Rapid Multiphase Flow Dynamics Mapped by Single‐Shot MRI Velocimetry

A new, fast magnetic resonance imaging (MRI) method is described and applied to map flow fields in systems with internal velocities rapidly varying along the streamlines. While conventional MRI techniques encode the velocity information in a preparatory period prior to the imaging acquisition module, our technique repeatedly refreshes the velocity encoding during a single‐shot imaging sequence. In this way, the maximum acceleration responsible for velocity variation of the molecules is increased by up to two orders of magnitude compared to standard procedures. Besides being compatible with high acceleration, this pulse sequence is suited to acquiring in a single scan the multiple velocity images required to construct a full velocity vector map. The power of this new methodology is demonstrated by following the internal dynamics of toluene droplets levitating in a counterflow of water during mass transfer of acetone from the water phase into the drop in the presence of surface‐active impurities. The dramatic reduction in measurement time allows visualization for the first time of the important impact of even small concentrations of acetone on accumulation of surfactants at the drop’s surface.     

Characterization of bacterial lipid profiles by using rapid sample preparation and fast comprehensive two‐dimensional gas chromatography in combination with mass spectrometry

The bacteria fatty acid profile has been extensively studied for taxonomic classification purposes, since bacteria, in general, contain particular and rare fatty acids, compared with animal and plant tissues. As for any real‐world sample type, the development of rapid and reliable methods for (i) sample identification (in this case, bacterium type), and (ii) constituent identification (in this instance, the fatty acid profile) is desirable. In this research, a half‐an‐hour procedure, to analyze bacteria, was developed: a 2‐min one‐step sample preparation step was followed by a relatively fast comprehensive 2D GC‐MS separation (25 min). Furthermore, dedicated MS libraries were constructed for the identification of bacteria and fatty acids. Finally, data processing, only qualitative at this stage, was carried out with the support of a novel comprehensive 2D GC software.     

Similarities and Differences of the Active Sites in Basic and Advanced MgCl2‐Supported Ziegler‐Natta Propylene Polymerization Catalysts

Though preparation procedures of heterogeneous Ziegler‐Natta catalysts for propylene polymerization are sophisticated, it is uncertain whether the nature of the active sites is similar or different for different preparation procedures. In this study, the effects of preparation procedures on the nature of the active sites were investigated by stopped‐flow polymerization in combination with microstructure analysis of polymers. Both basic and advanced types of catalysts showed the same two kinds of isospecific active site, which indicated little influence of the preparation method on the active site structure. On the contrary, the ratios of the two kinds of isospecific sites were not the same, resulting in variation of average polymer properties.

     

载气流速对高场不对称波形离子迁移谱的影响

载气流速是影响高场不对称波形离子迁移谱(FAIMS)的重要参数.以自制的高场不对称波形离子迁移谱仪为实验平台,在射频电场幅值3 kV/cm,频率500 kHz,占空比0.36的条件下,研究了载气流速对苯离子迁移谱谱峰强度和半峰宽的影响.实验结果表明: 载气流速为3.7 L/min时,苯样品的谱峰强度最大,仪器的灵敏度最高.随着载气流速的增加,谱峰半峰宽变宽,仪器的分辨率下降.载气流速为3 .0～3.7 L/min时仪器综合性能最佳.此结果对于控制迁移谱仪载气流速有重要的参考意义.     

Analysis of trace degradation products (decarboxylated diastereoisomers) of S-adenosylmethionine by electrophoresis in capillaries with cationic coatings (N-methylpolyvinylpyridinium or divalent barium)

Commercial preparations of S‐adenosylmethionine (SAM) when analyzed in uncoated capillaries show a minute impurity believed to be decarboxylated (dc) SAM. By using two types of cationic coatings, thus reducing the electro‐endo‐osmotic flow (EOF), it was possible to separate this impurity into two diastereoisomers of dcSAM. The coatings evaluated for this purpose were: (i) N‐methylpolyvinylpyridinium, used under reversed EOF at acidic conditions (pH 4.0) and (ii) deposition of divalent barium at alkaline pH values (pH 9.4), providing reduced EOF. Under these conditions, it was possible to separate this impurity into two diastereoisomers, which by chemical synthesis were indeed proven to be dcSAM. It was further demonstrated that, in the alkylation of 5′‐methylthioadenosine by 3‐bromopropylamine in bromidric acid to dcSAM, another minute impurity was present, proven, via mass spectrometry, to consist of S‐(5′‐adenosyl)‐3‐thiopropylamine (decarboxylated and demethylated (dc‐SAH)). The LOD for the two dcSAM diastereoisomers was assessed as 17.5 μg/mL and their LOQ as 25.5 μg/mL. By the barium‐based protocol it was possible to quantify the dcSAM, present in a commercial sample of SAM, as a 0.1% impurity.     

Profiling of phospholipids in lipoproteins by multiplexed hollow fiber flow field-flow fractionation and nanoflow liquid chromatography–tandem mass spectrometry

This study describes a coupled analytical method to carry out the systematic profiling of phospholipids (PLs) in high-density lipoproteins (HDL) and low-density lipoproteins (LDL) from human blood plasma. HDL and LDL of healthy human plasma samples were separated by size and collected on a semi-preparative scale using multiplexed hollow fiber flow field-flow fractionation (MxHF5). Phospholipid mixtures contained in the resulting HDL and LDL fractions were analyzed by shotgun nanoflow liquid chromatography–tandem mass spectrometry (nLC–ESI-MS–MS). We utilized a dual scan method for the separation and simultaneous characterization of complicated PL mixtures by nLC–ESI-MS–MS, such that phosphatidylcholine (PC) and phosphatidylethanolamine (PE) molecules were detected in positive ion mode in a first LC run. In a second LC run, phosphatidylinositol (PI), phosphatidylglycerol (PG), and phosphatidic acid (PA) were detected in negative ion mode. In this study, a total of 56 PLs from HDL and 52 PLs from LDL particles were characterized by their molecular structures from data dependent collision-induced dissociation (CID) experiments, and their relative abundances were compared.     

Capillary electrophoresis-mass spectrometry of intact basic proteins using Polybrene-dextran sulfate-Polybrene-coated capillaries: System optimization and performance

A capillary electrophoresis-mass spectrometry (CE-MS) method using sheath liquid electrospray ionization interfacing was studied and optimized for the analysis of intact basic proteins. To prevent protein adsorption, capillaries with a noncovalent positively charged coating were utilized. Capillaries were coated by subsequent rinsing with solutions of Polybrene, dextran sulfate and Polybrene. The coating proved to be fully compatible with MS detection, causing no background signals and ionization suppression. The composition of the sheath liquid and BGE was optimized using the model proteins α-chymotrypsinogen A, ribonuclease A, lysozyme and cytochrome c. A sheath liquid of isopropanol-water-acetic acid (75:25:0.1, v/v/v) at 2 μL min⁻¹ resulted in optimal signal intensities for most proteins, but caused dissociation of the heme group of cytochrome c. Optimum protein responses were obtained with a BGE of 50 mM acetic acid (pH 3.0), which allowed a baseline separation of the test protein mixture. Several minor impurities present in the mixture could be detected and provisionally identified using accurate mass and a protein modification database. The selectivity of the CE-MS system was investigated by the analysis of acetylated lysozyme. Eight highly related species, identified as non-acetylated lysozyme and lysozyme acetylated in various degrees, could be distinguished. The CE-MS system showed good reproducibility yielding interday (three weeks period) RSDs for migration time and peak area within 2% and 10%, respectively. With the CE-MS system, determination coefficients (R²) for protein concentration and peak area were higher than 0.996, whereas detection limits were between 11 and 19 nM.     

Efficient access to new chemical space through flow--construction of druglike macrocycles through copper-surface-catalyzed azide-alkyne cycloaddition reactions

A series of 12‐ to 22‐membered macrocycles, with druglike functionality and properties, have been generated by using a simple and efficient copper‐catalyzed azide–acetylene cycloaddition reaction, conducted in flow in high‐temperature copper tubing, under environmentally friendly conditions. The triazole‐containing macrocycles have been generated in up to 90 % yield in a 5 min reaction, without resorting to the high‐dilution conditions typical of macrocyclization reactions. This approach represents a very efficient method for constructing this important class of molecules, in terms of yield, concentration, and environmental considerations.     

Chemical markers’ fishing and knockout for holistic activity and interaction evaluation of the components in herbal medicines

A strategy based on chemical markers’ fishing and knockout has been proposed for holistic activity and interaction evaluation of the bioactive components in herbal medicines (HMs). It was devised to screen bioactive-compound group that represents the efficacy of HM, estimate the bioactivity contribution of each component and elucidate the interactions of multi-components. This strategy was accomplished through the following steps: (1) screen out the chemical markers (target peaks) in a HM fingerprint using online two-dimensional turbulent flow chromatography/liquid chromatography–mass spectrometry technique, (2) fish target peaks and knockout any interested peak, and (3) evaluate the bioactivities of fishing and knockout portions. After comparison of the bioactivities of samples containing different target peaks, the efficacy of target-peak group, bioactivity contribution of each compound, and the interactions of multi-components are elucidated. Using Acetylcholinesterase (AChE) and Bulbs of Lycoris radiata (L. Herit.) Herb. (BLR) as the experimental materials, four target peaks were screened out as the AChE binders. By target peaks’ fishing and knockout, combined with activity evaluation, we observed that the bioactivity of the four-peak mixture is similar with the global bioactivity of BLR extract, and there are significant suppressive actions among these four target peaks. These results indicate that this proposed strategy is a useful approach for holistic screening of bioactive-compound group and elucidation of the multi-component interactions in HM.