Raman spectroelectrochemical studies and crystal structure of a binuclear copper(I) complex with a bridging diimine ligand

Raman spectroelectrochemical and X-ray crystallographic studies have been made for the binuclear copper(I) complex, [(Ph(3)P)(2)Cu(dpq)Cu(PPh(3))(2)][BF4](2), where dpq is the bridging ligand 2,3-di(2-pyridyl)quinoxaline. The X-ray data show that the pyridine rings are twisted out of plane with respect to the quinoxaline ring which is itself non-planar. The UV/VIS spectra of the metal-to-ligand charge-transfer excited state and those of the electrochemically reduced complex are similar. The resonance-Raman spectrum of the latter species exhibits little change in the frequency of the pyridinylquinoxaline inter-ring C-C bond stretching mode, compared to the ground electronic state. This suggests minimum change in the inter-ring C-C bond order in the electrochemically or charge-transfer generated radical anion. Semiempirical molecular-orbital calculations on both the neutral dpq and radical anion show two near-degenerate lowest unoccupied orbitals in the neutral species. One is strongly bonding across the inter-ring C-C bond while the other is almost nun-bonding. The Raman data suggest that it is this latter orbital which is populated in the transient and electrochemical experiments.

TRANSIENT RESONANCE RAMAN AND RAMAN SPECTROELECTROCHEMICAL STUDIES OF CUI COMPLEXES WITH POLYPYRIDYL LIGANDS

Studies by laser flash photolysis, transient Raman spectroscopy, and Raman and UV-vis spectroelectrochemistry are described in which the techniques have been used in parallel to compare the lowest energy charge-transfer excited states of Cu (1) complexes ([Cu(L)2]+ and [ (PPh3)2Cu(L)]+ [L = 2,2'-biquinoline (BIQ) or 6,7-dihydro-5,8-dimethyldibenzo[b,j] [1,10]-phenanthroline (DMCH)) with the species produced by electrochemical reduction in the same group of complexes. Transient resonance Raman spectra for the metal-to-ligand charge-transfer (MLCT) states of [Cu(DMCH)2]+ (1), [Cu(BIQ)2]+ (2), [Cu(DMCH)(PPh3)2]+ (3), and [Cu(BIQ)(PPh3)2]+ (4) are compared with the resonance Raman spectra of the same group of complexes following one-electron electrochemical reduction of the DMCH and BIQ ligands. The UV-vis and resonance Raman evidence suggests that the electrochemical reduction of the [Cu(I)L2]+ species proceeds according to the sequence [LCu(I)L]+ -->e- [LCu0L] -->e- [L.-Cu(I)L.-]-. Several features assignable to modes of the electrochemically generated DMCH.-and BIQ'- radical anions exhibit a close correspondence in both frequency and relative intensity with counterparts in the spectra of the MLCT states of 1 and 2. A notable exception is a band near 1590 cm-1 in the spectra of the electrochemically reduced species which occurs some 15 cm-1 lower in the corresponding spectra of the excited-state species. It is suggested that the shift may reflect the change in oxidation state of the metal center from Cu(I) to Cu(II) which occurs as a result of charge-transfer excitation.

A potential lag between the open solar magnetic source flux and solar EUV and X-ray emissions as measured by the Earth's ionosphere during total solar eclipses

Measurements of the ionospheric E-region during total solar eclipses have been used to provide information about the evolution of the solar magnetic field and EUV and X-ray emissions from the solar corona and chromosphere. By measuring levels of ionisation during an eclipse and comparing these measurements with an estimate of the unperturbed ionisation levels (such as those made during a control day, where available) it is possible to estimate the percentage of ionising radiation being emitted by the solar corona and chromosphere. Previously unpublished data from the two eclipses presented here are particularly valuable as they provide information that supplements the data published to date. The eclipse of 23 October 1976 over Australia provides information in a data gap that would otherwise have spanned the years 1966 to 1991. The eclipse of 4 December 2002 over Southern Africa is important as it extends the published sequence of measurements. Comparing measurements from eclipses between 1932 and 2002 with the solar magnetic source flux reveals that changes in the solar EUV and X-ray flux lag the open source flux measurements by approximately 1.5 years. We suggest that this unexpected result comes about from changes to the relative size of the limb corona between eclipses, with the lag representing the time taken to populate the coronal field with plasma hot enough to emit the EUV and X-rays ionising our atmosphere.

Mecânica quântica e sua relação com terapias alternativas

Este trabalho propôs uma discussão crítica sobre os conceitos e fenômenos da Mecânica Quântica (MQ) empregados na explicação cientifíca que dá suporte quanto ao princípio de funcionamento de algumas terapias alternativas ou sobre a elaboração de seus respectivos medicamentos, em especial, Homeopatia e Cura Quântica. Essa discussão se faz importante para munir o leitor com argumentos sólidos calcados na teoria quântica e confrontá-los coma as ideias de simpatizantes leigos dessas terapias. Portanto, o trabalho visou descrever fatos históricos que tornaram possível a construção teórica da Mecânica Quântica, elaborou um resumo da loso a dominante que norteava o pensamento imediatamente anterior a MQ e o conflito que se seguiu em decorrência das implicações deste novo ramo da Física. Explorou o paradoxo EPR e o consequente teorema de John Bell sobre as desigualdades até chegar no experimento de Alain Aspect envolvendo laser para responder de forma prática e definitiva o paradoxo EPR. Finalmente, o trabalho apresentou um resumo das abordagens e argumentações defendidas pelos proponentes das terapias alternativas e confrontou com os conceitos da Mecânica Quântica, para enfim apresentar ao público um estudo científico sobre Homeopatia e Cura Quântica, e compreender os limites e equívocos empregados a essas terapias

Account books of Thomas Cradock, 1786-1818 (inclusive)

Account books listing patients, medicines administered, and fees charged by Dr. Thomas Cradock (1752-1821), primarily in Maryland, from 1786 to 1818. In addition to recording names, Cradock occasionally noted demographic information, the patient's location, or their occupation: from 1813 to 1816, he treated Richard Gent, a free African-American man; in 1813, he attended to John Bell, who lived in the Foggy Bottom neighborhood of Washington, D.C. Cradock further noted if the patient was a slave and the name of his or her owner. He would also administer care on behalf of corporate entities, such as Powhatan Factory, which apparently refused him payment. He also sometimes included a diagnosis: in the cases of a Mr. Rowles and Mrs. Violet West, he administered unspecified medicines for gonorrhea at a cost of ten dollars. Commonly prescribed drugs included emetics, cathartics, and anodynes. Cradock also provided smallpox vaccination for his patients. He accepted both cash and payment-in-kind. Tipped into the first volume is an envelope containing a letter from the Medical and Chirurgical Faculty of Maryland to Mrs. Thomas Craddock in 1899 requesting a loan of portrait of Dr. Thomas Craddock [sic]. The three volumes also each contain an index to patient names.

The electrical researches, written between 1771 and 1781,

Mode of access: Internet.

The miracles of Jesus Christ : explained according to their spiritual meaning, in the way of question and answer /

Mode of access: Internet.

Char-ee-kar and service there with the 4th Goorkha Regiment (Shah Shooja's force) in 1841 : an episode of the first Afghan War /

Mode of access: Internet.