMs). We herein report synthetic, structural, magnetic, and computational studies of four mononuclear Co^II complexes, namely [Co(hfac)₂(MeCN)₂] ( 1 ), [Co(hfac)₂(Spy)₂] ( 2 ), [Co(hfac)₂(MBIm)₂] ( 3 ), and [Co(hfac)₂(DMF)₂] ( 4 ) (MeCN=acetonitrile, hfac=hexafluoroacetylacetone, Spy=4‐styrylpyridine, MbIm=5,6‐dimethylbenzimidazole, DMF=N,N‐dimethylformamide), with distorted octahedral geometry constructed from hexafluoroacetylacetone (hfac) and various axial ligands. By a building block approach, complexes 2 – 4 were synthesized by recrystallization of the starting material of 1 from various ligands containing solution. Magnetic and theoretical studies reveal that 1 – 4 possess large positive D values and relative small E parameters, indicating easy‐plane magnetic anisotropy with significant rhombic anisotropy in 1 – 4 . Dynamic alternative current (ac) magnetic susceptibility measurements indicate that these complexes exhibit slow magnetic relaxation under external fields, suggesting field‐induced single‐ion magnets (SIMs) of 1 – 4 . These results provide a promising platform to achieve fine tuning of magnetic anisotropy through varying the axial ligands based on Co(II) bis(hexafluoroacetylacetonate) complexes.     

Hybrid-triggered control for fuzzy Markov jump systems under input saturation

Nonlinear Dynamics - This article investigates the issue of hybrid-triggered control for fuzzy Markov jump system under input saturation. First, a hybrid-triggered control scheme is presented,...     

α稳定噪声下基于随机共振的微弱诱发电位潜伏期延长检测

提出了一种基于分数低阶统计量及随机共振技术的鲁棒性时问延迟估计新方法--随机共振共变时间延迟估计(SRCTDE)算法,用于在低混合信噪比条件下及a稳定噪声下微弱诱发电位信号潜伏期延长的检测.SRCTDE算法首先利用带嗓诱发电位信号与双稳态非线性动力系统之间的随机共振效应提高参考及待测诱发电位信号的混合信噪比,在最大对称...     

基于可靠度与置信度的双可靠性指标安全系数方法

在可靠度指标的基础上引入了置信度指标,提出可靠度与置信度的双可靠性指标的安全系数概念,并根据可靠性理论推导出新计算公式.该公式考虑了实验数据样本容量的影响,给出了小子样实验数据条件下的安全系数取值.将新安全系数应用于结构可靠性设计,算例结果表明,与其他方法相比,此方法计算结果安全系数更合理,且简单实用,能满足结构可靠性设计的要求,可取得显著的减重效果.