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71.
A recently characterized oviposition-deterring pheromone (ODP, structure 1) of the European cherry fruit fly was used as a test case for probing the potential of tandem mass spectrometry (MS/MS) in structure elucidation as a stand-alone technique. The glycolipid-taurinate 1 was subjected to MS/MS analyses under a variety of conditions with and without preceding chemical degradation. Acidic methanolysis of 1 and subsequent in-batch derivatization (trideuterioacetylation) yielded methyl 2,3,4,6-tetrakis-O-trideuterioacetyl-glucopyranoside (2), methyl 8,15-bis-trideuterioacetoxy-palmitate (3), and taurine (4) as suitable target compounds for direct mixture analysis.Low energy collision induced dissociation (CID) on selected precursor ions (MS/MS on [M + H – CH3OH]+ and [M + H]+ produced by fast atom bombardment (FAB)) allowed direct identification of 2 and 4, respectively, by comparison with appropriate reference ions. In the case of 3, low energy CID (desorption chemical ionization (DCI) instead of FAB, MS/MS on [M + H]+) permitted deduction of gross molecular structure, but failed to provide positional detail. In sharp contrast,high energy CID of trideuterioacetylated intact 1 (FAB-MS/MS on [M – H]– ions of la) clearly revealed a linear 8,15-hydroxylated palmitic acid backbone. Less certain was assignment of 15-O-glucosylation by this approach. 相似文献
72.
Robin D. Rogers Philip D. Richards 《Journal of inclusion phenomena and macrocyclic chemistry》1987,5(5):631-638
The title complex was crystallized from a saturated solution of 18-crown-6 in nitromethane at 5°C and cooled to –150°C prior to X-ray diffraction data collection. At –150° C 18-crown-6·2(CH3NO2) is monoclinic,P21/n witha=9.290(2),b=7.864(6),c=13.627(8) Å, =1000.84(4)° andD
calc=1.31 g cm–3 for Z=2. Leastsquares refinement using 1521 independent observed reflections [F
o5(F
o)] led to a final conventionalR value of 0.041. The complex at –150°C is isostructural with its room temperature structure with the exception of the orientation of the methyl hydrogen atoms and their crown ether oxygen interactions. The methyl group hydrogen atoms were fully refined isotropically. The crown ether resides around a center of inversion and hasD
3d symmetry. There is one methyl hydrogen...crown interaction at 2.35(3) Å, one apparently bifurcated hydrogen bond utilizing a second methyl hydrogen atom (2.55(3), 2.65(3) Å) and the third hydrogen atom is actually directed away from the crown ring (closest H...O contact=2.67(3) Å).
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82048 (5 pages).For part 2, see reference [24]. 相似文献
73.
74.
《Arabian Journal of Chemistry》2022,15(7):103933
In this study, a fingerprint-activity relationship modeling between chemical fingerprints and antirheumatic activity was established, and multivariate statistical analysis was used to evaluate the quality of Taxilli Herba (TH) from different hosts. Characteristic fingerprints of 20 batches of TH samples were generated by high-performance liquid chromatography coupled with triple quadrupole-time of flight tandem mass spectrometry (HPLC-Triple TOF-MS/MS), and the similarity analysis was calculated based on thirteen common characteristic peaks by hierarchical clustering analysis (HCA). Subsequently, nine efficacy markers were discovered by combining fingerprints and antirheumatic activity through grey correlation analysis (GCA) and bivariate correlation analysis (BCA). Meanwhile, the content of 5 constituents in 9 markers was determined by high-performance liquid chromatography coupled with triple quadrupole-linear ion trap tandem mass spectrometry (HPLC-QTRAP-MS/MS). The comprehensive quality of TH was assessed using multivariate statistical analysis, including principal components analysis (PCA) and technique for order preference by similarity to ideal solution (TOPSIS). The results showed that a high dose of TH extract could markedly ameliorate arthritis damage compared to other doses, with flavonoids playing an important role in the antirheumatic activity. The comprehensive quality of samples from Morus alba L. (SS) was superior to those from Liquidambar formosana Hance (FXS). The present study will demonstrate the markers associated with efficacy, and provide an applicable strategy for more comprehensive quality control and evaluation of TH. 相似文献
75.
Rheological investigation of the influence of molecular structure on natural and accelerated UV degradation of linear low density polyethylene 总被引:1,自引:0,他引:1
Ibnelwaleed A. Hussein 《Polymer Degradation and Stability》2007,92(11):2026-2032
Metallocene and Ziegler-Natta (ZN) linear low density polyethylenes (LLDPEs) of different branch types and contents as well as linear high density polyethylene (HDPE) were exposed to natural and accelerated weather conditions. The degree of UV degradation of exposed samples was measured by rheological techniques and results were compared with unexposed polymers. Dynamic shear measurements were performed in an ARES rheometer in the linear viscoelastic range. The degree of enhancement or reduction in viscosity and elasticity was used as a measure of the degree of cross-linking or chain scission, respectively. The degradation results of LLDPE suggest that both cross-linking and chain scission are taking place. Chain scission dominated the degradation at high levels of short chain branching (SCB) and long exposure times. The degradation mechanism of m-LLDPE and ZN-LLDPE is similar; however, m-LLDPE showed a higher degradation rate than ZN-LLDPE of similar Mw and average SCB. ZN-LLDPE was found to be more stable than a similar m-LLDPE. Comonomer type had little influence on degradation. Dynamic shear rheology was very useful in revealing the influence of different molecular parameters and it exposed the degradation mechanism. 相似文献
76.
Proteins with molecular mass (M(r)) <20 kDa are often poorly separated in 2-D sodium dodecyl sulfate polyacrylamide gel electrophoresis. In addition, low-M(r) proteins may not be readily identified using peptide mass fingerprinting (PMF) owing to the small number of peptides generated in tryptic digestion. In this work, we used a 2-D liquid separation method based on chromatofocusing and non-porous silica reversed-phase high-performance liquid chromatography to purify proteins for matrix-assisted laser desorption/ionization time-of-flight mass spectrometric (MALDI-TOFMS) analysis and protein identification. Several proteins were identified using the PMF method where the result was supported using an accurate M(r) value obtained from electrospray ionization TOFMS. However, many proteins were not identified owing to an insufficient number of peptides observed in the MALDI-TOF experiments. The small number of peptides detected in MALDI-TOFMS can result from internal fragmentation, the few arginines in its sequence and incomplete tryptic digestion. MALDI-QTOFMS/MS can be used to identify many of these proteins. The accurate experimental M(r) and pI confirm identification and aid in identifying post-translational modifications such as truncations and acetylations. In some cases, high-quality MS/MS data obtained from the MALDI-QTOF spectrometer overcome preferential cleavages and result in protein identification. 相似文献
77.
Electron ionization (EI) mass spectra of 46 compounds from several different compound classes were measured. Their molecular ion abundances were compared as obtained with 70‐eV EI, with low eV EI (such as 14 eV), and with EI mass spectra of vibrationally cold molecules in supersonic molecular beams (Cold EI). We further compared these mass spectra in their National Institute of Standards and Technology (NIST) library identification probabilities. We found that
- Low eV EI is not a soft ionization method, and it has little or no influence on the molecular ion relative abundances for large molecules and those with weak or no molecular ions.
- Low eV EI for compounds with abundant or dominant molecular ions in their 70 eV mass spectra results in the reduction of low mass fragment ions abundances thereby reducing their NIST library identification probabilities thus rarely justifies its use in real‐world applications.
- Cold EI significantly enhances the relative abundance of the molecular ions particularly for large compounds; yet, it retains the low mass fragment ions; hence, Cold EI mass spectra can be effectively identified by the NIST library.
- Different standard EI ion sources provide different 70 eV EI mass spectra. Among the Agilent technologies ion sources, the “Extractor” exhibits relatively abundant molecular ions compared with the “Inert” ion source, while the “High efficiency source” (HES) provides mass spectra with depleted molecular ions compared with the “Inert” ion source or NIST library mass spectra.
78.
Well established routes for obtaining stiff and strong polyethylene (PE) involve solid state drawing either of solution crystallized gel films or melt crystallized spherulitic PE. The aim of this work is to show the potential of melt deformation as an alternative route for obtaining highly oriented products. Our previous work on the melt deformation route showed that oriented PE fibers could be directly extruded under appropriately controlled conditions [8,9]. Here, we show that PE films (or filaments) can also be melt drawn in the temperature window 130–160 °C, thus yielding oriented products. The advantage of melt drawing over direct melt extrusion is that it allows a wider operational latitude and thus does not require such carefully controlled conditions.The morphology produced by melt deformation is different from solid state deformation and consists of extended chain fibrils with platelet overgrowths. The relative amount of fibrils and platelets depends on operating parameters. The temperature window of PE melt drawing is identified with the regime where some flow induced crystallization takes place. The conditions for melt drawability are of wider generality for crystallizable flexible chain polymers. They are: (i) adequate strain rate to overcome entropie resistance to chain extension, (ii) but not high enough to activate the elastic response of the transient networks in the entangled system, (iii) sufficient strain to fully extend the chain, (iv) appropriate temperature for flow-induced crystallization and strain hardening, and (v) cooling to freeze the oriented structure.Ultra high molecular weight PEs were not the most suitable for melt drawing due to their high recoverable elongation in the melt (melt elasticity) in addition to added limitations imposed by their nascent grain systeme. Our work suggests that an optimum molecular weight for melt drawing is¯M
w(400–900)×103 with further possibilities for improvement through multimodal distributions. 相似文献
79.
锂离子电池正极材料LiMn2O4的低热固相合成与性能表征 总被引:6,自引:0,他引:6
锂离子电池具有比能量高、环境污染小等优点,广泛应用于手提电话、便携式电脑、摄像机等设备中。其正极材料的研究是锂离子电池的研究重点。层状结构的LiCoO2、LiNiO2和尖晶石结构的LiMn2O4是仅有的三种能在3.5V以上电位可嵌入Li的正极材料[1~3]。目前市售的锂离子电池主要采用LiCoO2作正极材料,但由于Co资源缺乏和价格相对昂贵,而锰资源丰富,价格低廉且无毒,对环境友好,因此世界各国都在大力进行以LiMn2O4为正极材料的锂离子电池的实用化研究。LiMn2O4传统的制备方法是高温固相反应合成法[4~7],但由于Mn的变价多,与Li形成贫Li或… 相似文献
80.