51 research outputs found
The denatured state of N-PGK is compact and predominantly disordered
The Organisation of the structure present in the chemically denatured N-terminal domain of phosphoglycerate kinase (N-PGK) has been determined by paramagnetic relaxation enhancements (PREs) to define the conformational landscape accessible to the domain. Below 2.0 M guanidine hydrochloride (GuHCl), a species of N-PGK (denoted I-b) is detected, distinct from those previously characterised by kinetic experiments [folded (F), kinetic intermediate (I-k) and denatured (D)]. The transition to I-b is never completed at equilibrium, because F predominates below 1.0 M GuHCl. Therefore, the ability of PREs to report on transient or low population species has been exploited to characterise I-b. Five single cysteine variants of N-PGK were labelled with the nitroxide electron spin-label MTSL [(1-oxyl-2,2,5,5-tetramethyl-3-pyrroline-3-methyl)methanesulfonate] and the denaturant dependences of the relaxation properties of the amide NMR signals between 1.2 and 3.6 M GuHCl were determined. Significant PREs for I-b were obtained, but these were distributed almost uniformly throughout the sequence. Furthermore, the PREs indicate that no specific short tertiary contacts persist. The data indicate a collapsed state with no coherent three-dimensional structure, but with a restricted radius beyond which the protein chain rarely reaches. The NMR characteristics Of I-b indicate that it forms from the fully denatured state within 100 mu s, and therefore a rapid collapse is the initial stage of folding of N-PGK from its chemically denatured state. By extrapolation, I-b is the predominant form of the denatured state under native conditions, and the non-specifically collapsed structure implies that many non-native contacts and chain reversals form early in protein folding and must be broken prior to attaining the native state topology. (C) 2008 Elsevier Ltd. All rights reserved
Patterns on liquid surfaces: cnoidal waves, compactons and scaling
Localized patterns and nonlinear oscillation formation on the bounded free
surface of an ideal incompressible liquid are analytically investigated .
Cnoidal modes, solitons and compactons, as traveling non-axially symmetric
shapes are discused. A finite-difference differential generalized Korteweg-de
Vries equation is shown to describe the three-dimensional motion of the fluid
surface and the limit of long and shallow channels one reobtains the well known
KdV equation. A tentative expansion formula for the representation of the
general solution of a nonlinear equation, for given initial condition is
introduced on a graphical-algebraic basis. The model is useful in multilayer
fluid dynamics, cluster formation, and nuclear physics since, up to an overall
scale, these systems display liquid free surface behavior.Comment: 14 pages RevTex, 5 figures in p
Finite Temperature Properties of Quantum Antiferromagnets in a Uniform Magnetic Field in One and Two Dimensions
Consider a -dimensional antiferromagnet with a quantum disordered ground
state and a gap to bosonic excitations with non-zero spin. In a finite external
magnetic field, this antiferromagnet will undergo a phase transition to a
ground state with non-zero magnetization, describable as the condensation of a
dilute gas of bosons. The finite temperature properties of the Bose gas in the
vicinity of this transition are argued to obey a hypothesis of ZERO
SCALE-FACTOR UNIVERSALITY for , with logarithmic violations in .
Scaling properties of various experimental observables are computed in an
expansion in , and exactly in .Comment: 27 pages, REVTEX 3.0, 8 Postscript figures appended, YCTP-xyz
Dimensional Crossover of Localisation and Delocalisation in a Quantum Hall Bar
The 2-- to 1--dimensional crossover of the localisation length of electrons
confined to a disordered quantum wire of finite width is studied in a
model of electrons moving in the potential of uncorrelated impurities. An
analytical formula for the localisation length is derived, describing the
dimensional crossover as function of width , conductance and
perpendicular magnetic field . On the basis of these results, the scaling
analysis of the quantum Hall effect in high Landau levels, and the
delocalisation transition in a quantum Hall wire are reconsidered.Comment: 12 pages, 7 figure
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The kinetics of the gas-phase reactions of selected monoterpenes and cyclo-alkenes with ozone and the NO3 radical
The relative rate method has been used to measure the room-temperature rate constants for the gasphase reactions of ozone and NO3 with selected monoterpenes and cyclo-alkenes with structural similarities to monoterpenes. Measurements were carried out at 298 ! 2 K and 760 ! 10 Torr. The following rate constants (in units of 10"18 cm3 molecule"1 s"1) were obtained for the reaction with ozone: methyl cyclohexene (132 ! 17), terpinolene (1290 ! 360), ethylidene cyclohexane (223 ! 57), norbornene (860 ! 240), t-butyl isopropylidene cyclohexane (1500 ! 460), cyclopentene (543 ! 94), cyclohexene (81 ! 18), cyclooctene (451 ! 66), dicyclopentadiene (1460 ! 170) and a-pinene (107 ! 13). For the reaction with NO3 the rate constants obtained (in units of 10"12 cm3 molecule"1 s"1) were: methyl cyclohexene (7.92 ! 0.95), terpinolene (47.9 ! 4.0), ethylidene cyclohexane (4.30 ! 0.24), norbornene (0.266 ! 0.029), cyclohexene (0.540 ! 0.017), cyclooctene (0.513 ! 0.029), dicyclopentadiene (1.20 ! 0.10) and a-pinene (5.17 ! 0.62). Errors are quoted as the root mean square of the statistical error (95% con!dence) and the quoted error in the rate constant for the reference compound. Combining these results with previous studies, new recommendations for the rate constants are presented. Molecular orbital energies were calculated for each alkene and the kinetic data are discussed in terms of the deviation from the structureeactivity relationship obtained from the rate constants for a series of simple alkenes. Lifetimes with respect to key initiators of atmospheric oxidation have been calculated suggesting that the studied reactions play dominant roles in the night-time removal of these compounds from the atmosphere
Factors Associated with Revision Surgery after Internal Fixation of Hip Fractures
Background: Femoral neck fractures are associated with high rates of revision surgery after management with internal fixation. Using data from the Fixation using Alternative Implants for the Treatment of Hip fractures (FAITH) trial evaluating methods of internal fixation in patients with femoral neck fractures, we investigated associations between baseline and surgical factors and the need for revision surgery to promote healing, relieve pain, treat infection or improve function over 24 months postsurgery. Additionally, we investigated factors associated with (1) hardware removal and (2) implant exchange from cancellous screws (CS) or sliding hip screw (SHS) to total hip arthroplasty, hemiarthroplasty, or another internal fixation device. Methods: We identified 15 potential factors a priori that may be associated with revision surgery, 7 with hardware removal, and 14 with implant exchange. We used multivariable Cox proportional hazards analyses in our investigation. Results: Factors associated with increased risk of revision surgery included: female sex, [hazard ratio (HR) 1.79, 95% confidence interval (CI) 1.25-2.50; P = 0.001], higher body mass index (fo
Effect of Vitamin B12 Status on Performance of the Lactating Ewe and Gluconeogenesis from Propionate
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