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.     

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.     

Interpreting early land management through compound specific stable isotope analyses of archaeological soils

Compound specific stable isotope analyses of managed soils using isotope ratio mass spectrometry have been undertaken as a means of determining early land use practices. delta (15)N amino acid signals demonstrate differences between manured grassland, unmanured grassland and continuous cereal cultivation under long-term experimental land use control conditions, with delta (15)N in hydrophobic amino acids providing the most distinctive signals. Analysis of early modern/medieval and of Bronze age anthropogenic soils from Orkney demonstrates that such signals are retained in archaeological contexts. delta (13)C analyses of n- alkanoic acid components of the fossil, Bronze Age, anthropogenic soils suggest a major terrestrial input to these soils, with uniform composition of formation materials. Surficial soils demonstrate the assimilation of isotopically lighter carbon, providing a means of assessing the mobility of the n- alkanoic acids within soils and sediments. Copyright 1999 John Wiley & Sons, Ltd.     

Sensitivity enhancement and compensation of RF penetration artifact with planar actively detunable quadrature surface coil

An actively detunable planar quadrature surface coil for human body imaging at 4 T has been constructed and compared with a conventional linear surface coil. The coil could be used as a transmit/receive or a receive-only device in combination with a volume transmit coil. Transmission, reception profiles and the corresponding images acquired with each coil, as well as with both individual modes of the quadrature coil, are presented. Data collected using a tissue equivalent loaded phantom recorded with the linear surface coil demonstrated significant intensity distortions due to RF penetration artifact. The quadrature surface coil, on the other hand, provided compensation of the artifact, separately in its transmission and reception profiles as well as in the resultant images. Substantial sensitivity gain was also observed for the quadrature coil compared to the linear device. Significant advantages of using the quadrature surface coil over the linear device at 4 T have, therefore, been demonstrated.     

Tuning stability of coiled-coil heterotrimers by selection of steric matching partners

Coiled-coil trimers of differing stability have been designed by judicious choice of hydrophobic core side chain identity. Steric matching of two alanines with one large side chain at three core positions affords stable heterotrimers. Use of either cyclohexylalanine (Cha) or phenylalanine (Phe) as the large side chain is effective, and unfolding free energies can be varied by over 3 kcal/mol by mixing Cha- and Phe-containing subunits.     

Specific control of peptide assembly with combined hydrophilic and hydrophobic interfaces

Designed coiled-coil heterotrimers are described whose assembly is governed by both hydrophobic and hydrophilic forces. Sterically matched hydrophobic core side-chain packing of alanine and cyclohexylalanine has been shown to promote formation of a 1:1:1 heterotrimer. Manipulation of hydrophilic glutamic acid (Glu)/lysine (Lys) pairs at each of three helical contact interfaces provides a secondary recognition mechanism. Peptides with matched cores and hydrophilic contacts form stable heterotrimers (DeltaG(unf) at 25 degrees C = 17.93 kcal/mol; MW(app) = 11362 vs 11563 calcd for trimer), as do those with a single Lys/Lys (but not Glu/Glu) interface. The additional specificity engendered by simultaneous operation of two interfaces was used to design a system in which six different peptides are mixed to form three specific and independent heterotrimers in the same solution.     

Simultaneous directed assembly of three distinct heterodimeric coiled coils

We describe simultaneous formation of three distinct heterodimeric coiled coils from a mixture of six different peptides. The choice among electrostatically viable complexes is governed by alignment of buried core residues, including a fundamentally new interaction that exploits urea-terminated side chains. Buried urea/urea contacts lead to extremely stable dimeric coiled coils, with T(m) values between 63 and 79 degrees C. Core ureas can also form stable complexes with a variety of other polar groups, including guanidines, acids, and amides.     

Variable stability heterodimeric coiled-coils from manipulation of electrostatic interface residue chain length

The design of variable-stability coiled-coil heterodimers is described. The electrostatic interface between helices, formed by contact between side chains in heptad e/g positions, is manipulated to produce complexes ranging in stability from ones that are essentially unstructured to those that cannot be thermally denatured. The tuning is accomplished by incremental extension or contraction of parent glutamic acid and lysine side chains by single methylene units, producing peptides that bear either carboxylic acids or amines separated from the peptide backbone by one to four CH2 groups. Detailed examination of all homodimers and electrostatically compatible heterodimers generates interesting combinations, particularly those in which longer-chain acids are incorporated into peptides paired with lysine-bearing ones. The discovery of very stable dimers allows exchange experiments in which one strand of an original heterodimer is specifically replaced by an added one, even in cases where the original complex features the native-like glutamic acid/lysine pairing. The reported results add significantly to the available design templates for coiled-coil construction and enable the future implementation of various triggered-recognition strategies.