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31.
32.
Nelson BN Schieber LJ Barich DH Lubach JW Offerdahl TJ Lewis DH Heinrich JP Munson EJ 《Solid state nuclear magnetic resonance》2006,29(1-3):204-213
Solid-state NMR spectroscopy (SSNMR) is an extremely powerful technique for the analysis of pharmaceutical dosage forms. A major limitation of SSNMR is the number of samples that can be analyzed in a given period of time. A solid-state magic-angle spinning (MAS) probe that can simultaneously acquire up to seven SSNMR spectra is being developed to increase throughput/signal-to-noise ratios. A prototype probe incorporating two MAS modules has been developed and spectra of ibuprofen and aspirin have been acquired simultaneously. This version is limited to being a two-module probe due to large amounts of space required for the tuning elements located next to the MAS modules. A new probe design incorporating coaxial transmission lines and smaller MAS modules has been constructed. This probe allows for close proximity of the MAS modules (within 3 cm), adequate proton decoupling power (>50 kHz), and the capability of remote tuning and sample changing. Spectra of hexamethylbenzene (HMB) have been acquired and show signal-to-noise ratios comparable to existing SSNMR probes. Adamantane line widths are also comparable to conventional probe technology. Decoupling powers of 70 kHz have been achieved using a MAS module suitable for 3 cm spacing between modules. Remote tuning has also been achieved with this new coaxial transmission line design. This probe design can be easily scaled to incorporate multiple MAS modules, which is a limitation of the previous design. The number of modules that can be incorporated is only limited by the number of transmission lines that will fit in a cross-sectional diameter of the bore and the axial field length of the magnet. 相似文献
33.
The calibration of a solid-state NMR spectrometer requires setting the magic angle, setting the reference and decoupler frequencies, ensuring that the magnetic field is homogeneous across the sample volume, optimizing the signal-to-noise ratio, determining the pi/2 pulse durations, and optimizing the Hartman-Hahn matching condition. Each task has one or more widely accepted standards, such as potassium bromide for setting the magic angle, adamantane for optimizing magnet homogeneity, and hexamethylbenzene or glycine for measuring the signal-to-noise ratio. We show that all of these tasks can be performed using 3-methylglutaric acid (MGA). In the case of high-powered decoupling, the CH(2) and CH carbon peaks of MGA provide an opportunity to evaluate the decoupling in a manner that is superior to any of the commonly used standard compounds. Thus, MGA can be used as a single solid-state NMR standard compound to perform all calibration steps except for magnet shimming. 相似文献
34.
Yu. A. Mostovoi I. A. Kuznetsov V. A. Solovei A. P. Serebrov I. V. Stepanenko T. K. Baranova A. V. Vasiliev Yu. P. Rudnev B. G. Yerozolimsky M. S. Dewey F. Wietfeldt O. Zimmer V. V. Nesvizhevsky 《Physics of Atomic Nuclei》2001,64(11):1955-1960
A new experimental value of the fundamental weak-interaction parameter λ=G A/GV (?1.2686±0.0046) is obtained for the first time by an original method that consists in measuring both P-odd correlations in free-neutron decay. 相似文献
35.
Fred P. Dewey 《Fresenius' Journal of Analytical Chemistry》1891,30(1):344-347
Ohne Zusammenfassung 相似文献
36.
37.
Dewey Holten Martin Gouterman William W. Parson† Maurice W. Windsor Mark G. Rockley ‡ 《Photochemistry and photobiology》1976,23(6):415-423
Abstract— Nanosecond and picosecond. kinetic techniques have been used to study electron transfer from the first excited singlet state (Bph*) and the first excited triplet state (Bph T ) of bacteriopheophytin to p -benzoquinone. Quenching of the first excited singlet state by 40 m M p -benzoquinone results in a decrease in the lifetime of Bph* but does not lead directly to the formation of the π-cation radical (Bph†). In the presence of 8 M methyl iodide and 40 m M p -benzoquinone together, the singlet lifetime is reduced further; however, the quantum yield of Bph T is enhanced due to the increased rate of intersystem crossing between Bph* and Bph T . Electron transfer from Bph T to p -benzoquinone leads to the formation and detection of Bph†. The results are discussed in terms of the spin-selectivity of the reverse electron transfer process within the intermediate charge transfer complexes. 相似文献
38.
39.
Tomizaki KY Loewe RS Kirmaier C Schwartz JK Retsek JL Bocian DF Holten D Lindsey JS 《The Journal of organic chemistry》2002,67(18):6519-6534
We present the synthesis and characterization of new light-harvesting arrays containing two, four, or eight perylene-monoimide accessory pigments attached to a zinc porphyrin. Each perylene is substituted with one or three 4-tert-butylphenoxy substituents. A 4,3'- or 4,2'-diarylethyne linker joins the perylene N-imide position and the porphyrin meso-position, affording divergent or convergent architectures, respectively. The architectures are designed to provide high solubility in organic media and facile perylene-to-porphyrin energy transfer, while avoiding charge-transfer quenching of the excited porphyrin product. For the array containing four perylenes per porphyrin in both nonpolar (toluene) and polar (benzonitrile) media and for the array containing eight perylenes per porphyrin in toluene, the photoexcited perylene-monoimide dye (PMI) decays rapidly ( approximately 3.5 ps) and predominantly (>or=90%) by energy transfer to the zinc porphyrin to form the excited zinc porphyrin (Zn), which has excited-state characteristics (lifetime, fluorescence yield) comparable (within approximately 10%) to those of the isolated chromophore. For the array containing eight perylenes in benzonitrile, PMI decays approximately 80% by energy transfer (forming Zn) and approximately 20% by hole transfer (forming PMI- Zn+); Zn subsequently decays approximately 20% by electron transfer (also forming PMI- Zn+) and approximately 80% by the normal routes open to the porphyrin monomer (intersystem crossing, internal conversion, fluorescence). In addition to rapid and efficient perylene-to-porphyrin energy transfer, the broad blue-green to yellow absorption of the perylene dyes complements the blue absorption of the porphyrin, resulting in excellent light harvesting across a significant spectral region. Collectively, the work described herein identifies multiperylene-porphyrin arrays that exhibit suitable photochemical properties for use as motifs in larger light-harvesting systems. 相似文献
40.
Zharov I Weng TC Orendt AM Barich DH Penner-Hahn J Grant DM Havlas Z Michl J 《Journal of the American Chemical Society》2004,126(38):12033-12046
Oxidation of Me(6)M(2) (M = Ge, Sn) and Me(4)Pb with the CB(11)Me(12)(*) radical in alkane solvents produced the insoluble salts Me(3)M(+)CB(11)Me(12)(-), characterized by CP-MAS NMR and EXAFS. The cations interact with methyl groups of CB(11)Me(12)(-) with coordination strength increasing from Pb to Ge. Density functional theory (DFT) calculations for the isolated ion pairs, Me(3)M(+)CB(11)Me(12)(-) (M = Ge, Sn), revealed three isomers with the cation above methyl 2, 7, or 12, and not above a BB edge or a BBB triangle. The interaction has a considerable covalent component, with the cation attempting to perform a backside S(E)2 substitution on the methyl carbon. In a fourth less favorable isomer the cation is near methyl 1, inclined toward methyl 2, and interacts with hydrogens. DFT atomic charge distributions and plots of the electrostatic potential on the surface of spheres centered at the CB(11)H(12)(-) and CB(11)Me(12)(-) icosahedra display the effects of uneven charge distribution within the anion and contradict the common belief that the negative charge of the cage anion is concentrated primarily on the cage boron atoms 7-12; in CB(11)Me(12)(-), roughly half is on the cage carbon and the rest on methyls 7-12. 相似文献