998 resultados para Michael, Robert
Resumo:
Solar electromagnetic radiation powers Earth’s climate system and, consequently, it is often naively assumed that changes in this solar output must be responsible for changes in Earth’s climate. However, the Sun is close to a blackbody radiator and so emits according to its surface temperature and the huge thermal time constant of the outer part of the Sun limits the variability in surface temperature and hence output. As a result, on all timescales of interest, changes in total power output are limited to small changes in effective surface temperature (associated with magnetic fields) and potential, although as yet undetected, solar radius variations. Larger variations are seen in the UV part of the spectrum which is emitted from the lower solar atmosphere (the chromosphere) and which influences Earth’s stratosphere. There is interest in“top-down” mechanisms whereby solar UV irradiance modulates stratospheric temperatures and winds which, in turn, may influence the underlying troposphere where Earth’s climate and weather reside. This contrasts with “bottom-up” effects in which the small total solar irradiance (dominated by the visible and near-IR) variations cause surface temperature changes which drive atmospheric circulations. In addition to these electromagnetic outputs, the Sun modulates energetic particle fluxes incident on the Earth. Solar Energetic Particles (SEP) are emitted by solar flares and from the shock fronts ahead of supersonic (and super-Alfvenic) ejections of material from the solar atmosphere. These SEPs enhance the destruction of polar stratospheric ozone which could be an additional form of top-down climate forcing. Even more energetic are Galactic Cosmic Rays (GCRs). These particles are not generated by the Sun, rather they originate at the shock fronts emanating from violent galactic events such as supernovae explosions; however, the expansion of the solar magnetic field into interplanetary space means that the Sun modulates the number of GCRs reaching Earth. These play a key role in enabling Earth’s global electric (thunderstorm) circuit and it has been proposed that they also modulate the formation of clouds. Both electromagnetic and corpuscular solar effects are known to vary over the solar magnetic cycle which is typically between 10 and 14 yrs in length (with an average close to 11 yrs). The solar magnetic field polarity at any one phase of one of these activity cycles is opposite to that at the same phase of the next cycle and this influences some phenomena, for example GCRs, which therefore show a 22 yr (“Hale”) cycle on average. Other phenomena, such as irradiance modulation, do not depend on the polarity of the magnetic field and so show only the basic 11-yr activity cycle. However, any effects on climate are much more significant for solar drifts over centennial timescales. This chapter discusses and evaluates potential effects on Earth’s climate system of variations in these solar inputs. Because of the great variety of proposed mechanisms, the wide range of timescales studied (from days to millennia) and the many debates (often triggered by the application of inadequate statistical methods), the literature on this subject is vast, complex, divergent and rapidly changing: consequently the number of references cited in this review is very large (yet still only a small fraction of the total).
Resumo:
Acrylamide and pyrazine formation, as influenced by the incorporation of different amino acids, was investigated in sealed low-moisture asparagine-glucose model systems. Added amino acids, with the exception of glycine and cysteine and at an equimolar concentration to asparagine, increased the rate of acrylamide formation. The strong correlation between the unsubstituted pyrazine and acrylamide suggests the promotion of the formation of Maillard reaction intermediates, and in particular glyoxal, as the determining mode of-action. At increased amino acid concentrations, diverse effects were observed. The initial rates of acrylamide formation remained high for valine, alanine, phenylalanine, tryptophan, glutamine, and Ieucine, while a significant mitigating effect, as evident from the acrylamide yields after 60 min of heating at 160 degrees C, was observed for proline, tryptophan, glycine, and cysteine. The secondary amine containing amino acids, proline and tryptophan, had the most profound mitigating effect on acrylamide after 60 min of heating. The relative importance of the competing effect of added amino acids for alpha-dicarbonyls and acrylamide-amino, acid alkylation reactions is discussed and accompanied by data on the relative formation rates of selected amino acid-AA adducts.
Resumo:
A new homo-proline tetrazole derivative 7 has been prepared and shown to have improved properties for achieving asymmetric Michael addition of carbonyl compounds to nitro-olefins.
Resumo:
Tetrazole and acylsulfonamide organocatalysts derived from proline have been synthesised and applied to the asymmetric Mannich, nitro-Michael and aldol reactions to give results that are superior to the proline-catalysed counterpart.