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71.
Comprehensive two-dimensional gas chromatography combined with time-of-flight mass spectrometry (GC × GC-TOFMS) provides high resolution separations of complex samples with a mass spectrum at every point in the separation space. The large volumes of multidimensional data obtained by GC × GC-TOFMS analysis are analyzed using a principal component analysis (PCA) method described herein to quickly and objectively discover differences between complex samples. In this work, we submitted 54 chromatograms to PCA to automatically compare the metabolite profiles of three different species of plants, namely basil (Ocimum basilicum), peppermint (Mentha piperita), and sweet herb stevia (Stevia rebaudiana), where there were 18 chromatograms for each type of plant. The 54 scores of the m/z 73 data set clustered in three groups according to the three types of plants. Principal component 1 (PC 1) separated the stevia cluster from the basil and peppermint clusters, capturing 61.84% of the total variance. Principal component 2 (PC 2) separated the basil cluster from the peppermint cluster, capturing 16.78% of the total variance. The PCA method revealed that relative abundances of amino acids, carboxylic acids, and carbohydrates were responsible for differentiating the three plants. A brief list of the 16 most significant metabolites is reported. After PCA, the 54 scores of the m/z 217 data set clustered in three groups according to the three types of plants, as well, yielding highly loaded variables corresponding with chemical differences between plants that were complementary to the m/z 73 information. The PCA data mining method is applicable to all of the monitored selective mass channels, utilizing all of the collected data, to discover unknown differences in complex sample profiles. 相似文献
72.
The reaction of 2-(diphenylmethylene)thietan-3-one (2) with 1,2,4,5-tetrazines (3a-c) in KOH/MeOH/THF gives 4H-pyrazolo[5,1-c]thiazines (7a-c). This novel condensation reaction proceeds via the intermediacy of an 8-(diphenylmethylene)-2H-1,4,5-thiadiazocin-7(8H)-one (5), which undergoes a multi-step rearrangement including a rare anti-Michael addition. 相似文献
73.
Klukovich HM Kean ZS Black Ramirez AL Lenhardt JM Lin J Hu X Craig SL 《Journal of the American Chemical Society》2012,134(23):9577-9580
Epoxidized polybutadiene and epoxidized polynorbornene were subjected to pulsed ultrasound in the presence of small molecules capable of being trapped by carbonyl ylides. When epoxidized polybutadiene was sonicated, there was no observable small molecule addition to the polymer. Concurrently, no appreciable isomerization (cis to trans epoxide) was observed, indicating that the epoxide rings along the backbone are not mechanically active under the experimental conditions employed. In contrast, when epoxidized polynorbornene was subjected to the same conditions, both addition of ylide trapping reagents and net isomerization of cis to trans epoxide were observed. The results demonstrate the mechanical activity of epoxides, show that mechanophore activity is determined not only by the functional group but also the polymer backbone in which it is embedded, and facilitate a characterization of the reactivity of the ring-opened dialkyl epoxide. 相似文献
74.
Photonic crystal waveguides are optimized for modal confinement and loss related to slow light with high group index. A detailed comparison between optimized circular-hole based waveguides and optimized waveguides with free topology is performed. Design robustness with respect to manufacturing imperfections is enforced by considering different design realizations generated from under-, standard- and over-etching processes in the optimization procedure. A constraint ensures a certain modal confinement, and loss related to slow light with high group index is indirectly treated by penalizing field energy located in air regions. It is demonstrated that slow light with a group index up to ng = 278 can be achieved by topology optimized waveguides with promising modal confinement and restricted group-velocity-dispersion. All the topology optimized waveguides achieve a normalized group-index bandwidth of 0.48 or above. The comparisons between circular-hole based designs and topology optimized designs illustrate that the former can be efficient for dispersion engineering but that larger improvements are possible if irregular geometries are allowed. 相似文献
75.
Grgić J Ott JR Wang F Sigmund O Jauho AP Mørk J Mortensen NA 《Physical review letters》2012,108(18):183903
A common strategy to compensate for losses in optical nanostructures is to add gain material in the system. By exploiting slow-light effects it is expected that the gain may be enhanced beyond its bulk value. Here we show that this route cannot be followed uncritically: inclusion of gain inevitably modifies the underlying dispersion law, and thereby may degrade the slow-light properties underlying the device operation and the anticipated gain enhancement itself. This degradation is generic; we demonstrate it for three different systems of current interest (coupled-resonator optical waveguides, Bragg stacks, and photonic crystal waveguides). Nevertheless, a small amount of added gain may be beneficial. 相似文献
76.
Chaudhuri D Li D Sigmund E Wettach H Höger S Lupton JM 《Chemical communications (Cambridge, England)》2012,48(53):6675-6677
Dual singlet-triplet fluorescence-phosphorescence emitting compounds demonstrate that plasmonic surface enhancement is controlled solely by the underlying oscillator strength of a transition: metal-free compounds with weak spin-orbit coupling show no enhancement in phosphorescence efficiency even though fluorescence is amplified. 相似文献
77.
Manson JL Baldwin AG Scott BL Bendix J Del Sesto RE Goddard PA Kohama Y Tran HE Ghannadzadeh S Singleton J Lancaster T Möller JS Blundell SJ Pratt FL Zapf VS Kang J Lee C Whangbo MH Baines C 《Inorganic chemistry》2012,51(14):7520-7528
[Ni(HF(2))(3-Clpy)(4)]BF(4) (py = pyridine) is a simple one-dimensional (1D) coordination polymer composed of compressed NiN(4)F(2) octahedra that form chains with bridging HF(2)(-) ligands. In spite of significant distortion of the HF(2)(-) bridge, a quasi-1D antiferromagnetic (AFM) behavior was observed with J(FHF) = 4.86 K. 相似文献
78.
79.
Rajind Mendis Cezary Sydlo Jochen Sigmund Michael Feiginov Peter Meissner Hans L. Hartnagel 《International Journal of Infrared and Millimeter Waves》2005,26(2):201-207
We report on a completely coherent, tunable, continuous-wave THz system where, for the first-time, both the transmitter and receiver are log-periodic-antenna coupled LTG-GaAs based finger-photomixers. This compact room-temperature system exhibits signal-to-noise ratios (> 103) comparable to or better than what is reported in the literature, and has potential applications in high-resolution spectroscopy and imaging. For the purpose of demonstration, we also present results of spectroscopy measurements carried out on fused silica, which are in agreement with previously published THz-TDS measurements. 相似文献
80.
Duncan A. J. Harding Eric G. Hope Gregory A. Solan John Fawcett 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(7):m321-m322
The reaction between carbonyl fluoride and [Ir(COD)(PPh3)2]BF4 (COD is cycloocta‐1,5‐diene) in dichloromethane solution affords the novel title iridium salt, [IrCl2(C18H15P)2(CO)2]BF4. The cation lies across a twofold rotation axis in the space group P21212 and its structure confirms the presence in a cis relationship of two metal‐bound chlorides, while the phosphine ligands occupy a trans pair of sites. The anion also lies across a twofold rotation axis, and the F atoms are disordered over two sets of sites. 相似文献