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91.
92.
Functionalized 2,3-benzoxepins were prepared by cyclopropanation of benzopyrylium triflates with diazoesters and subsequent TFA-mediated ring enlargement. 相似文献
93.
Dr. Michael Georg Hoesl M. Sc. Stefan Oehm Dr. Patrick Durkin Dr. Elise Darmon Dr. Lauri Peil Dr. Hans‐Rudolf Aerni Prof. Dr. Juri Rappsilber Prof. Dr. Jesse Rinehart Prof. Dr. David Leach Prof. Dr. Dieter Söll Prof. Dr. Nediljko Budisa 《Angewandte Chemie (International ed. in English)》2015,54(34):10030-10034
We have changed the amino acid set of the genetic code of Escherichia coli by evolving cultures capable of growing on the synthetic noncanonical amino acid L ‐β‐(thieno[3,2‐b]pyrrolyl)alanine ([3,2]Tpa) as a sole surrogate for the canonical amino acid L ‐tryptophan (Trp). A long‐term cultivation experiment in defined synthetic media resulted in the evolution of cells capable of surviving Trp→[3,2]Tpa substitutions in their proteomes in response to the 20 899 TGG codons of the E. coli W3110 genome. These evolved bacteria with new‐to‐nature amino acid composition showed robust growth in the complete absence of Trp. Our experimental results illustrate an approach for the evolution of synthetic cells with alternative biochemical building blocks. 相似文献
94.
Eva Vergucht Björn De Samber Andrei Izmer Bart Vekemans Karen Appel Sergei Tolmachev Laszlo Vincze Frank Vanhaecke 《Analytical and bioanalytical chemistry》2015,407(6):1559-1566
This study aims at evaluating the capabilities of synchrotron radiation micro X-ray fluorescence spectrometry (SR micro-XRF) for qualitative and semi-quantitative elemental mapping of the distribution of actinides in human tissues originating from individuals with documented occupational exposure. The investigated lymph node tissues were provided by the United States Transuranium and Uranium Registries (USTUR) and were analyzed following appropriate sample pre-treatment. Semi-quantitative results were obtained via calibration by external standards and demonstrated that the uranium concentration level in the detected actinide hot spots reaches more than 100 μg/g. For the plutonium hot spots, concentration levels up to 31 μg/g were found. As illustrated by this case study on these unique samples, SR micro-XRF has a high potential for this type of elemental bio-imaging owing to its high sensitivity, high spatial resolution, and non-destructive character.
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相似文献
95.
In this study, a coupled regional air quality modeling system is applied to investigate the time spatial variations in airborne particulate matters (PM10), originating from Mentougou to Beijing municipal area in the period of April 1-7, 2004, and the influences of complex terrain and meteorological conditions upon boundary layer structure and PM10 concentration distributions. An intercomparison of the performance with CALPUFF against the observed data is presented and an examination of scatter plots is provided. The statistics show that the correlation coefficient and STD between the modeled and observed data are 0.86 and 0.03, respectively. Analysis of model results illustrates that the pollutants emitted from Mentougou can be transported to Beijing municipal area along certain transport pathways, and PM10 concentration distributions show heterogeneity characteristics. Contributions of the Mentougou sources to the PM10 concentrations in Beijing municipal area are up to 0.1-15 μg/m^3. 相似文献
96.
We deal here with Sb and Bi doping effects of the n-type half-Heusler (HH) Ti0.3Zr0.35Hf0.35NiSn alloy on the measured thermoelectric properties. To date, the thermoelectric effects upon Bi doping on the Sn site of HH alloys have rarely been reported, while Sb has been widely used as a donor dopant. A comparison between the measured transport properties following arc melting and spark plasma sintering of both Bi- and Sb-doped samples indicates a much stronger doping effect upon Sb doping, an effect which was explained thermodynamically. Due to similar lattice thermal conductivity values obtained for the various doped samples, synthesized in a similar experimental route, no practical variations in the thermoelectric figure of merit values were observed between the various investigated samples, an effect which was attributed to compensation between the power factor and electrical thermal conductivity values regardless of the various investigated dopants and doping levels. 相似文献
97.
Cole JJ Barry CR Knuesel RJ Wang X Jacobs HO 《Langmuir : the ACS journal of surfaces and colloids》2011,27(11):7321-7329
Contact electrification creates an invisible mark, overlooked and often undetected by conventional surface spectroscopic measurements. It impacts our daily lives macroscopically during electrostatic discharge and is equally relevant on the nanoscale in areas such as soft lithography, transfer, and printing. This report describes a new conceptual approach to studying and utilizing contact electrification beyond prior surface force apparatus and point-contact implementations. Instead of a single point contact, our process studies nanocontact electrification that occurs between multiple nanocontacts of different sizes and shapes that can be formed using flexible materials, in particular, surface-functionalized poly(dimethylsiloxane) (PDMS) stamps and other common dielectrics (PMMA, SU-8, PS, PAA, and SiO(2)). Upon the formation of conformal contacts and forced delamination, contacted regions become charged, which is directly observed using Kelvin probe force microscopy revealing images of charge with sub-100-nm lateral resolution. The experiments reveal chemically driven interfacial proton exchange as the dominant charging mechanism for the materials that have been investigated so far. The recorded levels of uncompensated charges approach the theoretical limit that is set by the dielectric breakdown strength of the air gap that forms as the surfaces are delaminated. The macroscopic presence of the charges is recorded using force-distance curve measurements involving a balance and a micromanipulator to control the distance between the delaminated objects. Coulomb attraction between the delaminated surfaces reaches 150 N/m(2). At such a magnitude, the force finds many applications. We demonstrate the utility of printed charges in the fields of (i) nanoxerography and (ii) nanotransfer printing whereby the smallest objects are ~10 nm in diameter and the largest objects are in the millimeter to centimeter range. The printed charges are also shown to affect the electronic properties of contacted surfaces. For example, in the case of a silicon-on-insulator field effect transistors are in contact with PDMS and subsequent delamination leads to threshold voltage shifts that exceed 500 mV. 相似文献
98.
The properties of TiO(2) and polyphenyl oxide (PPO) blocking layers were compared using a highly positive redox shuttle in dye-sensitized solar cells. The dark current versus applied potential curve was found to be composed of two separate current features. Cyclic voltammetric and impedance measurements were performed to identify the source of the two features. The first feature results from electron transfer from the TiO(2) blocking layer and the first layer of the TiO(2) nanoparticle film contacting the substrate. The second onset of dark current results from the transport resistance in the nanoparticle film decreasing, thus allowing electron transfer to occur throughout the film. It is further demonstrated that PPO prevents back electron transfer from the conductive substrate to the redox shuttle across the entire potential range studied; however, the TiO(2) blocking layer is active and participates in electron transfer at rates similar to those of the TiO(2) nanoparticle film. 相似文献
99.
Mercedes Vázquez Dermot BrabazonFengjun Shang Jesse O. OmamoghoJeremy D. Glennon Brett Paull 《Trends in analytical chemistry : TRAC》2011,30(10):1575-1586
Centrifugally-driven microfluidic compact discs (μ-CDs) have attracted significant interest within the analytical science community in the past decade, with the primary focus on the potential of such platforms for performing parallel and/or multiplex biological assays and further application in biomedical diagnostics. More recently, μ-CD-based devices were also applied to environmental analysis as platforms for multi-sample extraction and transportation, prior to off-disc analysis in the laboratory. This review critically summarizes recent developments in μ-CD platforms for sample extraction, preconcentration, fractionation and purification in bioanalytical and environmental applications. We also summarize the common methods employed in the fabrication of μ-CD platforms. Further, we discuss preparation of stationary phases in microfluidic channels embedded in μ-CDs, as applications of μ-CDs in sample extraction are generally based on enclosed series of extraction phases and microcolumns. 相似文献
100.
To address the impact of electron correlations in the linear and non-linear response regimes of interacting many-electron systems exposed to time-dependent external fields, we study one-dimensional (1D) systems where the interacting problem is solved exactly by exploiting the mapping of the 1D N-electron problem onto an N-dimensional single electron problem. We analyze the performance of the recently derived 1D local density approximation as well as the exact-exchange orbital functional for those systems. We show that the interaction with an external resonant laser field shows Rabi oscillations which are detuned due to the lack of memory in adiabatic approximations. To investigate situations where static correlations play a role, we consider the time-evolution of the natural occupation numbers associated to the reduced one-body density matrix. Those studies shed light on the non-locality and time-dependence of the exchange and correlation functionals in time-dependent density and density-matrix functional theories. 相似文献