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81.
Meike Koenig Tadas Kasputis Daniel Schmidt Keith B. Rodenhausen Klaus-Jochen Eichhorn Angela K. Pannier Mathias Schubert Manfred Stamm Petra Uhlmann 《Analytical and bioanalytical chemistry》2014,406(28):7233-7242
A combined setup of quartz crystal microbalance and generalized ellipsometry can be used to comprehensively investigate complex functional coatings comprising stimuli-responsive polymer brushes and 3D nanostructures in a dynamic, noninvasive in situ measurement. While the quartz crystal microbalance detects the overall change in areal mass, for instance, during a swelling or adsorption process, the generalized ellipsometry data can be evaluated in terms of a layered model to distinguish between processes occurring within the intercolumnar space or on top of the anisotropic nanocolumns. Silicon films with anisotropic nanocolumnar morphology were prepared by the glancing angle deposition technique and further functionalized by grafting of poly-(acrylic acid) or poly-(N- isopropylacrylamide) chains. Investigations of the thermoresponsive swelling of the poly-(N-isopropylacrylamide) brush on the Si nanocolumns proved the successful preparation of a stimuli-responsive coating. Furthermore, the potential of these novel coatings in the field of biotechnology was explored by investigation of the adsorption of the model protein bovine serum albumin. Adsorption, retention, and desorption triggered by a change in the pH value is observed using poly-(acrylic acid) functionalized nanostructures, although generalized ellipsometry data revealed that this process occurs only on top of the nanostructures. Poly-(N-isopropylacrylamide) is found to render the nanostructures non-fouling properties. 相似文献
82.
In most of the mass range encompassed by the limits from the direct search and the electroweak precision tests, the Higgs boson of the standard model preferably decays to bottom quarks. We present, in analytic form, the dominant two-loop electroweak correction, of O(GF2mt4), to the partial width of this decay. It amplifies the familiar enhancement due to the O(GFmt2) one-loop correction by about +16% and thus more than compensates the screening by about -8% through strong-interaction effects of order O(alphasGFmt2). 相似文献
83.
A novel magnetic resonance imaging approach, called diffusion-direction-dependent imaging (DDI), is introduced. Due to inherent anisotropic diffusion properties, peripheral nerves can be visualized on diffusion tensor imaging (DTI). The largest signal attenuation on DTI correlates with the direction of a nerve fiber, and the least signal attenuation correlates with the direction perpendicular to the nerve fiber. Since low signal-to-noise ratio is a concern in peripheral nerve DTI, we explored a new approach focusing on the perpendicular diffusion direction. A 36-gradient diffusion direction scheme was used. A mean expected curve specific for peripheral nerves was calculated based on the sciatic nerve and its division into the common peroneal nerve and the tibial nerve in three healthy volunteers. By a simple postprocessing method, a comparison of the mean expected curve and the measured curve was made voxel by voxel, and the sciatic nerve and its division were reconstructed, excluding other tissues. More studies are needed to investigate whether other postprocessing methods or other diffusion direction schemes are more suited for peripheral nerve imaging with DDI. Further studies may also be of interest to investigate whether DDI can be a complementary method to conventional T(1)-weighted and T(2)-weighted sequences in the imaging of peripheral nerve pathology or even in the visualization of other tissues, possibly with different diffusion direction schemes. 相似文献
84.
The present study aimed describing the ovaries of the sugarcane spittlebug Mahanarva fimbriolata which are meroistic telotrophic with nurse cells and oocytes located in the tropharium. SEM revealed paired ovaries located dorsolaterally around the intestine, and oocytes exhibiting shapes ranging from round (less developed) to elliptic (more developed), suggesting a simultaneous, although, asynchronous development. Based on histological data we classified the oocytes in stages from I to V. Stage I oocytes exhibit follicular epithelium with cubic and/or prismatic cells, fine cytoplasmic granules. Stage II oocytes present intercellular spaces in the follicular epithelium due to the incorporation of yolk elements from the hemolymph. Small granules are present in the periphery of oocytes while larger granules are observed in the center. Stage III oocytes are larger and intercellular spaces in the follicular epithelium are evident, as well as the interface between follicular epithelium and oocyte. Yolk granules of different sizes are present in the cytoplasm. During this stage, chorion deposition initiates. Stage IV oocytes exhibit squamous follicular cells and larger intercellular spaces when compared to those observed in the previous stage. The oocyte cytoplasm present granular and viscous yolk, the latter is the result of the breakdown of granules. Stage V oocytes exhibit a follicular epithelium almost completely degenerated, smaller quantities of granular yolk and large amounts of viscous yolk. Based on our findings we established the sequence of yolk deposition in M. fimbriolata oocyte as follows: proteins and lipids, which are first produced by endogenous processes in stages I and II oocytes. Exogenous incorporation begins in stage III. In stages I and II oocytes, lipids are also produced by follicular epithelial cells. The third element to be deposited is polysaccharides, mainly found as complexes. Therefore, the yolk present in the oocytes of this species consists of glycolipoproteins. Molecular weights of proteins present in M. fimbriolata oocytes ranged from 10 to 92 KDa, differently from vitellogenin, the most common protein present in insect oocytes, weighing approximately 180 KDa. 相似文献
85.
Maria Haimerl Dr. Christian Graßl Dr. Michael Seidl Dr. Martin Piesch Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(72):18129-18134
The reactivity of white phosphorus and yellow arsenic towards two different nickel nacnac complexes is investigated. The nickel complexes [(L1Ni)2tol] ( 1 , L1=[{N(C6H3iPr2-2,6)C(Me)}2CH]−) and [K2][(L1Ni)2(μ,η1 : 1-N2)] ( 6 ) were reacted with P4, As4 and the interpnictogen compound AsP3, respectively, yielding the homobimetallic complexes [(L1Ni)2(μ-η2,κ1:η2,κ1-E4)] (E=P ( 2 a ), As ( 2 b ), AsP3 ( 2 c )), [(L1Ni)2(μ,η3 : 3-E3)] (E=P ( 3 a ), As ( 3 b )) and [K@18-c-6(thf)2][L1Ni(η1 : 1-E4)] (E=P ( 7 a ), As ( 7 b )), respectively. Heating of 2 a , 2 b or 2 c also leads to the formation of 3 a or 3 b . Furthermore, the reactivity of these compounds towards reduction agents was investigated, leading to [K2][(L1Ni)2(μ,η2 : 2-P4)] ( 4 ) and [K@18-c-6(thf)3][(L1Ni)2(μ,η3 : 3-E3)] (E=P ( 5 a ), As ( 5 b )), respectively. Compound 4 shows an unusual planarization of the initial Ni2P4-prism. All products were comprehensively characterized by crystallographic and spectroscopic methods. 相似文献
86.
Development of a Simple and Fast Electrochemical Method for Screening and Stoichiometric Determination of Dimenhydrinate 下载免费PDF全文
Jhonys Machado Freitas Thiago da Costa Oliveira Polyana Luiza Silva Denise Tofanello Gimenes Rodrigo Alejandro Abarza Munoz Eduardo Mathias Richter 《Electroanalysis》2014,26(9):1905-1911
Dimenhydrinate (DIM) is a salt composed by the combination of two active pharmaceutical ingredients: diphenhydramine (DIP) and 8‐chlorotheophylline (CTP). In this work, the use of batch injection analysis with multiple pulse amperometric detection (BIA‐MPA) was proposed for the first time for fast stoichiometric determination of DIM. DIP (cation) and CTP (anion) were determined simultaneously in pharmaceutical samples with a simple and fast injection procedure (70 injections h?1). Additional strategies were also proposed for rapid screening of samples containing the DIM salt. By a simple injection of a sample into the BIA system (without using of calibration curve), reliable information about stoichiometry of the DIM salt (1 : 1; DIP:CTP) and presence or absence of interfering species (electroactive) can be achieved. 相似文献
87.
Oxidizing Elemental Platinum with Oleum under Harsh Conditions: The Unique Tris(disulfato)platinate(IV) [Pt(S2O7)3]2− Anion 下载免费PDF全文
Jörn Bruns Prof. Dr. Thorsten Klüner Prof. Dr. Mathias S. Wickleder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7222-7227
For the first time, direct oxidation of elemental platinum by a mineral acid to its tetravalent state was observed in course of the reaction of platinum with oleum (65 % SO3) in the presence of barium carbonate. The reaction has been carried out in torch‐sealed glass ampoules at 160 °C and gave yellow single crystals of Ba[Pt(S2O7)3](H2SO4)0.5(H2S2O7)0.5 (triclinic, P$\bar 1$ , Z=2, a=992.05(2), b=1069.07(3), c=1114.22(3) pm, α=69.49(7), β=72.96(2), γ=72.93(1)°, V=1033.95(5) Å3). The structure of Ba[Pt(S2O7)3](H2SO4)0.5(H2S2O7)0.5 exhibits the unique tris‐(disulfato)‐platinate anion [Pt(S2O7)3]2? with three chelating disulfate groups coordinated to the platinum atom. Charge balance is achieved by the Ba2+ ions, which are coordinated by (S2O7)2? groups from the platinate complex and by disordered sulfuric acids and disulfuric acid molecules. Thermal decomposition of the bulk material revealed elemental platinum and barium sulfate as decomposition residual. 相似文献
88.
Aryl–Phenyl Scrambling in Intermediate Organopalladium Complexes: A Gas‐Phase Study of the Mizoroki–Heck Reaction 下载免费PDF全文
Lukas Fiebig Dr. Nils Schlörer Prof. Hans‐Günther Schmalz Priv.‐Doz. Dr. Mathias Schäfer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(17):4906-4910
The intramolecular aryl–phenyl scrambling reaction within palladium–DPPP–aryl complex (DPPP=1,3‐bis(diphenylphosphino)propane) ions was analyzed by state‐of‐the‐art tandem MS, including gas‐phase ion/molecule reactions. The Mizoroki–Heck cross‐coupling reaction was performed in the gas phase, and the intrinsic reactivity of important intermediates could be examined. Moreover, linear free‐energy correlations were applied, and a mechanism for the scrambling reaction proceeding via phosphonium cations was assumed. 相似文献
89.
Eric Mädl Dr. Mikhail V. Butovskii Dr. Gábor Balázs Dr. Eugenia V. Peresypkina Dr. Alexander V. Virovets Michael Seidl Prof. Dr. Manfred Scheer 《Angewandte Chemie (International ed. in English)》2014,53(29):7643-7646
Unprecedented functionalized products with an η4‐P5 ring are obtained by the reaction of [Cp*Fe(η5‐P5)] ( 1 ; Cp*=η5‐C5Me5) with different nucleophiles. With LiCH2SiMe3 and LiNMe2, the monoanionic products [Cp*Fe(η4‐P5CH2SiMe3)]? and [Cp*Fe(η4‐P5NMe2)]?, respectively, are formed. The reaction of 1 with NaNH2 leads to the formation of the trianionic compound [{Cp*Fe(η4‐P5)}2N]3?, whereas the reaction with LiPH2 yields [Cp*Fe(η4‐P5PH2)]? as the main product, with {[Cp*Fe(η4‐P5)]2PH}2? as a byproduct. The calculated energy profile of the reactions provides a rationale for the formation of the different products. 相似文献
90.
Martin Piesch Dr. Fabian Dielmann Stephan Reichl Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(7):1518-1524
A systematic study on the reactivity of the triple-decker complex [(Cp’’’Co)2(μ,η4:η4-C7H8)] ( A ) (Cp’’’=1,2,4-tritertbutyl-cyclopentadienyl) towards sandwich complexes containing cyclo-P3, cyclo-P4, and cyclo-P5 ligands under mild conditions is presented. The heterobimetallic triple-decker sandwich complexes [(Cp*Fe)(Cp’’’Co)(μ,η5:η4-P5)] ( 1 ) and [(Cp’’’Co)(Cp’’’Ni)(μ,η3:η3-P3)] ( 3 ) (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) were synthesized and fully characterized. In solution, these complexes exhibit a unique fluxional behavior, which was investigated by variable temperature NMR spectroscopy. The dynamic processes can be blocked by coordination to {W(CO)5} fragments, leading to the complexes [(Cp*Fe)(Cp’’’Co)(μ3,η5:η4:η1-P5){W(CO)5}] ( 2 a ), [(Cp*Fe)(Cp’’’Co)(μ4,η5:η4:η1:η1-P5){(W(CO)5)2}] ( 2 b ), and [(Cp’’’Co)(Cp’’’Ni)(μ3,η3:η2:η1-P3){W(CO)5}] ( 4 ), respectively. The thermolysis of 3 leads to the tetrahedrane complex [(Cp’’’Ni)2(μ,η2:η2-P2)] ( 5 ). All compounds were fully characterized using single-crystal X-ray structure analysis, NMR spectroscopy, mass spectrometry, and elemental analysis. 相似文献