The onset of coulomb explosions in polyatomic molecules

With the development of high intensity femtosecond lasers, the ionisation and dissociation dynamics of molecules has become an area of considerable interest. Using the technique of femtosecond laser mass spectrometry (FLMS), the molecules carbon disulphide, pyrimidine, toluene, cyclohexanone and benzaldehyde are studied with pulse widths of 50 fs in the near infrared (IR) wavelength region (790 nm). Results are presented and contrasted for laser beam intensities around 10(15) and 10(16) W cm(-2). For the lower intensities, the mass spectra yield dominant singly charged parent ions. Additionally, the appearance of doubly charged parent ions is evident for carbon disulphide, toluene and benzaldehyde with envelopes of doubly charged satellite species existing in these local regions. Carbon disulphide also reveals a small triply charged component. Such atomic-like features are thought to be a strong fingerprint of FLMS at these intensities. However, upon increasing the laser intensity to approximately 10(16) W cm(-2), parent ion dominance decreases and the appearance of multiply charged atomic species occurs, particularly carbon. This phenomenon has been attributed to Coulomb explosions in which the fast absorption of many photons may produce transient highly ionised parent species which can subsequently blow apart. Copyright 1999 John Wiley & Sons, Ltd.     

Stable isotopic studies of earthworm feeding ecology in tropical ecosystems of Puerto Rico

Feeding strategies of earthworms and their influence on soil processes are often inferred from morphological, behavioral and physiological traits. We used (13)C and (15)N natural abundance in earthworms, soils and plants to explore patterns of resource utilization by different species of earthworms in three tropical ecosystems in Puerto Rico. In a high altitude dwarf forest, native earthworms Trigaster longissimus and Estherella sp. showed less (15)N enrichment ((15)N = 3-6 per thousand) than exotic Pontoscolex corethrurus ((15)N =7-9 per thousand) indicating different food sources or stronger isotopic discrimination by the latter. Conversely, in a lower altitude tabonuco forest, Estherella sp. and P. corethrurus overlapped completely in (15)N enrichment ((15)N = 6-9 per thousand), suggesting the potential for interspecific competition for N resources. A tabonuco forest converted to pasture contained only P. corethrurus which were less enriched in (15)N than those in the forest sites, but more highly enriched in (13)C suggesting assimilation of C from the predominant C(4) grass. These results support the utility of stable isotopes to delineate resource partitioning and potential competitive interactions among earthworm species. Copyright 1999 John Wiley & Sons, Ltd.     

Uniform molecular analysis using femtosecond laser mass spectrometry

The potential of femtosecond laser time-of-flight mass spectrometry (FLMS) for uniform quantitative analysis of molecules has been investigated. Various samples of molecular gases and vapours have been studied, using ultra-fast ( approximately 50 fs) laser pulses with very high intensity (up to 1.6 x 10(16) Wcm(-2)) for non-resonant multiphoton ionisation/tunnel ionisation. Some of these molecules have high ionisation potentials, requiring up to ten photons for non-resonant ionisation. The relative sensitivity factors (RSF) have been determined as a function of the laser intensity and it has been demonstrated that for molecules with very different masses and ionisation potentials, uniform ionisation has been achieved at the highest laser intensities. Quantitative laser mass spectrometry of molecules is therefore a distinct possibility. Copyright 1999 John Wiley & Sons, Ltd.     

Interferometry of flashboard and cable-gun plasma opening switcheson Hawk

Interferometry of plasma opening switch (POS) plasmas on the Hawk generator has shown many important features of the plasma evolution during conduction and opening. Opening occurs when a low-density region forms at a radial location determined by plasma redistribution during the conduction phase, consistent with J×B forces and the measured plasma distributions produced by the sources alone. High neutral densities have been detected in the POS region during conduction. Low-density plasma appears between the POS and the load at the time current appears in the load, and high-density plasmas appear there later in time. There are two important differences between the density evolution of POS's utilizing flashboard and cable-gun plasma sources. 1) There is a substantial (two-three times) increase in the electron inventory during conduction using cable guns that is not detected using flashboards. This is attributed, primarily, to ionization of ions and neutrals for the cable-gun case. 2) The conduction scaling with plasma density implies that the cable-gun POS has an effective ion mass/charge ratio about double that for the flashboard POS     

Scaling microsecond-conduction-time plasma opening switch operationfrom 2 to 5 MA

We describe experiments in which conduction currents were successfully scaled from 2 to 5 MA for conduction times around 1 μs in a coaxial geometry plasma opening switch (POS) on the 4 MJ ACE 4 driver. Simple models of POS operation, derived from previous work, were used to scale successful results from drivers that operate at microsecond conduction times, but at currents below 1 MA. An MHD model for the conduction phase was verified in which the square root of the plasma density is approximately proportional to the product of conduction time and peak conduction current divided by the switch radius and length. For the opening phase, a model where the POS gap is approximately constant when the local plasma conditions at the beginning of the conduction phase are kept roughly the same is consistent with the observed POS opening voltages of at least 1 MV. The conduction current was increased by increasing the POS cathode radius from 6 to 20 cm while maintaining roughly the same plasma density. This increase in radius resulted in the observed increase in the conduction-current/conduction-time product from 2 to 5 MA μs while maintaining MV POS voltages     

Experimental calibration and field investigation of the oxygen isotopic fractionation between biogenic aragonite and water

Marine molluscs have long been recognised as potential records of palaeoclimate change using the patterns and differences in the stable isotopic composition of the carbonate shells. The aim of this study is to improve the robustness of this approach for aragonitic molluscs by completing the first experimental calibration of the fractionation between water and biogenic aragonite. Fractionation factors were calibrated by growing specimens of the freshwater mollusc Lymnaea peregra under controlled conditions of water temperature and isotopic composition. Fifteen populations of L. peregra were maintained at constant temperature and isotopic conditions for five months (at five different temperatures and using three different water compositions). Water samples and temperature measurements were taken regularly throughout the experiment. The temperature dependence of the fractionation factor, between 8 and 24 degrees C, is given by: 1000 ln alpha=16.74x(1000T(-1))-26.39 (T in Kelvin) and the relationship between temperature (T), delta(18)O(carb) and delta(18)O(wat) is given by: T=21.36-4.83xdelta(+ degrees )O(carb)-delta(+ degrees )O(wat) (T is in degrees C, delta(18)O(carb) is with respect to Vienna Pee Dee Belemnite (PDB), the International Atomic Energy Agency (IAEA) replacement standard for PDB, and delta(18)O(wat) is with respect to Vienna standard mean ocean water (VSMOW)) The outcome of the controlled experiment is compared with previous studies on synthetic, and biogenic, calcite and aragonite from field and laboratory investigations. These comparisons suggest that although a vital offset exists between the fractionation of isotopes in synthetic and biogenic aragonite for molluscs in general, there is no vital effect that is specific either to freshwater, or to individual, genera. Therefore, the calibrated relationship may be used for any freshwater or marine mollusc to derive palaeotemperatures providing the isotopic composition of the environmental water can be reliably constrained. Copyright 1999 John Wiley & Sons, Ltd.     

Optimization of a Sustainable Protocol for the Extraction of Anthocyanins as Textile Dyes from Plant Materials

Anthocyanins are the largest group of polyphenolic pigments in the plant kingdom. These non-toxic, water-soluble compounds are responsible for the pink, red, purple, violet, and blue colors of fruits, vegetables, and flowers. Anthocyanins are widely used in the production of food, cosmetic and textile products, in the latter case to replace synthetic dyes with natural and sustainable alternatives. Here, we describe an environmentally benign method for the extraction of anthocyanins from red chicory and their characterization by HPLC-DAD and UPLC-MS. The protocol does not require hazardous solvents or chemicals and relies on a simple and scalable procedure that can be applied to red chicory waste streams for anthocyanin extraction. The extracted anthocyanins were characterized for stability over time and for their textile dyeing properties, achieving good values for washing fastness and, as expected, a pink-to-green color change that is reversible and can therefore be exploited in the fashion industry.     

Conformational behaviour of phenylpyrimidines. a quantum mechanical study

The conformational behaviour of isomeric phenylpyrimidines has been studied by STO-3G ab-initio computations. The results show that the torsional angle between the two rings increases with the number of H-H v$\text{i}$cinal interactions and a planar equilibrium conformation is obtained only in the absence of these interactions (2-phenylpyrimidine). A Fourier expansion of the torsional potential suggests that the first two terms are sufficient for a good fitting, except in the case of two H-H interactions (5-phenylpyrimidine), where the second term dominates and the first and third terms are of the same order of magnitude.