Proton NMR relaxometry as a useful tool to evaluate swelling processes in peat soils

Dramatic physical and physico-chemical changes in soil properties may arise due to temperature and moisture variations as well as swelling of soil organic matter (SOM) under constant conditions. Soil property variations may influence sorption/desorption and transport processes of environmental contaminants and nutrients in natural-organic-matterrich soils. Notwithstanding the studies reported in literature, a mechanistic model for SOM swelling is unavailable yet. The objective of the present study was the evaluation of the swelling of peat soils, considered as SOM models, by 1H NMR relaxometry and differential scanning calorimetry (DSC). Namely, information on the processes governing physical and physicochemical changes of peat during re-hydration were collected. The basic hypothesis of the present study was that the changes are slow and may affect water state as well as amounts of different water types into the peats. For this reason, such changes can be evidenced through the variations of mobility and thermal behaviour of the involved H2O molecules by using 1H NMR relaxometry and DSC. According to the experimental results, a mechanistic model, describing the fundamental processes of peat swelling, was obtained. Two different peats re-wetted at three temperatures were used. The swelling process was monitored by measuring spin-spin relaxation time (T2) over a hydration time of several months. Moreover, DSC, T1 – T2 and T2 – D correlation measurements were done at the beginning and at the end of the hydration. Supplementary investigations were also done in order to discriminate between the swelling effects and the contributions from soil solution, internal magnetic field gradients and/or soil microorganisms to proton relaxation. All the results revealed peat swelling. It was evidenced by pore size distribution changes, volumetric expansion and redistribution of water, increasing amounts of nonfreezable and loosely bound water, as well as formation of gel phases and reduction of the translational and rotational mobility of H2O molecules. All the findings implied that changes of the physical and physicochemical properties of peats were obtained. In particular, three different processes having activation energies comprised in the interval 5 – 50 kJ mol-1 were revealed. The mechanistic model which was, then, developed included water reorientation in bound water phases, water diffusion into the peat matrix and reorientation of SOM chains as fundamental processes governing SOM swelling. This study is of environmental significance in terms of re-naturation and re-watering of commercially applied peatlands and of sorption/desorption and transport processes of pollutants and nutrients in natural organic matter rich soil

The bend stiffness of S-DNA

We formulate and solve a two-state model for the elasticity of nicked, double-stranded DNA that borrows features from both the Worm Like Chain and the Bragg--Zimm model. Our model is computationally simple, and gives an excellent fit to recent experimental data through the entire overstretching transition. The fit gives the first value for the bending stiffness of the overstretched state as about 10 nm*kbt, a value quite different from either B-form or single-stranded DNA.Comment: 7 pages, 1 figur

Multi-site H-bridge breathers in a DNA--shaped double strand

We investigate the formation process of nonlinear vibrational modes representing broad H-bridge multi--site breathers in a DNA--shaped double strand. Within a network model of the double helix we take individual motions of the bases within the base pair plane into account. The resulting H-bridge deformations may be asymmetric with respect to the helix axis. Furthermore the covalent bonds may be deformed distinctly in the two backbone strands. Unlike other authors that add different extra terms we limit the interaction to the hydrogen bonds within each base pair and the covalent bonds along each strand. In this way we intend to make apparent the effect of the characteristic helicoidal structure of DNA. We study the energy exchange processes related with the relaxation dynamics from a non-equilibrium conformation. It is demonstrated that the twist-opening relaxation dynamics of a radially distorted double helix attains an equilibrium regime characterized by a multi-site H-bridge breather.Comment: 27 pages and 10 figure

Morphological aspects of male and female hands

This is an electronic version of an article published in Annals of Human Biology, 1996, 23(6), 491-494. Annals of Human Biology is available online at informaworldTM http://www.informaworld.com/smpp/content~content=a739339013~db=all~order=pageThis journal article discusses a series of hand radiographs from Gwynedd, North Wales, which were assessed for frequencies in digital and metacarpal formulae between the genders

Mechanically induced silyl ester cleavage under acidic conditions investigated by AFM-based single-molecule force spectroscopy in the force-ramp mode

AFM-based dynamic single-molecule force spectroscopy was used to stretch carboxymethylated amylose (CMA) polymers, which have been covalently tethered between a silanized glass substrate and a silanized AFM tip via acid-catalyzed ester condensation at pH 2.0. Rupture forces were measured as a function of temperature and force loading rate in the force-ramp mode. The data exhibit significant statistical scattering, which is fitted with a maximum likelihood estimation (MLE) algorithm. Bond rupture is described with a Morse potential based Arrhenius kinetics model. The fit yields a bond dissociation energy De = 35 kJ mol−1 and an Arrhenius pre-factor A = 6.6 × 104 s−1. The bond dissociation energy is consistent with previous experiments under identical conditions, where the force-clamp mode was employed. However, the bi-exponential decay kinetics, which the force-clamp results unambiguously revealed, are not evident in the force-ramp data. While it is possible to fit the force-ramp data with a bi-exponential model, the fit parameters differ from the force-clamp experiments. Overall, single-molecule force spectroscopy in the force-ramp mode yields data whose information content is more limited than force-clamp data. It may, however, still be necessary and advantageous to perform force-ramp experiments. The number of successful events is often higher in the force-ramp mode, and competing reaction pathways may make force-clamp experiments impossible

Global Optimization by Energy Landscape Paving

We introduce a novel heuristic global optimization method, energy landscape paving (ELP), which combines core ideas from energy surface deformation and tabu search. In appropriate limits, ELP reduces to existing techniques. The approach is very general and flexible and is illustrated here on two protein folding problems. For these examples, the technique gives faster convergence to the global minimum than previous approaches.Comment: to appear in Phys. Rev. Lett. (2002

Einfluss von Bewässerung und Düngung auf die organische Bodensubstanz in extensiv genutzten Heuwiesen - Thermische Eigenschaften und Evolved Gasanalyse

Wiesen beherbergen etwa 40 % der in Deutschland geschützten Arten. Neben ihrer Funktion zur Erhaltung der Biodiversität dienen sie als Überschwemmungsflächen dem Hochwasserschutz und sorgen für eine Filterung des Grund- und Oberflächenwassers. Aufgrund dieser wichtigen Funktionen wurden in der Vergangenheit viele Untersuchungen gemacht, wie sich unterschiedliche landwirtschaftliche Bewirtschaftungsformen auf die Biodiversität von Wiesen auswirken. Um diese Prozesse besser zu verstehen ist es nötig, auch die unterirdisch ablaufenden biogeochemischen Prozesse zu berücksichtigen. Neben Bodenflora und –fauna spielen dabei auch abiotische Bodeneigenschaften wie z.B. Nährstoffgehalt und –verfügbarkeit oder Wasserhaltekapazität eine entscheidende Rolle. Der Nährstoff- und Wasserhaushalt eines Bodens hängt wiederum stark vom Gehalt und der Qualität der organische Bodensubstanz ab. Um die Kopplung von unterirdischen biogeochemischen Prozessen mit der oberirdischen Pflanzendiversität besser zu verstehen, haben wir in einem ersten Schritt die Auswirkung von Bewässerung und Düngung auf ausgewählte Eigenschaften der organischen Bodensubstanz mithilfe von Thermogravimetrie (TGA) gekoppelt mit Differential Scanning Calorimetry (DSC) und Evolved Gasanalyse mit Massenspektrometrie (EGA-MS) untersucht. Hierzu wurden 12 extensiv genutzte Heuwiesen, die sogenannten „Wässerwiesen“, entlang der Queich bei Landau (Rheinland-Pfalz) beprobt. Diese Wiesen wurden seit dem Mittelalter traditionell nach einem festgelegten Bewässerungskalender zwei bis dreimal im Jahr für ein bis drei Tage durch Überflutung mit dem Wasser der Queich bewässert. Auf einigen dieser Wiesen wurde diese Form der Bewässerung seit den 50iger Jahren eingestellt. Dadurch ergab sich die einmalige Möglichkeit vergleichbare Wiesen mit und seit über 50 Jahren ohne Überflutungsbewässerung sowie mit und ohne anorganische Düngung zu untersuchen. Im vorliegenden Beitrag werden die Ergebnisse dieser Studie vorgestellt und die Möglichkeiten und Grenzen thermischer Methoden zur Charakterisierung von organischer Bodensubstanz diskutiert

Unzipping Kinetics of Double-Stranded DNA in a Nanopore

We studied the unzipping kinetics of single molecules of double-stranded DNA by pulling one of their two strands through a narrow protein pore. PCR analysis yielded the first direct proof of DNA unzipping in such a system. The time to unzip each molecule was inferred from the ionic current signature of DNA traversal. The distribution of times to unzip under various experimental conditions fit a simple kinetic model. Using this model, we estimated the enthalpy barriers to unzipping and the effective charge of a nucleotide in the pore, which was considerably smaller than previously assumed.Comment: 10 pages, 5 figures, Accepted: Physics Review Letter

Classification of Invariant Star Products up to Equivariant Morita Equivalence on Symplectic Manifolds

In this paper we investigate equivariant Morita theory for algebras with momentum maps and compute the equivariant Picard groupoid in terms of the Picard groupoid explicitly. We consider three types of Morita theory: ring-theoretic equivalence, *-equivalence and strong equivalence. Then we apply these general considerations to star product algebras over symplectic manifolds with a Lie algebra symmetry. We obtain the full classification up to equivariant Morita equivalence.Comment: 28 pages. Minor update, fixed typos

Theory of High-Force DNA Stretching and Overstretching

Single molecule experiments on single- and double stranded DNA have sparked a renewed interest in the force-extension of polymers. The extensible Freely Jointed Chain (FJC) model is frequently invoked to explain the observed behavior of single-stranded DNA. We demonstrate that this model does not satisfactorily describe recent high-force stretching data. We instead propose a model (the Discrete Persistent Chain, or ``DPC'') that borrows features from both the FJC and the Wormlike Chain, and show that it resembles the data more closely. We find that most of the high-force behavior previously attributed to stretch elasticity is really a feature of the corrected entropic elasticity; the true stretch compliance of single-stranded DNA is several times smaller than that found by previous authors. Next we elaborate our model to allow coexistence of two conformational states of DNA, each with its own stretch and bend elastic constants. Our model is computationally simple, and gives an excellent fit through the entire overstretching transition of nicked, double-stranded DNA. The fit gives the first values for the elastic constants of the stretched state. In particular we find the effective bend stiffness for DNA in this state to be about 10 nm*kbt, a value quite different from either B-form or single-stranded DNAComment: 33 pages, 11 figures. High-quality figures available upon reques