Real-time organic aerosol chemical speciation in the indoor environment using extractive electrospray ionization mass spectrometry

Understanding the sources and composition of organic aerosol (OA) in indoor environments requires rapid measurements, since many emissions and processes have short timescales. However, real-time molecular-level OA measurements have not been reported indoors. Here, we present quantitative measurements, at a time resolution of five seconds, of molecular ions corresponding to diverse aerosol-phase species, by applying extractive electrospray ionization mass spectrometry (EESI-MS) to indoor air analysis for the first time, as part of the highly instrumented HOMEChem field study. We demonstrate how the complex spectra of EESI-MS are screened in order to extract chemical information and investigate the possibility of interference from gas-phase semivolatile species. During experiments that simulated the Thanksgiving US holiday meal preparation, EESI-MS quantified multiple species, including fatty acids, carbohydrates, siloxanes, and phthalates. Intercomparisons with Aerosol Mass Spectrometer (AMS) and Scanning Mobility Particle Sizer suggest that EESI-MS quantified a large fraction of OA. Comparisons with FIGAERO-CIMS shows similar signal levels and good correlation, with a range of 100 for the relative sensitivities. Comparisons with SV-TAG for phthalates and with SV-TAG and AMS for total siloxanes also show strong correlation. EESI-MS observations can be used with gas-phase measurements to identify co-emitted gas- and aerosol-phase species, and this is demonstrated using complementary gas-phase PTR-MS observations.     

Analysis of the polyethylene glycol glucosides and FA esters thereof by atmospheric-pressure ionization MS

Polyethylene glycol (PEG) glucosides (PEGG) and the PEGG esters of lauric acid were analyzed by atmospheric-pressure ionization MS (API-MS) with electrospray ionization. Straightforward mass characterization of the complex mixtures could be achieved without prior chromatographic separation. The constituents were identified on the basis of quasi-molecular ions. Individual components could be observed as protonated molecular ions [M+H]⁺ and/or as their NH₄ ⁺, Na⁺, or K⁺ adducts in positive ion mode. The mass spectrometric investigation showed that mixtures of PEGG consisted of monoglucoside, diglucoside, polyglucoside, and free PEG. The esterification product is a mixture of two types of nonionic surfactants: PEG-laurates and PEGG-laurates. The reasons for distortion of the quasi-molecular ion intensities and the stabilization of adduct ions were discussed. The rapid and highly sensitive API-MS analysis technique proposed here is well suited for direct characterization of complex mixtures and suitable for development as a routine analytical method.     

Electrospray‐deposited nickel ferrite thin film electrode for hydrogen production in PV‐assisted water electrolysis system

Nanocrystalline Ni ferrite thin film was prepared by electrospray deposition technique and characterized by different analytical techniques at different annealing temperatures. All these films were studied by photovoltaic‐assisted water electrolysis system for solar to hydrogen production efficiency measurement. Highly dense and uniform surface morphology was observed in as‐deposited film, which changed into agglomerated nanocrystalline grains of irregular size and shape with change in annealing temperature. The X‐ray photoelectron spectroscopy study showed that the as‐deposited film was a mixture of an oxyhydroxide form of iron and an Ni₂O₃ form of nickel, whereas it changed into ferrite phase with change in annealing temperature. The as‐deposited film was observed to be of amorphous phase, which changed to crystalline cubic spinel structure with change in annealing temperature. The solar to hydrogen production efficiency was found to increase in a film with an increase in annealing temperature. The film annealed at 500°C showed a high solar to hydrogen production efficiency (8.29%) with constant performance of up to initial 500 h. Thereafter, the performance slowly declined by 11% when up to 1000 h. Copyright © 2011 John Wiley & Sons, Ltd.     

Mass spectrometry of peptides and proteins from human blood

It is difficult to convey the accelerating rate and growing importance of mass spectrometry applications to human blood proteins and peptides. Mass spectrometry can rapidly detect and identify the ionizable peptides from the proteins in a simple mixture and reveal many of their post‐translational modifications. However, blood is a complex mixture that may contain many proteins first expressed in cells and tissues. The complete analysis of blood proteins is a daunting task that will rely on a wide range of disciplines from physics, chemistry, biochemistry, genetics, electromagnetic instrumentation, mathematics and computation. Therefore the comprehensive discovery and analysis of blood proteins will rank among the great technical challenges and require the cumulative sum of many of mankind's scientific achievements together. A variety of methods have been used to fractionate, analyze and identify proteins from blood, each yielding a small piece of the whole and throwing the great size of the task into sharp relief. The approaches attempted to date clearly indicate that enumerating the proteins and peptides of blood can be accomplished. There is no doubt that the mass spectrometry of blood will be crucial to the discovery and analysis of proteins, enzyme activities, and post‐translational processes that underlay the mechanisms of disease. At present both discovery and quantification of proteins from blood are commonly reaching sensitivities of ～1 ng/mL. © 2010 Wiley Periodicals, Inc., Mass Spec Rev 30:685–732, 2011     

基于电喷雾质谱的反应监测研究进展

电喷雾质谱(ESI-MS)因具有灵敏度高、响应速度快、分辨率高、原位在线监测等特点,广泛应用于反应监测领域。本文主要从不同离子化技术角度,综述了电喷雾质谱在反应监测和机理研究方面的进展。重点介绍了在线电喷雾质谱技术,其中包括解吸附电喷雾离子化质谱（DESI-MS）、萃取电喷雾离子化质谱（EESI-MS）、纳升电喷雾离子化质谱（nESI-MS）、超声喷雾离子化质谱（SSI-MS）以及其他在线电喷雾离子化质谱在反应监测中的应用。最后,对电喷雾质谱在反应监测的发展趋势进行总结和展望。     

Dendrimer as nanocarrier for drug delivery

Dendrimers are novel three dimensional, hyperbranched globular nanopolymeric architectures. Attractive features like nanoscopic size, narrow polydispersity index, excellent control over molecular structure, availability of multiple functional groups at the periphery and cavities in the interior distinguish them amongst the available polymers. Applications of dendrimers in a large variety of fields have been explored. Drug delivery scientists are especially enthusiastic about possible utility of dendrimers as drug delivery tool. Terminal functionalities provide a platform for conjugation of the drug and targeting moieties. In addition, these peripheral functional groups can be employed to tailor-make the properties of dendrimers, enhancing their versatility. The present review highlights the contribution of dendrimers in the field of nanotechnology with intent to aid the researchers in exploring dendrimers in the field of drug delivery.     

冠脉支架表面PLGA涂层制备及其血液相容性研究

采用静电喷涂沉积(electrospray deposition ESD)法在冠脉支架表面制备了PLGA涂层.采用OLYMPUS体式显微镜、原子力显微镜(AFM)观察了涂层宏观表面形貌及三维形貌;通过对涂层支架进行球囊扩张考察了PLGA涂层与支架的结合力;通过血小板粘附实验和动态凝血时间测定研究PLGA涂层的血液相容性.结果表明:ESD法在冠脉支架表面制备PLGA涂层,支架筋拐角处无明显的聚合物胶体缠绕、粘连且涂层表面光滑;PLGA涂层将316L不锈钢基体的微坑覆盖,基体Ra=16.174nm,PLGA涂层Ra=0.149nm,涂层表面粗糙度小;涂层支架撑开后在最大塑性变形位置无涂层撕裂、翘起等缺陷,涂层与支架有良好结合力;PLGA涂层血小板粘附量少,变形小,未引起血小板激活,动态凝血时间长,直到50min未产生凝血,PLGA涂层具有较好的血液相容性.     

Profiling and Imaging of Phospholipids in Brains of Abcd1‐Deficient Mice

ABCD1 is a gene responsible for X‐linked adrenoleukodystrophy (X‐ALD), and is critical for the transport of very long‐chain fatty acids (VLCFA) into peroxisomes and subsequent β‐oxidation. VLCFA‐containing lipids accumulate in X‐ALD patients, although the effect of ABCD1‐deficiency on each lipid species in the central nervous system has not been fully characterized. In this study, each phospholipid and lysophospholipid species in Abcd1‐deficient mice brains were profiled by liquid chromatography‐mass spectrometry. Among the phospholipid and lysophospholipid species that are significantly more enriched in Abcd1‐deficient mice brains, VLCFA were present in 75, 15, 5, 4, and 1 species of phosphatidylcholine, phosphatidylethanolamine, sphingomyelin, lysophosphatidylcholine, and lysophosphatidylethanolamine, respectively. Most VLCFA were incorporated at the sn‐1 position of phosphatidylcholine and phosphatidylethanolamine. Among the phospholipid species that are significantly less enriched in Abcd1‐deficient mice brains, odd‐numbered saturated or mono‐unsaturated fatty acyl moieties are contained in all phosphatidylcholine species. In addition, a number of phosphatidylglycerol, phosphatidylinositol, and phosphatidylserine species contained highly unsaturated fatty acyl moieties. Intriguingly, 44:1 phosphatidylcholine with VLCFA was mainly distributed in the gray matter, such as the cortex, but not in the white matter in the cerebrum and cerebellum. These results show that ABCD1‐deficiency causes metabolic alternation of long‐chain fatty acids and VLCFA. Moreover, our results imply a molecular mechanism for the incorporation of saturated or monounsaturated VLCFA into the sn‐1 position of phospholipids, and also indicate that the distribution of phospholipids with VLCFA may correlate with the development of X‐ALD.     

含芳香氨基酸三肽及其衍生物自由基离子的形成和解离机理研究

铜-配体(L)-三肽组成的三元复合物［Cu(L)M］²⁺,其中,L表示4′-氯-2,2′:6′,2″-三联吡啶(缩写为4Cl-tpy);M表示酪氨酰-甘氨酰-色氨酸(YGW)及其修饰型三肽(CH₃CO-YGW-OCH₃,缩写 Ac-YGW-OMe)。使用该复合物,通过碰撞诱导解离 (collision-induced dissociation, CID)产生两种自由基离子 (［YGW］^·+和［Ac-YGW-OMe］^·+)。采用串联质谱结合密度泛函理论 (density functional theory, DFT)得到气相稳定结构,并研究其气相解离行为。研究结果表明,［YGW］^·+和［Ac-YGW-OMe］^·+的气相解离行为截然不同,［YGW］^·+主要产生［M-CO₂-116］⁺和［M-CO₂］^·+碎片离子;而［Ac-YGW-OMe］^·+在气相中主要产生［M-CH₃OH］^·+碎片离子。推测这两种离子的气相裂解机理分别为：［YGW］^·+羧基上的质子重排到多肽骨架中羰基氧上,经历 C_α-C键的断裂产生［M-CO₂］^·+、断裂色氨酸侧链 C_β-C_γ键产生［M-CO₂-116］⁺离子;［Ac-YGW-OMe］^·+则先经历质子重排到酯基氧上,然后经过C-O酯键的断裂形成［M-CH₃OH］^·+离子。参与重排的质子可能有3个来源：Ac-YGW-OMe中甘氨酸的C_α-H、色氨酸的C_α-H 或C_β-H,该机理有待进一步验证。本研究将为其他类型多肽及衍生物的结构及气相反应机理研究提供参考。     

水相中酒石酸铀酰形态的电喷雾串联质谱研究

铀的水溶液化学形态是高放废物处置研究的重要内容之一。本实验采用电喷雾串联质谱（ESI-MS/MS）研究酒石酸-硝酸铀酰水溶液中铀酰形态,共分析出14种酒石酸铀酰和5种无机铀酰形态。每个铀酰基团可紧密结合1个酒石酸阴离子,并继续以较弱的形式络合1~2个酒石酸分子。实验中还发现了［(UO₂HTarH₂Tar)₂］²⁺、［(UO₂)₃Tar(HTar)₂(H₂Tar)₂］²⁺等酒石酸铀酰团簇形态。酒石酸铀酰形态中各络合键解离所需能量大小顺序为：铀酰间结合键＞酒石酸阴离子-铀酰结合键＞酒石酸分子-铀酰结合键。该研究对实际条件下铀与有机酸的水溶液形态研究具有指导意义。