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Y. Kudriavtsev A. Hernandez R. Asomoza S. Gallardo M. Lopez K. Moiseev 《Surface and interface analysis : SIA》2017,49(2):145-148
We have performed secondary ion mass spectrometry depth profiling analysis of III–V based hetero‐structures at different target temperatures and found that both the surface segregation and surface roughness caused by ion sputtering can be radically reduced if the sample temperature is lowered to ?150 °C. The depth profiling of ‘frozen’ samples can be a good alternative to sample rotation and oxygen flooding used for ultra‐low‐energy depth profiling of compound semiconductors. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
104.
Véronique Raverot Jonathan Lopez Catherine Grenot Henri Déchaud 《Analytica chimica acta》2010,658(1):87-9857
Testosterone (T) circulates in the blood tightly bound to sex hormone-binding globulin (SHBG) and weakly to albumin. Measuring protein unbound T (free) or non-SHBG-bound T rather than total T has been recommended for the evaluation of androgen disorders in humans. Ammonium sulfate precipitation has been widely used to separate [SHBG-T] complex from free and albumin-bound T. To achieve more specificity in this separation, we used monoclonal anti-SHBG antibody and developed a suitable and convenient immunoassay for measuring non-SHBG-bound T. Magnetic beads were covalently coupled to a monoclonal anti-SHBG antibody to capture [SHBG-T] complex from plasma samples. Magnetic separation was then performed to allow measurement of non-SHBG-bound T in the supernatant by direct radioimmunoassay. When 300 μL of plasma samples were incubated at room temperature with 10 μL of anti-SHBG beads, residual SHBG concentration was undetectable in the supernatant. The specificity of proteins retained on anti-SHBG beads was further demonstrated by peptide mass fingerprint on a MALDI-TOF analyzer. The non-specific adsorption of T on beads was low (5%), and dissociation of T from SHBG-T complex was less than 5% after 180 min of incubation. The plasma concentrations of non-SHBG-bound T using anti-SHBG beads were highly correlated to those obtained using ammonium sulfate precipitation. We conclude that SHBG immunocapture is a highly specific and useful tool for an experimental direct measurement of plasma non-SHBG-bound T. This methodology is also convenient and appropriate for routine and automated assay. 相似文献
105.
Katrin Hartl Karl J.J. Mayrhofer Marco Lopez Dan Goia Matthias Arenz 《Electrochemistry communications》2010,12(11):1487-1489
In the presented work, the evaluation of an unsupported AuPt core–shell catalyst for the oxygen reduction reaction is introduced. Applying only basic chemicals in an upscalable synthesis route, it is demonstrated that uniform, flat, and complete Pt layers around a spherical Au core are obtained. The electrocatalytic measurements show that the surface area specific activity of the AuPt core–shell catalyst towards the important oxygen reduction reaction equals the one of polycrystalline bulk Pt. To our knowledge, this is the first time that the unfavorable particle size effect of Pt nanoparticles could be by-passed for a nanoscale catalyst. 相似文献
106.
Kiran Kumar Morishetti Betty De Suan Huang Jessica Marney Yates Jianhua Ren 《Journal of the American Society for Mass Spectrometry》2010,21(4):603-614
The sequence and conformational effects on the gas-phase acidities of peptides have been studied by using two pairs of isomeric
cysteine-polyglycine peptides, CysGly3,4NH2 and Gly3,4CysNH2. The extended Cooks kinetic method was employed to determine the gas-phase acidities using a triple quadrupole mass spectrometer
with an electrospray ionization source. The ion activation was achieved via collision-induced dissociation experiments. The
deprotonation enthalpies (Δacid
H) were determined to be 323.9 ± 2.5 kcal/mol (CysGly3NH2), 319.2 ± 2.3 kcal/mol (CysGly4NH2), 333.8 ± 2.1 kcal/mol (Gly3CysNH2), and 321.9 ± 2.8 kcal/mol (Gly4CysNH2), respectively. The corresponding deprotonation entropies (Δacid
S) of the peptides were estimated. The gas-phase acidities (Δacid
G) were derived to be 318.4 ± 2.5 kcal/mol (CysGly3NH2), 314.9 ± 2.3 kcal/mol (CysGly4NH2), 327.5 ± 2.1 kcal/mol (Gly3CysNH2), and 317.4 ± 2.8 kcal/mol (Gly4CysNH2), respectively. Conformations and energetic information of the neutral and anionic peptides were calculated through simulated
annealing (Tripos), geometry optimization (AM1), and single point energy calculations (B3LYP/6-31+G(d)), respectively. Both
neutral and deprotonated peptides adopt many possible conformations of similar energies. All neutral peptides are mainly random
coils. The two C-cysteine anionic peptides, Gly3,4(Cys-H)−NH2, are also random coils. The two N-cysteine anionic peptides, (Cys-H)−Gly3,4NH2, may exist in both random coils and stretched helices. The two N-cysteine peptides, CysGly3NH2 and CysGly4NH2, are significantly more acidic than the corresponding C-terminal cysteine ones, Gly3CysNH2 and Gly4CysNH2. The stronger acidities of the former may come from the greater stability of the thiolate anion resulting from the interaction
with the helix-macrodipole, in addition to the hydrogen bonding interactions. 相似文献
107.
Petiot P Charnay C Martinez J Puttergill L Galindo F Lamaty F Colacino E 《Chemical communications (Cambridge, England)》2010,46(46):8842-8844
The synthesis of a new hydrophilic ammonium-based poly(ethylene glycol)-ionic liquid (PEG-IL) is reported; the structure was assigned by NMR ((1)H, (13)C) and MALDI mass spectrometry. The viscosity and thermal stability were also studied, as well as its polarity. Its application as an alternative solvent in the synthesis of dipeptides under microwave irradiation is also described. 相似文献
108.
Laura Saa Dr. Ana Virel Dr. Jose Sanchez‐Lopez Valery Pavlov Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(21):6187-6192
We have developed an analytical assay to detect the enzymatic activity of acetylcholine esterase and alkaline phosphatase based on the generation of quantum dots by enzymatic products. Acetylcholine esterase converts acetylthiocholine into thiocholine. The latter enhances the rate of decomposition of sodium thiosulfate into H2S, which in the presence of cadmium sulfate yields CdS quantum dots showing a time dependent exponential growth, typical of autocatalytic processes. This assay was also applied to detect acetylcholine esterase inhibitors. Alkaline phosphatase hydrolyzes thiophosphate and yields H2S, which instantly reacts with Cd2+ to give CdS quantum dots. The formation of CdS quantum dots in both reactions was followed by fluorescence spectroscopy and showed dependence on the concentration of enzyme and substrate. 相似文献
109.
Berdeaux O Juaneda P Martine L Cabaret S Bretillon L Acar N 《Journal of chromatography. A》2010,1217(49):7738-7748
The retina is one of the vertebrate tissues with the highest content in polyunsaturated fatty acids (PUFA). A large proportion of retinal phospholipids, especially those found in photoreceptor membranes, are dipolyunsaturated molecular species. Among them, dipolyunsaturated phosphatidylcholine (PC) molecular species are known to contain very-long-chain polyunsaturated fatty acids (VLC-PUFA) from the n-3 and n-6 series having 24-36 carbon atoms (C24-C36) and four to six double bonds. Recent interest in the role played by VLC-PUFA arose from the findings that a protein called elongation of very-long-chain fatty acids 4 (ELOVL4) is involved in their biosynthesis and that mutations in the ELOVL4 gene are associated with Stargardt-like macular dystrophy (STD3), a dominantly inherited juvenile macular degeneration leading to vision loss. The aim of the present study was to develop an HPLC-ESI-MS/MS method for the structural characterisation and the quantification of dipolyunsaturated PC molecular species containing VLC-PUFA and validate this methodology on retinas from bovines and human donors. Successful separation of phosphatidylethanolamine (PE), phosphatidylinositol (PI), phosphatidylserine (PS), PC, lyso-phosphatidylcholine (LPC) and sphingomyelin (SM) was achieved using a silica gel column and a gradient of hexane/isopropanol/water containing ammonium formate as a mobile phase. A complete structural characterisation of intact phosphatidylcholine species was obtained by collision-induced dissociation (CID) in the negative mode. Fatty acid composition and distribution can be clearly assigned based on the intensity of sn-2/sn-1 fragment ions. The PC species were characterised on bovine retina, 28 of which were dipolyunsaturated PC species containing one VLC-PUFA (C24-C36) with three to six double bonds. VLC-PUFA was always in the sn-1 position while PUFA at the sn-2 position was exclusively docosahexaenoic acid (DHA, C22:6n-3). Most of these VLC-PUFA-containing dipolyunsaturated PCs were detected and quantified in human retinas. The quantitative analysis of the different PC molecular species was performed in the positive mode using precursor ion scanning of m/z 184 and 14:0/14:0-PC and 24:0/24:0-PC as internal standards. The relationship between the MS peak intensities of different PC species and their carbon chain length was included for calibration. The main compounds represented were those having VLC-PUFA with 32 carbon atoms (C32:3, C32:4, C32:5 and C32:6) and 34 carbon atoms (C34:3, C34:4, C34:5 and C34:6). Dipolyunsaturated PCs with 36:5 and 36:6 were detected but in smaller quantities. In conclusion, this new HPLC-ESI-MS/MS method is sensitive and specific enough to structurally characterise and quantify all molecular PC species, including those esterified with VLC-PUFA. This technique is valuable for a precise characterisation of PC molecular species containing VLC-PUFA in retina and may be useful for a better understanding of the pathogenesis of STD3. 相似文献
110.