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801.
Goj LA Lail M Pittard KA Riley KC Gunnoe TB Petersen JL 《Chemical communications (Cambridge, England)》2006,(9):982-984
Stoichiometric reactions of TpRu(CO)(NCMe)(Ph) with electron-rich olefins result in metal-mediated cleavage of C-S and C-O bonds. 相似文献
802.
Treatment of 1,2-diols with diphenylphosphinoyl chloride in pyridine produces beta-chloroethyl phosphinates which react with complete control of stereochemistry to give epoxides and azido-alcohols, useful intermediates in cyclopropane synthesis. 相似文献
803.
The hydrated proton was studied in methanol-water solutions of varying methanol concentrations using the multistate empirical valence bond simulation method. Amphiphile-like behavior of the hydrated proton was noted from its anisotropic association with the methanol methyl groups. Molecular length immiscibility was also characterized through the enumeration of water and protonated water clusters. Excess proton diffusion was calculated across the varying methanol concentrations and found to be in good agreement with experiment after correcting for nuclear quantum effects. 相似文献
804.
A new synthetic pathway to the parent and substituted ABCD ring cores of the camptothecin family of alkaloids was developed. The N-alkylation of 1,6-dihydro-6-oxo-2-pyridinecarbonitrile (2) with 3-bromo-1-phenylpropyne provided 3a using Curran's protocol. Treatment of 3a with a catalytic amount of DBU (5 mol %) at 110 degrees C for 12 h produced indolizino[1,2-b]quinolin-9(11H)-one (6a), the parent ABCD ring core of camptothecin, in essentially quantitative yield. 相似文献
805.
Anderson MG Haraszti T Petersen GE Wirick S Jacobsen C John SW Grunze M 《Micron (Oxford, England : 1993)》2006,37(8):689-698
Melanosomes are specialized intracellular membrane bound organelles that produce and store melanin pigment. The composition of melanin and distribution of melanosomes determine the color of many mammalian tissues, including the hair, skin, and iris. However, the presence of melanosomes within a tissue carries potentially detrimental risks related to the cytotoxic indole–quinone intermediates produced during melanin synthesis. In order to study melanosomal molecules, including melanin and melanin-related intermediates, we have refined methods allowing spectromicroscopic analysis of purified melanosomes using scanning transmission X-ray microscopy. Here, we present for the first time absorption data for melanosomes at the carbon absorption edge ranging from 284 to 290 eV. High-resolution images of melanosomes at discrete energies demonstrate that fully melanized mature melanosomes are internally non-homogeneous, suggesting the presence of an organized internal sub-structure. Spectra of purified melanosomes are complex, partially described by a predominating absorption band at 288.4 eV with additional contributions from several minor bands. Differences in these spectra were detectable between samples from two strains of inbred mice known to harbor genetically determined melanosomal differences, DBA/2J and C57BL/6J, and are likely to represent signatures arising from biologically relevant and tractable phenomena. 相似文献
806.
Reduction of primary freeze-drying time by electric field induced ice nucleus formation 总被引:1,自引:0,他引:1
The potential of a high electric field was utilized to induce ice nucleus formation in aqueous solutions. Using this technique it was possible to reduce the primary drying time during lyophilization. Samples of 10% (w/v) hydroxyethylstarch (HES) solution were frozen at a constant rate of −1 K/min, while nucleation was initiated at temperatures of −1.5, −4.5 and −8.5°C. In contrast, spontaneous nucleation was observed in a range between −11.5 and −17.1°C. Electrically induced nucleus formation has proved to be a reliable method to start crystallization at a desired temperature. Continuous measurement of the weight allowed to determine the drying rate and to detect at which time primary drying was completed. The drying time and the drying rate were found to be strongly dependent on the nucleation temperature during freezing. A relation between the nucleation temperature, the structure of the frozen samples and the drying times could be established.
相似文献
Ansgar PetersenEmail: |
807.
Csaba László Sajti Svea Petersen Ana Menéndez-Manjón Stephan Barcikowski 《Applied Physics A: Materials Science & Processing》2010,101(2):259-264
In-situ functionalization of gold nanoparticles with fluorophore-tagged oligonucleotides is studied by comparing femtosecond
laser ablation in stationary liquid and in biomolecule flow. Femtosecond laser pulses induce significant degradation to sensitive
biomolecules when ablating gold in a stationary solution of oligonucleotides. Contrary, in-situ conjugation of nanoparticles
in biomolecule flow considerably reduces the degree of degradation studied by gel electrophoresis and UV–Vis spectrometry.
Ablating gold with 100 μJ femtosecond laser pulses DNA sequence does not degrade, while the degree of fluorophore tag degradation
was 84% in stationary solution compared to 5% for 1 mL/min liquid flow. It is concluded that femtosecond laser-induced degradation
of biomolecules is triggered by absorption of nanoparticle conjugates suspended in the colloid and not by ablation of the
target. Quenching of nanoparticle size appears from 0.5 μM biomolecule concentration for 0.3 μg/s nanoparticle productivity
indicating the successful surface functionalization. Finally, increasing the liquid flow rate from stationary to 450 mL/min
enhances nanoparticle productivity from 0.2 μg/s to 1.5 μg/s, as increasing liquid flow allows removal of light absorbing
nanoparticles from the ablation zone, avoiding attenuation of subsequent laser photons. 相似文献
808.
Crepin C Broquier M Dubost H Galaup JP Le Gouet JL Ortega JM 《Physical review letters》2000,85(5):964-967
Infrared picosecond accumulated photon echo experiments have been performed for the first time, using the Orsay Free Electron Laser, on the v = 0-->v = 1 transition of CO in solid nitrogen. The vibrational dephasing time is found to be exceptionally long ( T2>/=120 ns) at low temperature. The analysis of the observed spectral diffusion leads one to assume different energy transfer mechanisms depending on the CO concentration. 相似文献
809.
This paper is an expository survey of recent research on the application of Szegö polynomials and PPC-continuedfractions to the frequency analysis problem described as follows: We want to determine the unknown frequencies 1, 2, ...,
I
from a sample of N observed values x
N
(m), m = 0, 1, ..., N– 1, arising from a continuous waveform that is the superposition of a finite number of sinusoidal waves with frequencies 1,2, ...,
I
. The method is based on the property that certain zerosof the Szegö polynomials (and poles of the PPC-fraction approximants) converge (as N ) to the frequency points e
i
j
, j = ±1, ± 2, ..., ± I. The remaining zeros are bounded away from the unit circle |z|=1, asN . The Levinson algorithm is used to construct the Szegö polynomials and PPC-fractions from the values x
N
(m). A discussion is given on connections between the topics: Carathéodory functions,the trigonometric moment problem, Szegö polynomials and PPC-fractions. We also describe applications to Doppler radar, medicine, speech processing, speech therapy, meteorology and ocean tides. 相似文献
810.