10,000 publications from this institution
The excited state of an organic molecule is a crossroads which can lead to many directions, such as non-radiative emission as heat, fluorescence, intersystem crossing and phosphorescence. Due to the unpredictable nature of the excited molecular structure, manipulation of this represents significant challenges for physicists and chemists. However, the successful management of the excited state provides a number of benefits with innumerable applications to fields like photonics and medicine. One such property of the excited state with powerful ramifications in medical diagnostics is fluorescence lifetime.
Continuous electroencephalogram (EEG) sleep studies were obtained on healthy full-term and preterm infants at matched conceptional ages. Studies were recorded under environmentally controlled conditions. Eighteen healthy preterm infants were matched to 18 full-term infants based on conceptional age, sex, race and socioeconomic class. The initial 3 hours of a 12-hour recording were simultaneously recorded on paper and computer. The visually scored data based on the paper recordings for sleep architecture and continuity measures were studied. Differences in each sleep organization for the preterm infants included the following: a longer ultradian sleep cycle (70 minutes vs. 53 minutes, p = 0.02) was noted. More abundant tracé alternant (34% vs. 28%, p = 0.02) and less abundant low-voltage irregular active sleep (13% vs. 17%, p = 0.05) were noted. Although no differences were observed for sleep latency and efficiency, the preterm infants had fewer numbers and shorter durations of arousals, fewer body movements and rapid eye movement (REM) (p < 0.01), particularly during quiet sleep. The extrauterine experience or the earlier birth of the preterm infant may influence specific sleep architecture and continuity measures when compared with the sleep of full-term infants who experienced a complete intrauterine gestation.
In classical sampled quantization, the signal is sampled at discrete times and at discrete values, resulting in uncertainty of the signal amplitude. However, the sampling times and the boundaries of the quantization intervals are still assumed to be known with infinite precision. The aim of this paper is to study quantization and sampling when these quantities are not known with infinite precision by considering quantized sampling in a general framework as sampling with uncertainty in time and amplitude. We define the concept of a valid quantized sample and consider a quantized sampling of a signal as a collection of valid quantized samples. We show that for continuous signals, a set of valid quantized samples generates a secondary set of valid quantized samples. We illustrate that oversampling can reduce reconstruction errors because oversampling can reduce the uncertainty in the secondary quantized samples. In particular, these secondary quantized samples have uncertainty approaching zero as oversampling increases, provided the sampling time and quantization thresholds are known with infinite precision. For a class of T-periodic bandlimited signals, this implies that the reconstruction error is a function of the oversampling ratio, the uncertainty in the sampling time, the stepsize of the quantizer, and the uncertainty in the quantization thresholds.
Paleomagnetic data from the Guadelupian (Upper Permian) Nosoni Formation of the Redding Section (RS) consistently exhibit two directional components of magnetization in addition to a late Quaternary normal weathering overprint. Six sites in ash flow tuffs and tuffaceous sedimentary rocks, spanning 200 m of section, yield data that allow precise characterization of all components. Two additional sites in calcareous mudstones were too heavily overprinted to yield stable paleomagnetic directions. Thermal demagnetization of the tuffaceous samples in 16–18 steps between natural remanent magnetization and 660°C provides a detailed data base from which to calculate directional components. Analysis of demagnetization trends identifies a prefolding reversed direction carried by both magnetite and hematite and a postfolding normal direction carried by hematite only. Petrologic considerations suggest paragenesis of these oxides in the Permian (primary magnetite and hematite) and Early‐Middle Jurassic (metamorphic hematite). Least squares analysis of progressively demagnetized vector endpoint trends between 540° and 600°C yields a formation mean direction in magnetite having D =156.4°, I =−29.7°, k = 101, α 95 =7.6°. This result is in close agreement with the composite prefolding direction ( D = 160.3°, I =−31.5°), carried by both magnetite and hematite, determined by the intersection of remagnetization circles. The postfolding hematite‐carried overprint direction calculated by the latter technique has D =352.3°, I =35.0°. Paleopoles corresponding to these two directions are located at 57.6°N, 103.0°E (magnetite formation mean) and 67.0°N, 104.1°E (hematite overprint), coinciding within error to Upper Permian and Early Jurassic (respectively) reference poles from the North American craton. These data indicate no significant rotation or latitudinal translation of the sample sites with respect to cratonic North America since the Permian. This conclusion contrasts with seemingly reliable paleomagnetic results from elsewhere in the RS, which indicate major post‐Permian clockwise rotations. These rotations are evidently specific to individual structural domains and are probably manifestations of oroclinal bending about vertical axes.
The passive state of iron in borate buffer solutions containing EDTA (ethylenediaminetetraacetic acid, disodium salt, C10H14N2Na2O8) ranging in pH from 8.15 to 12.87 at ambient temperature, has been explored using electrochemical impedance spectroscopy (EIS) and steady-state polarization methods. EDTA prevents the formation of the outer layer of the passive film, thereby permitting interrogation of the barrier layer alone. It has been found that, in the passive state, the impedance is only weakly-dependent on the solution pH and film formation voltage, but at high pH (pH > 12) and especially at high voltages, the impedance becomes very pH- and voltagedependent. Under the steady-state conditions achieved in this work, passive iron is shown to satisfy the conditions of linearity, causality, stability, and finiteness, as required by Linear Systems Theory, on the basis of Kramers-Kronig (K-K) transformation of experimental impedance data. The experimental data have been interpreted in terms of the Point Defect Model (PDM), the predictions of which for an -type, semi-conducting passive film have been experimentally observed. An impedance model for passive iron, based on the PDM, has been developed and optimized on the impedance data to yield values for fundamental parameters (transfer coefficients and standard rate constants) for the interfacial reactions occurring in the barrier oxide layer. We conclude that the dominant defect(s) in the barrier layer of the passive film on iron must be the oxygen vacancy or cation interstitial, with the latter being favored by the values of the kinetic parameters.
Abstract We report Ir‐catalyzed, enantioselective allylic substitution reactions of unstabilized silyl enolates derived from α,β‐unsaturated ketones. Asymmetric allylic substitution of a variety of allylic carbonates with silyl enolates gave allylated products in 62–94 % yield with 90–98 % ee and >20:1 branched‐to‐linear selectivity. The synthetic utility of this method was illustrated by the short synthesis of an anticancer agent, TEI‐9826.
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTKinetic Control of Pore Formation in Macroporous Polymers. Formation of "Molded" Porous Materials with High Flow Characteristics for Separations or CatalysisFrantisek Svec and Jean M. J. FrechetCite this: Chem. Mater. 1995, 7, 4, 707–715Publication Date (Print):April 1, 1995Publication History Published online1 May 2002Published inissue 1 April 1995https://pubs.acs.org/doi/10.1021/cm00052a016https://doi.org/10.1021/cm00052a016research-articleACS PublicationsRequest reuse permissionsArticle Views1458Altmetric-Citations293LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose Get e-Alerts
Abstract The first gold‐catalyzed dearomative Rautenstrauch rearrangements of N‐tosyl indoles of type (I) and (V) are described.