960 resultados para FLUORESCENCE ENERGY-TRANSFER
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Tracing interisland and interarchipelago movements of people and artifacts in prehistoric Polynesia has posed a challenge to archaeologists due to the lack of pottery and obsidian, two materials most readily used in studies of prehistoric trade or exchange. Here we report the application of nondestructive energy-dispersive x-ray fluorescence (EDXRF) analysis to the sourcing of Polynesian artifacts made from basalt, one of the most ubiquitous materials in Polynesian archaeological sites. We have compared excavated and surface-collected basalt adzes and adze flakes from two sites in Samoa (site AS-13-1) and the Cook Islands (site MAN-44), with source basalts from known prehistoric quarries in these archipelagoes. In both cases, we are able to demonstrate the importing of basalt adzes from Tutuila Island, a distance of 100 km to Ofu Island, and of 1600 km to Mangaia Island. These findings are of considerable significance for Polynesian prehistory, as they demonstrate the movement of objects not only between islands in the same group (where communities were culturally and linguistically related) but also between distant island groups. Further applications of EDXRF analysis should greatly aid archaeologists in their efforts to reconstruct ancient trade and exchange networks, not only in Polynesia but also in other regions where basalt was a major material for artifact production.
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"No. 122."
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"Part of this work done under ARPA Order 631, Program Code No. 5820."
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Item 1070-M
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The metal-to-metal charge transfer (MMCT) transitions of a series of Class II mixed valence dinuclear complexes bearing cyano bridging ligands may be varied systematically by variations to either the hexacyanometallate(II) donor or Co-III acceptor moieties. Specifically, the new dinuclear species trans-[(LCoNCFe)-Co-14S(CN)(5)](-) (L-14S = 6-methyl-1,11-diaza-4,8-dithia- cyclotetradecane-6-amine) and trans-[(LCoNCRu)-Co-14(CN)(5)]-(L-14 = 6-methyl-1,4,8,11-tetraazacyclotetradecane-6-amine) have been prepared and their spectroscopic and electrochemical properties are compared with the relative trans-[(LCoNCFe)-Co-14(CN)(5)](-). The crystal structures of Na{trans-[(LCoNCFe)-Co-14S(CN)(5)]}.51/2H(2)O.1/2EtOH, Na{trans-[(LCoNCRu)-Co-14(CN)(5)]}.3H(2)O and Na{trans-[(LCoNCRu)-Co-14(CN)(5)]}.8H(2)O are also reported. The ensuing changes to the MMCT energy have been examined within the framework of Hush theory, and it was found that the free energy change between the redox isomers was the dominant effect in altering the energy of the MMCT transition.
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An accurate knowledge of the fluorescence yield and its dependence on atmospheric properties such as pressure, temperature or humidity is essential to obtain a reliable measurement of the primary energy of cosmic rays in experiments using the fluorescence technique. In this work, several sets of fluorescence yield data (i.e. absolute value and quenching parameters) are described and compared. A simple procedure to study the effect of the assumed fluorescence yield on the reconstructed shower parameters (energy and shower maximum depth) as a function of the primary features has been developed. As an application, the effect of water vapor and temperature dependence of the collisional cross section on the fluorescence yield and its impact on the reconstruction of primary energy and shower maximum depth has been studied. Published by Elsevier B.V.
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In this letter, we consider wireless powered communication networks which could operate perpetually, as the base station (BS) broadcasts energy to the multiple energy harvesting (EH) information transmitters. These employ “harvest then transmit” mechanism, as they spend all of their energy harvested during the previous BS energy broadcast to transmit the information towards the BS. Assuming time division multiple access (TDMA), we propose a novel transmission scheme for jointly optimal allocation of the BS broadcasting power and time sharing among the wireless nodes, which maximizes the overall network throughput, under the constraint of average transmit power and maximum transmit power at the BS. The proposed scheme significantly outperforms “state of the art” schemes that employ only the optimal time allocation. If a single EH transmitter is considered, we generalize the optimal solutions for the case of fixed circuit power consumption, which refers to a much more practical scenario.
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New materials for OLED applications with low singlet–triplet energy splitting have been recently synthesized in order to allow for the conversion of triplet into singlet excitons (emitting light) via a Thermally Activated Delayed Fluorescence (TADF) process, which involves excited-states with a non-negligible amount of Charge-Transfer (CT). The accurate modeling of these states with Time-Dependent Density Functional Theory (TD-DFT), the most used method so far because of the favorable trade-off between accuracy and computational cost, is however particularly challenging. We carefully address this issue here by considering materials with small (high) singlet–triplet gap acting as emitter (host) in OLEDs and by comparing the accuracy of TD-DFT and the corresponding Tamm-Dancoff Approximation (TDA), which is found to greatly reduce error bars with respect to experiments thanks to better estimates for the lowest singlet–triplet transition. Finally, we quantitatively correlate the singlet–triplet splitting values with the extent of CT, using for it a simple metric extracted from calculations with double-hybrid functionals, that might be applied in further molecular engineering studies.
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Organic Light-Emitting Diodes (OLEDs) technology has matured over recent years, reaching the commercialization level and being used in various applications. The required efficiency can be achieved by transforming triplet excitons into singlet states via Reverse InterSystem Crossing (RISC), which a general mechanism called thermally activated delayed fluorescence (TADF). Two prototypical molecules in the field, 2CzBN and 4CzBN, Carbazole Benzonitrile (donor-acceptor) derivatives, possess similar energy gap between singlet and triplet (∆EST, a key parameter in the RISC rate), but different TADF performance. In this sense, other parameter must be considered to explain these different behaviors. In this work, we theoretically investigate 2CzBN and 4CzBN and address the problem of how flexible donor-acceptor (D-A) or donor-acceptor-donor (D-A-D) molecular architectures affect the nature of excited state, and the oscillator strength. Furthermore, we analyze the RISC rates as a function of the conformation of the carbazole side groups, considering the S0, S1, T1 and T2 states. The oscillator strength of 4CzBN is higher than of 2CzBN, which, in turn, is almost vanishing, resulting in only 4CzBN being a TADF active molecule. We also note the presence of a second triplet state T2 lower in energy than S1, and that the reorganization energies, associated to the RISC processes involving T1 and T2, are both important factor in differentiating the rates in 2CzBN and 4CzBN. However, the 4CzBN RISC rate from T2 to S1 is surprisingly high with respect to the one from T1 to S1, although, according to EL-Sayed rules, since T2 (CT/LE) is more similar to S1 (CT) than in 2CzBN (LE, CT), this transition should be less favored. These insights are important to understand the photophysics of the TADF process and to design novel TADF emitters based on the benzo-carbazole architecture.
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Histological and histochemical observations support the hypothesis that collagen fibers can link to elastic fibers. However, the resulting organization of elastin and collagen type complexes and differences between these materials in terms of macromolecular orientation and frequencies of their chemical vibrational groups have not yet been solved. This study aimed to investigate the macromolecular organization of pure elastin, collagen type I and elastin-collagen complexes using polarized light DIC-microscopy. Additionally, differences and similarities between pure elastin and collagen bundles (CB) were investigated by Fourier transform-infrared (FT-IR) microspectroscopy. Although elastin exhibited a faint birefringence, the elastin-collagen complex aggregates formed in solution exhibited a deep birefringence and formation of an ordered-supramolecular complex typical of collagen chiral structure. The FT-IR study revealed elastin and CB peptide NH groups involved in different types of H-bonding. More energy is absorbed in the vibrational transitions corresponding to CH, CH2 and CH3 groups (probably associated with the hydrophobicity demonstrated by 8-anilino-1-naphtalene sulfonic acid sodium salt [ANS] fluorescence), and to νCN, δNH and ωCH2 groups of elastin compared to CB. It is assumed that the α-helix contribution to the pure elastin amide I profile is 46.8%, whereas that of the B-sheet is 20% and that unordered structures contribute to the remaining percentage. An FT-IR profile library reveals that the elastin signature within the 1360-1189cm(-1) spectral range resembles that of Conex-Toray aramid fibers.
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The surface detector array of the Pierre Auger Observatory is sensitive to Earth-skimming tau neutrinos that interact in Earth's crust. Tau leptons from nu(tau) charged-current interactions can emerge and decay in the atmosphere to produce a nearly horizontal shower with a significant electromagnetic component. The data collected between 1 January 2004 and 31 August 2007 are used to place an upper limit on the diffuse flux of nu(tau) at EeV energies. Assuming an E(nu)(-2) differential energy spectrum the limit set at 90% C. L. is E(nu)(2)dN(nu tau)/dE(nu) < 1: 3 x 10(-7) GeV cm(-2) s(-1) sr(-1) in the energy range 2 x 10(17) eV< E(nu) < 2 x 10(19) eV.