Simultaneous quantification of five biogenic amines based on LC–MS/MS and its application in honeybee venom from different subspecies

The use of honeybee venom in traditional medicine is increasing due to its unexpected beneficial effects in the treatment of diseases. In this study, a simple and environmentally friendly sample preparation procedure was developed to quantify five biogenic amines—histamine, 5-hydroxytryptamine, dopamine, adrenaline, and noradrenaline—in honeybee venom using high-performance liquid chromatography tandem mass spectrometry. The instrument and sample preparation method were optimized to achieve stable, sensitive, and accurate quantification of the five biogenic amines. The peak purities of five biogenic amines in bee venom were examined using a diode array detector to ensure that endogenous impurities will not interfere with biogenic amines during the chromatographic separation procedure. The correlation coefficient of each compound was higher than 0.998 in the range of 0.5–1000 ng/mL. The limits of detection and quantification of the developed method ranged between 0.09 and 0.17, and 0.3 and 0.59 μg/g, respectively. The average recoveries of spiked biogenic amines with different concentrations were higher than 70.95%, and the intra- and intermediate-day precisions were lower than 7.51% and 10.17%, respectively. The carry-over between each injection and the stability of the target analytes were also evaluated to ensure the effectiveness of this method. The data obtained are presented in various formats, including boxplot, heat map, and principal component analysis diagram, to visualize the differences in the biogenic amine contents of the honeybee venoms from different subspecies. This method hopes to provide the opportunity to distinguish the bee venom produced by different subspecies.     

Synthesis of tertiary amine‐based pH‐responsive polymers by RAFT Polymerization

Well‐defined tertiary amine‐based pH‐responsive homopolymers and block copolymers were synthesized via reversible addition‐fragmentation chain transfer (RAFT) polymerization using 4‐cyanopentanoic acid dithiobenzoate (CPAD) as the RAFT agent for homopolymers and a poly(ethylene glycol) (PEG) macro‐RAFT agent for the block copolymers. ¹H NMR and gel permeation chromatography results confirmed the successful synthesis of these homopolymers and block copolymers. Kinetics studies indicated that the formation of both the homopolymers and the block copolymers were well defined. The pKa titration experiments suggested that the homopolymers and the related block copolymers have a similar pKa. The dynamic light scattering investigation showed that all of the block copolymers underwent a sharp transition from unimers to micelles around their pKa and the hydrodynamic diameter (D_h) was not only dependent on the molecular weight but also on the composition of the block copolymers. The polymer solution of PEG‐b‐PPPDEMA formed the largest micelle compare to the PEG‐b‐PDPAEMA and PEG‐b‐PDBAEMA with a similar molecular weight. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1010–1022     

Protein Staining Agents from Cationic and Neutral Luminescent Iridium(III) Complexes

Seven luminescent iridium(III) complexes were prepared to investigate the relationships between chemical structures and properties of protein staining. For the first time, the effect of the main ligand, the π conjugation effect of the ancillary ligand, and the charge effect of organometallic complexes on protein staining has been revealed. Most importantly, this study gives the first experimental evidence of the potential applications of charge‐neutral organometallic complexes in protein staining, which could open an avenue of exploiting novel protein staining agents in the future.     

Direct Estimation of the Surface Location of Immobilized Functional Groups for Concerted Catalysis Using a Probe Molecule

The location of active sites during concerted catalysis by a metal complex and tertiary amine on a SiO₂ surface is discussed based on the interaction between the functionalized SiO₂ surface and a probe molecule, p‐formyl phenylboronic acid. The interactions of the probe molecule with the surface functionalities, diamine ligand, and tertiary amine, were analyzed by FT‐IR and solid‐state ¹³C and ¹¹B MAS NMR. For the catalyst exhibiting high 1,4‐addition activity, the diamine ligand and tertiary amine base exist in closer proximity than in the catalyst with low activity.     

不同有机碱对铕-2-羟基喹啉-4-羧酸配合物发光性能的影响

分别在有机碱三乙胺、三丙胺和三丁胺的作用下,使用2-羟基喹啉-4-羧酸(H2hqc)与EuCl3·6H2O反应制备了3种配合物Eu(Hhqc)3(TEL)、Eu(Hhqc)3(TPL)和Eu(Hhqc)3(TBL)。通过元素分析、热重分析、摩尔电导率、紫外光谱、荧光光谱、荧光寿命和量子产率等对配合物进行了表征。所有配合物均在580,592,613,654,702 nm附近产生5条谱带,为Eu3+的特征发射,归属为5D0→7FJ(J=0,1,2,3,4)能级间的跃迁,荧光寿命分别为2.22,3.29,3.31 ms,量子产率分别为0.011,0.019,0.028。随着有机胺碳链长度的增加,配合物的荧光强度依次增大,表明有机碱参与了配合物的分子组成。     

强耦合腔-QED系统中原子的纳秒脉冲激发光谱研究

本文在多原子强耦合腔-QED系统中,利用脉冲宽度为5 ns的强脉冲光在垂直于腔轴方向直接激发原子,脉冲的峰值功率为40 mW,通过光学腔观测激发原子辐射到腔中的光子获得相应的激发光谱。我们发现当光场频率和原子跃迁失谐±80 MHz时原子激发率达到最大,而在共振时原子激发被抑制。我们建立了脉冲光与三能级原子相互作用的模型,通过缀饰态能够解释此现象。     

Implementation of a separate fluid-neutral energy equation in SOLPS-ITER and its impact on the validity range of advanced fluid-neutral models

In plasma edge transport codes for nuclear fusion devices, fluid-neutral models offer an interesting alternative to the currently used kinetic Monte Carlo simulations, especially for cases of high ion-neutral collisionality. In this paper, we elaborate a separate neutral energy equation in the state-of-the-art SOLPS-ITER code suite, which previously assumed perfect ion-neutral temperature equilibration. Furthermore, we study the coupled plasma-neutral solutions for a range of divertor operating regimes, proving the validity of these fluid-neutral models for high-recycling and detached regimes.     

Synthesis,characterization, and cytotoxic activity studies of new N4O complexes derived from 2-({3-[2-morpholinoethylamino]-N3-([pyridine-2-yl]methyl) propylimino} methyl)phenol

A new unsymmetrical five-coordinate Schiff base ligand (HL) with an N₄O donor set ( 2 ) has been prepared by condensation of N1-(2-morpholinoethyl)-N1-([pyridine-2-yl]methyl)propane-1,3-diamine with 2-hydroxy-benzaldehyde. Metal complexes [ML]ⁿ⁺ (M = Zn²⁺, Cd²⁺, Mn²⁺, Cu²⁺, Ni²⁺, Ag⁺, Fe³⁺, and Co²⁺ ( 3–10 ) were synthesized by the reaction of the ligand and metal salts in ethanol. The resulting products were characterized by elemental analyses, infrared, ¹H and ¹³C nuclear magnetic resonance spectra (in the case of Cd and Zn complexes), UV–Vis, electrospray ionization-mass spectrometric, and conductivity measurements. The structure of the complexes [ZnL](ClO₄) ( 3 ), [CdL](ClO₄) ( 4 ), and [CuL](ClO₄) ( 7 ) has been determined by single-crystal X-ray diffraction analysis. The metal complexes were determined to have a distorted trigonal bipyramidal (Zn and Cd) or a distorted square pyramidal (Cu) geometry. The cytotoxic potential of each compound (1–10) against MCF-7 and MDA-MB-231 (breast cancer cells), PC-3 (prostate cancer cells), and WI-38 human normal lung fibroblast cells was evaluated using the MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazolium bromide) assay. Compounds 1, 2, and 10 did not display any activity toward any cell line tested. None of the compounds except compound 8 was cytotoxic toward PC-3. Compounds 4 and 8 showed the highest cytotoxic activity against the MCF-7 and MDA-MB-231 cell lines. Because compounds 3, 6, and 9 have similar half-maximal inhibitory concentration values against cancer cells and normal cells, these compounds displayed poor selectivity between cancer and normal cells. More importantly, it was observed that compound 5 acts differently toward different types of cell lines. For example, it displays lower cytotoxicity against the WI-38 normal cell line than it does against the MDA-MB-231 cell line.