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991.
Andreas Bornø Carl J. Hulston Gerrit van Hall 《Journal of mass spectrometry : JMS》2014,49(8):674-680
In the present study, different MS methods for the determination of human muscle protein fractional synthesis rate (FSR) using [ring‐13C6]phenylalanine as a tracer were evaluated. Because the turnover rate of human skeletal muscle is slow, only minute quantities of the stable isotopically labeled amino acid will be incorporated within the few hours of a typical laboratory experiment. GC combustion isotope ratio MS (GC‐C‐IRMS) has thus far been considered the ‘gold’ standard for the precise measurements of these low enrichment levels. However, advances in liquid chromatography‐tandem MS (LC‐MS/MS) and GC‐tandem MS (GC‐MS/MS) have made these techniques an option for human muscle FSR measurements. Human muscle biopsies were freeze dried, cleaned, and hydrolyzed, and the amino acids derivatized using either N‐acetyl‐n‐propyl, phenylisothiocyanate, or N‐methyl‐N‐(tert‐butyldimethylsilyl)trifluoroacetamide (MTBSTFA) for GC‐C‐IRMS, LC‐MS/MS, and GC‐MS/MS analysis, respectively. A second derivative, heptafluorobutyric acid (HFBA), was also used for GC‐MS/MS analysis as an alternative for MTBSTFA. The machine reproducibility or the coefficients of variation for delta tracer‐tracee‐ratio measurements (delta tracer‐tracee‐ratio values around 0.0002) were 2.6%, 4.1%, and 10.9% for GC‐C‐IRMS, LC‐MS/MS, and GC‐MS/MS (MTBSTFA), respectively. FSR determined with LC‐MS/MS compared well with GC‐C‐IRMS and so did the GC‐MS/MS when using the HFBA derivative (linear fit Y = 1.08 ± 0.10, X + 0.0049 ± 0.0061, r = 0.89 ± 0.01, P < 0.0001). In conclusion, (1) IRMS still offers the most precise measurement of human muscle FSR, (2) LC‐MS/MS comes quite close and is a good alternative when tissue quantities are too small for GC‐C‐IRMS, and (3) If GC‐MS/MS is to be used, then the HFBA derivative should be used instead of MTBSTFA, which gave unacceptably high variability. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
992.
Single‐Layered Ultrasmall Nanoplates of MoS2 Embedded in Carbon Nanofibers with Excellent Electrochemical Performance for Lithium and Sodium Storage 下载免费PDF全文
Dr. Changbao Zhu Dr. Xiaoke Mu Prof. Peter A. van Aken Prof. Yan Yu Prof. Joachim Maier 《Angewandte Chemie (International ed. in English)》2014,53(8):2152-2156
The preparation and electrochemical storage behavior of MoS2 nanodots—more precisely single‐layered ultrasmall nanoplates—embedded in carbon nanowires has been studied. The preparation is achieved by an electrospinning process that can be easily scaled up. The rate performance and cycling stability of both lithium and sodium storage were found to be outstanding. The storage behavior is, moreover, highly exciting from a fundamental point of view, as the differences between the usual storage modes—insertion, conversion, interfacial storage—are beneficially blurred. The restriction to ultrasmall reaction domains allows for an almost diffusion‐less and nucleation‐free “conversion”, thereby resulting in a high capacity and a remarkable cycling performance. 相似文献
993.
Mixed IR/Vis Two‐Dimensional Spectroscopy: Chemical Exchange beyond the Vibrational Lifetime and Sub‐ensemble Selective Photochemistry 下载免费PDF全文
Dr. Luuk J. G. W. van Wilderen Dr. Andreas T. Messmer Prof. Dr. Jens Bredenbeck 《Angewandte Chemie (International ed. in English)》2014,53(10):2667-2672
Two‐dimensional exchange spectroscopy (2D EXSY) is a powerful method to study the interconversion (chemical exchange) of molecular species in equilibrium. This method has recently been realized in femtosecond 2D‐IR spectroscopy, dramatically increasing the time resolution. However, current implementations allow the EXSY signal (and therefore the chemical process of interest) only to be tracked during the lifetime (T1) of the observed spectroscopic transition. This is a severe limitation, as typical vibrational T1 are only a few ps. An IR/Vis pulse sequence is presented that overcomes this limit and makes the EXSY signal independent of T1. The same pulse sequence allows to collect time‐resolved IR spectra after electronic excitation of a particular chemical species in a mixture of species with strongly overlapping UV/Vis spectra. Different photoreaction pathways and dynamics of coexisting isomers or of species involved in different intermolecular interactions can thus be revealed, even if the species cannot be isolated because they are in rapid equilibrium. 相似文献
994.
Cell Tracking with Caged Xenon: Using Cryptophanes as MRI Reporters upon Cellular Internalization 下载免费PDF全文
Stefan Klippel Jörg Döpfert Dr. Jabadurai Jayapaul Martin Kunth Federica Rossella Matthias Schnurr Dr. Christopher Witte Dr. Christian Freund Dr. Leif Schröder 《Angewandte Chemie (International ed. in English)》2014,53(2):493-496
Caged xenon has great potential in overcoming sensitivity limitations for solution‐state NMR detection of dilute molecules. However, no application of such a system as a magnetic resonance imaging (MRI) contrast agent has yet been performed with live cells. We demonstrate MRI localization of cells labeled with caged xenon in a packed‐bed bioreactor working under perfusion with hyperpolarized‐xenon‐saturated medium. Xenon hosts enable NMR/MRI experiments with switchable contrast and selectivity for cell‐associated versus unbound cages. We present MR images with 103‐fold sensitivity enhancement for cell‐internalized, dual‐mode (fluorescence/MRI) xenon hosts at low micromolar concentrations. Our results illustrate the capability of functionalized xenon to act as a highly sensitive cell tracer for MRI detection even without signal averaging. The method will bridge the challenging gap for translation to in vivo studies for the optimization of targeted biosensors and their multiplexing applications. 相似文献
995.
Back Cover: Cell Tracking with Caged Xenon: Using Cryptophanes as MRI Reporters upon Cellular Internalization (Angew. Chem. Int. Ed. 2/2014) 下载免费PDF全文
996.
Casey A. Dougherty Joseph C. Furgal Dr. Mallory A. van Dongen Prof. Theodore Goodson III Prof. Mark M. Banaszak Holl Dr. Janet Manono Prof. Stassi DiMaggio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(16):4638-4645
Fluorescent dyes are commonly conjugated to nanomaterials for imaging applications using stochastic synthesis conditions that result in a Poisson distribution of dye/particle ratios and therefore a broad range of photophysical and biodistribution properties. We report the isolation and characterization of generation 5 poly(amidoamine) (G5 PAMAM) dendrimer samples containing 1, 2, 3, and 4 fluorescein (FC) or 6‐carboxytetramethylrhodamine succinimidyl ester (TAMRA) dyes per polymer particle. For the fluorescein case, this was achieved by stochastically functionalizing dendrimer with a cyclooctyne “click” ligand, separation into sample containing precisely defined “click” ligand/particle ratios using reverse‐phase high performance liquid chromatography (RP‐HPLC), followed by reaction with excess azide‐functionalized fluorescein dye. For the TAMRA samples, stochastically functionalized dendrimer was directly separated into precise dye/particle ratios using RP‐HPLC. These materials were characterized using 1H and 19F NMR spectroscopy, RP‐HPLC, UV/Vis and fluorescence spectroscopy, lifetime measurements, and MALDI. 相似文献
997.
Mono‐ and Bis(pyrrolo)tetrathiafulvalene Derivatives Tethered to C60: Synthesis,Photophysical Studies,and Self‐Assembled Monolayers 下载免费PDF全文
Dr. Marta Vico Solano Dr. Eduardo Antonio Della Pia Dr. Martyn Jevric Christina Schubert Xintai Wang Dr. Cornelia van der Pol Prof. Dr. Anders Kadziola Prof. Dr. Kasper Nørgaard Prof. Dr. Dirk M. Guldi Prof. Dr. Mogens Brøndsted Nielsen Prof. Dr. Jan O. Jeppesen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(32):9918-9929
A series of mono‐ (MPTTF) and bis(pyrrolo)tetrathiafulvalene (BPTTF) derivatives tethered to one or two C60 moieties was synthesized and characterized. The synthetic strategy for these dumbbell‐shaped compounds was based on a 1,3‐dipolar cycloaddition reaction between aldehyde‐functionalized MPTTF/BPTTF derivatives, two different tailor‐made amino acids, and C60. Electronic communication between the MPTTF/BPTTF units and the C60 moieties was studied by a variety of techniques including cyclic voltammetry and absorption spectroscopy. These solution‐based studies indicated no observable electronic communication between the MPTTF/BPTTF units and the C60 moieties. In addition, femtosecond and nanosecond transient absorption spectroscopy revealed, rather surprisingly, that no charge transfer from the MPTTF/BPTTF units to the C60 moieties takes place on excitation of the fullerene moiety. Finally, it was shown that the MPTTF–C60 and C60–BPTTF‐C60 dyad and triad molecules formed self‐assembled monolayers on a Au(111) surface by anchoring to C60. 相似文献
998.
Inside Cover: New Concepts for Designing d10‐M(L)n Catalysts: d Regime,s Regime and Intrinsic Bite‐Angle Flexibility (Chem. Eur. J. 36/2014) 下载免费PDF全文
999.
Localized Crystallization of Enantiomeric Organic Compounds on Chiral Micro‐patterns from Various Organic Solutions 下载免费PDF全文
Dr. Maarten W. van der Meijden Prof. Richard M. Kellogg Prof. David B. Amabilino 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10466-10474
The controlled crystallization of enantiomers of an organic compound (a cyclic phosphoric acid derivative) on templated micro‐patterned functionalised surfaces is demonstrated. Areas where a complementary chiral thiol has been located were effective heterogeneous nucleation centres when a solution of the compound is evaporated slowly. Various organic solvents were employed, which present a challenge with respect to other examples when water is used. The solvent and the crystallization method have an important influence on the crystal growth of these compounds. When chloroform was employed, well‐defined crystals grow away from the surface, whereas crystals grow in the plane from solutions in isopropanol. In both cases, nucleation is confined to the polar patterned regions of the surface, and for isopropanol growth is largely limited within the pattern, which shows the importance of surface chemistry for nucleation and growth. The apparent dependence on the enantiomer used in the latter case could imply stereo‐differentiation as a result of short‐range interactions (the templating monolayer is disordered, even at the nanometre scale). The size of the pattern of chiral monolayer also determines the outcome of the crystallization; 5 μm dots are most effective. Despite the low surface tension of the samples (relative to the high surface tension of water), differential solvation of the polar and hydrophobic layers of the solvents allows crystallization in the polar regions of the monolayer, therefore the polarity of the regions in which heterogeneous nucleation takes place is indeed very important. Despite the complex nature of the crystallization process, these results are an important step towards to the use of patterned surfaces for heterogeneous selective nucleation of enantiomers. 相似文献
1000.
Redox‐Induced Spin‐State Switching and Mixed Valency in Quinonoid‐Bridged Dicobalt Complexes 下载免费PDF全文
David Schweinfurth Yvonne Rechkemmer Stephan Hohloch Naina Deibel Irina Peremykin Jan Fiedler Raphael Marx Dr. Petr Neugebauer Prof. Dr. Joris van Slageren Prof. Dr. Biprajit Sarkar 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(12):3475-3486
The complexes [{(tmpa)CoII}2(μ‐L1)2?]2+ ( 12+ ) and [{(tmpa)CoII}2(μ‐L2)2?]2+ ( 22+ ), with tmpa=tris(2‐pyridylmethyl)amine, H2L1=2,5‐di‐[2‐(methoxy)‐anilino]‐1,4‐benzoquinone, and H2L2=2,5‐di‐[2‐(trifluoromethyl)‐anilino]‐1,4‐benzoquinone, were synthesized and characterized. Structural analysis of 22+ revealed a distorted octahedral coordination around the cobalt centers, and cobalt–ligand bond lengths that match with high‐spin CoII centers. Superconducting quantum interference device (SQUID) magnetometric studies on 12+ and 22+ are consistent with the presence of two weakly exchange‐coupled high‐spin cobalt(II) ions, for which the nature of the coupling appears to depend on the substituents on the bridging ligand, being antiferromagnetic for 12+ and ferromagnetic for 22+ . Both complexes exhibit several one‐electron redox steps, and these were investigated with cyclic voltammetry and UV/Vis/near‐IR spectroelectrochemistry. For 12+ , it was possible to chemically isolate the pure forms of both the one‐electron oxidized mixed‐valent 13+ and the two‐electron oxidized isovalent 14+ forms, and characterize them structurally as well as magnetically. This series thus provided an opportunity to investigate the effect of reversible electron transfers on the total spin‐state of the molecule. In contrast to 22+ , for 14+ the metal–ligand distances and the distances within the quinonoid ligand point to the existence of two low‐spin CoIII centers, thus showing the innocence of the quintessential non‐innocent ligands L. Magnetic data corroborate these observations by showing the decrease of the magnetic moment by roughly half (neglecting spin exchange effects) on oxidizing the molecules with one electron, and the disappearance of a paramagnetic response upon two‐electron oxidation, which confirms the change in spin state associated with the electron‐transfer steps. 相似文献