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91.
Gray TG Rudzinski CM Meyer EE Holm RH Nocera DG 《Journal of the American Chemical Society》2003,125(16):4755-4770
The electronic, vibrational, and excited-state properties of hexanuclear rhenium(III) chalcogenide clusters based on the [Re(6)(mu(3)-Q)(8)](2+) (Q = S, Se) core have been investigated by spectroscopic and theoretical methods. Ultraviolet or visible excitation of [Re(6)Q(8)](2+) clusters produces luminescence with ranges in maxima of 12 500-15 100 cm(-)(1), emission quantum yields of 1-24%, and emission lifetimes of 2.6-22.4 microseconds. Nonradiative decay rate constants and the luminescence maxima follow the trend predicted by the energy gap law (EGL). Examination of 24 clusters in solution and 14 in the solid phase establish that exocluster ligands engender the observed EGL behavior; clusters with oxygen- or nitrogen-based apical ligands achieve maximal quantum yields and the longest lifetimes. The excited-state decay mechanism was investigated by applying nonradiative decay models to temperature-dependent emission experiments. Solid-state Raman spectra were recorded to identify vibrational contributions to excited-state deactivation; spectral assignments were enabled by normal coordinate analysis afforded from Hartree-Fock and DFT calculations. Excited-state decay is interpreted with a model where normal modes largely centered on the [Re(6)Q(8)](2+) core induce nonradiative relaxation. Hartree-Fock and DFT calculations of the electronic structure of the hexarhenium family of compounds support such a model. These experimental and theoretical studies of [Re(6)Q(8)](2+) luminescence provide a framework for elaborating a variety of luminescence-based applications of the largest series of isoelectronic clusters yet discovered. 相似文献
92.
This study reports an optimized headspace-solid phase microextraction (HS-SPME) method for the determination of methoxypyrazines in wine. Analysis was performed by using comprehensive two-dimensional gas chromatography with novel detection capabilities, including nitrogen phosphorus detection (GC x GC-NPD) and time-of-flight mass spectrometry (GC x GC-TOFMS). In the latter, stable isotope dilution was performed for the quantitation of 2-methoxy-3-(2-methylpropyl) pyrazine (IBMP), using labelled 2-(2H3)methoxy-3-(2-methylpropyl)pyrazine (d3-IBMP) as the internal standard, and resolution of the two analogues was facilitated using the deconvolution capabilities of the TOFMS. This research represents the first report of HS-SPME with isotope dilution and GC x GC-TOFMS (GC x GC-IDTOFMS). Analysis by GC x GC-NPD enabled detection limits of 0.5 ng/L for the quantitation of IBMP, which was superior to that obtained using GC x GC-IDTOFMS (1.95 ng/L). Nevertheless, both methods were adequately sensitive for real wine analysis, yielding highly comparable IBMP concentrations of 26.1 and 27.8 ng/L, respectively, from a Sauvignon blanc wine. The complexity of the real wine headspace was simplified as a result of selective detection using GC x GC-NPD and, in the case of GC x GC-IDTOFMS, the use of extracted ion chromatograms (EICs). 相似文献
93.
94.
Dr. James P. Dombrowski Dr. Micah S. Ziegler Dr. Neelay M. Phadke Erum Mansoor Dr. Daniel S. Levine Dr. Ryan J. Witzke Prof. Dr. Martin Head-Gordon Prof. Dr. Alexis T. Bell Prof. Dr. T. Don Tilley 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(1):307-315
Anionic molecular models for nonhydrolyzed and partially hydrolyzed aluminum and gallium framework sites on silica, M[OSi(OtBu)3]4− and HOM[OSi(OtBu)3]3− (where M=Al or Ga), were synthesized from anionic chlorides Li{M[OSi(OtBu)3]3Cl} in salt metathesis reactions. Sequestration of lithium cations with [12]crown-4 afforded charge-separated ion pairs composed of monomeric anions M[OSi(OtBu)3]4− with outer-sphere [([12]crown-4)2Li]+ cations, and hydroxides {HOM[OSi(OtBu)3]3} with pendant [([12]crown-4)Li]+ cations. These molecular models were characterized by single-crystal X-ray diffraction, vibrational spectroscopy, mass spectrometry and NMR spectroscopy. Upon treatment of monomeric [([12]crown-4)Li]{HOM[OSi(OtBu)3]3} complexes with benzyl alcohol, benzyloxide complexes were formed, modeling a possible pathway for the formation of active sites for Meerwin–Ponndorf–Verley (MPV) transfer hydrogenations with Al/Ga-doped silica catalysts. 相似文献
95.
96.
Tryptanthrin is a natural product with numerous important pharmacological properties. Tryptanthrin and its analogs are commonly prepared by condensation of isatoic anhydride and isatin. In this Letter we investigate the formation of tryptanthrin derivatives upon Oxone-induced oxidative dimerization of indole-3-carbaldehydes. 相似文献
97.
J. William Helton J. E. Pascoe Ryan Tully-Doyle Victor Vinnikov 《Integral Equations and Operator Theory》2016,84(2):151-181
We establish several new relations between the discrete transition operator, the continuous Laplacian and the averaging operator associated with combinatorial and metric graphs. It is shown that these operators can be expressed through each other in a very explicit way. In particular, the averaging operator appears to be closely related to the solutions of the associated wave equation. The machinery used allows one to study a class of infinite graphs without assumption on the local finiteness. 相似文献
98.
Sergey S. Golotvin Rostislav Pol Ryan R. Sasaki Asya Nikitina Philip Keyes 《Magnetic resonance in chemistry : MRC》2012,50(6):429-435
Automated structure verification using 1H NMR data or a combination of 1H and heteronuclear single‐quantum correlation (HSQC) data is gaining more interest as a routine application for qualitative evaluation of large compound libraries produced by synthetic chemistry. The goal of this automated software method is to identify a manageable subset of compounds and data that require human review. In practice, the automated method will flag structure and data combinations that exhibit some inconsistency (i.e. strange chemical shifts, conflicts in multiplicity, or overestimated and underestimated integration values) and validate those that appear consistent. One drawback of this approach is that no automated system can guarantee that all passing structures are indeed correct structures. The major reason for this is that approaches using only 1H or even 1H and HSQC spectra often do not provide sufficient information to properly distinguish between similar structures. Therefore, current implementations of automated structure verification systems allow, in principle, false positive results. Presented in this work is a method that greatly reduces the probability of an automated validation system passing incorrect structures (i.e. false positives). This novel method was applied to automatically validate 127 non‐proprietary compounds from several commercial sources. Presented also is the impact of this approach on false positive and false negative results. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
99.
Molecular and morphological characterization of midblock‐sulfonated styrenic triblock copolymers
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Kenneth P. Mineart Justin J. Ryan Byeongdu Lee Steven D. Smith Richard J. Spontak 《Journal of Polymer Science.Polymer Physics》2017,55(6):490-497
Midblock‐sulfonated triblock copolymers afford a desirable opportunity to generate network‐forming amphiphilic materials that are suitable for use in a wide range of emerging technologies as fuel‐cell, water‐desalination, ion‐exchange, photovoltaic, or electroactive membranes. Employing a previously reported synthetic strategy wherein poly(p‐tert‐butylstyrene) remains unreactive, we have selectively sulfonated the styrenic midblock of a poly(p‐tert‐butylstyrene‐b‐styrene‐b‐p‐tert‐butylstyrene) (TST) triblock copolymer to different extents. Comparison of the resulting sulfonated copolymers with results from our prior study provides favorable quantitative agreement and suggests that a shortened reaction time is advantageous. An ongoing challenge regarding the morphological development of charged block copolymers is the competition between microphase separation of the incompatible blocks and physical cross‐linking of ionic clusters, with the latter often hindering the former. Here, we expose the sulfonated TST copolymers to solvent‐vapor annealing to promote nanostructural refinement. The effect of such annealing on morphological characteristics, as well as on molecular free volume, is explored. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 490–497 相似文献
100.
Andreas Dorian Emily J. Landgreen Hayley R. Petras Prof. James J. Shepherd Prof. Florence J. Williams 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(42):10839-10843
The facile production of ArCF2X and ArCX3 from ArCF3 using catalytic iron(III)halides is reported, which constitutes the first iron-catalyzed halogen exchange for non-aromatic C−F bonds. Theoretical calculations suggest direct activation of C−F bonds by iron coordination. ArCX3 and ArCF2X products of the reaction are synthetically valuable due to their diversification potential. In particular, chloro- and bromodifluoromethyl arenes (ArCF2Cl, ArCF2Br respectively) provide access to a myriad of difluoromethyl arene derivatives (ArCF2R). To optimize for mono-halogen exchange, a statistical method called Design of Experiments was used. Optimized parameters were successfully applied to electron rich and electron deficient aromatic substrates, and to the late stage diversification of flufenoxuron, a commercial insecticide. These methods are highly practical, being run at convenient temperatures and using inexpensive common reagents. 相似文献