Mass analysis in islands of stability with linear quadrupoles with added octopole fields

Mass analysis with linear quadrupole mass filters is possible by forming "islands" in the stability diagram with auxiliary quadrupole excitation. In this work, computer simulations are used to calculate stability boundaries, island positions, and peak shapes and ion transmission for mass analysis with linear quadrupole mass filters that have added octopole fields of about 2 to 4%. Rod sets with exact geometries that have quadrupole and octopole fields only in the potential, and round rod sets, with multipoles up to N = 10 (the twenty pole term) included in the calculations, show the same stability boundaries, island positions, and peak shapes. With the DC voltage applied to the rods so that the Mathieu parameter a < 0, conventional mass analysis is possible without the use of an island. With the DC polarity reversed so that a > 0, the resolution and transmission are poor preventing conventional mass analysis. In principle, mass analysis in an island is possible with operation at either of two tips. Provided the correct island tip is chosen for mass analysis, peak shapes comparable to those with a > 0 and no excitation are possible, both with a > 0 and with a < 0. In the latter case, the use of an island of stability allows mass analysis when the added octopole otherwise prevents conventional mass analysis.     

Structural characterization of intact proteins is enhanced by prevalent fragmentation pathways rarely observed for peptides

While collisionally activated dissociation (CAD) pathways for peptides are well characterized, those of intact proteins are not. We systematically assigned CAD product ions of ubiquitin, myoglobin, and bovine serum albumin generated using high-yield, in-source fragmentation. Assignment of >98% of hundreds of product ions implies that the fragmentation pathways described are representative of the major pathways. Protein dissociation mechanisms were found to be modulated by both source declustering potential and precursor ion charge state. Like peptides, higher charge states of proteins fragmented at lower energies next to Pro, via mobile protons, while lower charge states fragmented at higher energies after Asp and Glu, via localized protons. Unlike peptides, however, predominant fragmentation channels of proteins occurred at intermediate charge states via non-canonical mechanisms and produced extensive internal fragmentation. The non-canonical mechanisms include prominent cleavages C-terminal to Pro and Asn, and N-terminal to Ile, Leu, and Ser; these cleavages, along with internal fragments, led to a 45% increase in sequence coverage, improving the specificity of top-down protein identification. Three applications take advantage of the different mechanisms of protein fragmentation. First, modulation of declustering potential selectively fragments different charge states, allowing the source region to be used as the first stage of a low-resolution tandem mass spectrometer, facilitating pseudo-MS3 of product ions with known parent charge states. Second, development and integration of automated modulation of ion funnel declustering potential allows users access to a particular fragmentation mechanism, yielding facile cleavage on a liquid chromatography timescale. Third, augmentation of a top-down search engine improved protein characterization.     

Comparison of solid phase microextraction and hollow fiber liquid phase microextraction for the determination of pesticides in aqueous samples by gas chromatography triple quadrupole tandem mass spectrometry

This work compares two miniaturised sample preparation methods, solid phase microextraction (SPME) and hollow fiber liquid phase microextraction (HF-LPME), in combination with gas chromatography coupled to tandem mass spectrometry with a triple quadrupole analyzer for the determination of 77 pesticides in drinking water. In the case of SPME, extraction temperature and time were optimized by experimental design, although other parameters, as desorption time, pH, and ionic strength, were also evaluated. The extraction and desorption solvents [octanol/dihexyl ether (75:25, v/v) and cyclohexane, respectively], as well as the extraction and desorption time, ionic strength, and pH, were studied for the HF-LPME procedure. Under the optimal conditions, recoveries (70.2–113.5% for SPME and 70.0–119.5% for HF-LPME), intra-day precision (2.1–19.4% for SPME and 4.3–22.5% for HF-LPME), inter-day precision (5.2–21.5% for SPME and 8.4–27.3% for HF-LPME), and limits of detection, between 0.1 and 28.8 ng/L for SPME and 0.2 and 47.1 ng/L for HF-LPME and overall uncertainty (9.6–25.2% for SPME and 13.3–27.5% for HF-LPME) were established for both extraction procedures. Finally, the proposed methods were successfully applied to the analysis of 41 drinking water samples, and similar results were obtained with both extraction approaches.     

硝基四唑及其高氮化合物*

硝基四唑及其高氮化合物是指分子中含有5-硝基四唑结构的一类高氮化合物,优越的性能和突出的特点使其成为含能材料领域的研究热点之一,在起爆药、推进剂及其燃速催化剂、高能炸药、气体发生剂等领域有着广泛的应用前景。本文对硝基四唑的结构与热分解机理进行了分析介绍;全面系统地综述评价了硝基四唑及其盐类和配合物类衍生物的合成、性能表征与应用前景。根据其成盐阳离子的不同,硝基四唑盐类主要包括碱金属盐、碱土金属盐、过渡金属盐、胺盐和高氮杂环阳离子盐。根据配位方式的不同,其配合物可分为配阴离子型和配阳离子型。在此基础上,对硝基四唑及其高氮化合物的未来发展及应用提出了展望。     

Time and poling history dependent energy storage and discharge behaviors in poly(vinylidene fluoride-<Emphasis Type="Italic">co</Emphasis>-hexafluoropropylene) random copolymers

 We studied cycle time (0.01–10 s with triangular input waves) and poling history (continuous versus fresh poling) dependent electric energy storage and discharge behaviors in poly(vinylidene fluoride-co-hexafluoropropylene) [P(VDF-HFP)] films using the electric displacement ― the electric field (D-E) hysteresis loop measurements. Since the permanent dipoles in PVDF are orientational in nature, it is generally considered that both charging and discharging processes should be time and poling history dependent. Intriguingly, our experimental results showed that the charging process depended heavily on the cycle time and the prior poling history, and thus the D-E hysteresis loops had different shapes accordingly. However, the discharged energy density did not change no matter how the D-E loop shape varied due to different measurements. This experimental result could be explained in terms of reversible and irreversible polarizations. The reversible polarization could be charged and discharged fairly quickly (< 5 ms for each process), while the irreversible polarization depended heavily on the poling time and the prior poling history. This study suggests that it is only meaningful to compare the discharged energy density for PVDF and its copolymer films when different cycle times and poling histories are used.     

Distribution of Heavy Metal Contents and Chemical Fractions in Anaerobically Digested Manure Slurry

Digested slurry samples from twenty-one large-scale anaerobic digestion plants together with intensive pig and dairy farms in Jiangsu Province of China were collected and analyzed for total and dissolved concentrations of Zn, Cu and As, as well as chemical characteristics. The results showed that total concentrations of Zn, Cu and As in digested pig slurries were concentrated to <10, <5 and 0.02–0.1 mg/l, respectively; while <2 and 10–30, <1, and 0.02–0.1 mg/l, respectively, in digested dairy slurries. Lowering the dietary supply of these elements to pig and dairy would be the most effective way to control heavy metal contents in digested manure slurries. Dissolved fractions of Zn, Cu and As accounted for 1–74%, 1–33% and 2–53% of the total concentrations, respectively, in digested pig slurries; and 18–65%, 12–58% and 3–68% in digested dairy slurries. The chemical fractions of heavy metals in digested slurries were not only dependent on the total concentrations of heavy metals in raw manures but also on conditions of digestion and storage. Oxidation pond systems could significantly cripple the total contents of heavy metals in digested slurries, and the removal effect was better in multi-oxidation-pond systems than that in primary-oxidation-pond systems. However, the chemical fractions of heavy metals in digested slurries changed in a complicated manner when stored in oxidation ponds, due to the suspended solid deposition, elements reduction, as well as variations of pH values and oxidation-reduction potential.     

中国化学物相分析研究的新成就(下)

分两部分介绍了我国化学物相分析近十余年来研究的新成就。第二部分（下）则对物料物质组成的相态与元素(Fe,I,Mn,Mo,Na,P,Re,S,Sb,Se,Si,Sn,Sr,Ti,U和V等)价态分析、赋存状态分析以及非金属矿物相分析等的研究现状,分别予以简要评述。同时对其存在的问题和进一步研究的方向也进行了讨论。引用文献114篇。     

Coordination properties of N,O-carboxymethyl chitosan (NOCC). Synthesis and equilibrium studies of some metal ion complexes. Ternary complexes involving Cu(II) with (NOCC) and some biorelevant ligand

In the present study, the acid-base equilibria of N,O-carboxymethy chitosan abbreviated as (NOCC), is investigated. The complex formation equilibria with the metal ions Cu^(II), Ni^(II), Co^(II), Mn^(II), and Zn^(II) are investigated potentiometrically. The stability constant values of the binary and ternary complexes formed in solution were determined and the binding centers of the ligands were assigned. The relationships between the properties of the studied central metal ions as ionic radius, electronegativity, atomic number, and ionization potential, and the stability constants of the formed complexes were investigated in an effort to give information about the nature of chemical bonding in complexes and make possible the calculation of unknown stability constants. Cu^(II), Ni^(II), and U^(VI) complexes with NOCC are isolated as solid complexes and characterized by conventional chemical and physical methods. The structures of the isolated solid complexes are proposed on the basis of the spectral and magnetic studies. The ternary copper(II) complexes involving NOCC and various biologically relevant ligands containing different functional groups, as amino acids and DNA constituents are investigated. The stability constants of the complexes are determined and the concentration distribution diagrams of the complexes are evaluated.     

IVSPlat 1.0: an integrated virtual screening platform with a molecular graphical interface

Background  

The virtual screening (VS) of lead compounds using molecular docking and pharmacophore detection is now an important tool in drug discovery. VS tasks typically require a combination of several software tools and a molecular graphics system. Thus, the integration of all the requisite tools in a single operating environment could reduce the complexity of running VS experiments. However, only a few freely available integrated software platforms have been developed.     

新型水溶性超支化聚酰胺-酯的合成

均苯四甲酸酐与二乙醇胺经酰化反应制得中心核(4);4与AB2单体2,2-二羟甲基丙酸经熔融缩聚合成了一种新型水溶性的二代超支化聚酰胺-酯(1),其结构与性能经FT-IR,GPC,粘度法,化学滴定等表征。4的Mn=1 683,Mw=1 911,Mw/Mn=1.14,[ηinh]=0.067 6 dL·g-1;1的Mn=3 750,Mw=4 904,Mw/Mn=1.31,[ηinh]=0.086 1 dL·g-1。