Ensemble Inequivalence in Single Molecule Experiments

In bulk systems the calculation of the main thermodynamic quantities leads to the same expectation values in the thermodynamic limit, regardless of the choice of the statistical ensemble. Single linear molecules can be still regarded as statistical systems, where the thermodynamic limit is represented by infinitely long chains. The question of equivalence between different ensembles is not at all obvious and has been addressed in the literature, with sometimes contradicting conclusions. We address this problem by studying the scaling properties of the ensemble difference for two different chain models, as a function of the degree of polymerization. By characterizing the scaling behavior of the difference between the isotensional (Gibbs) and isometric (Helmholtz) ensembles in the transition from the low-stretching to the high-stretching regime, we show that ensemble equivalence cannot be reached for macroscopic chains in the low force regime, and we characterize the transition from the inequivalence to the equivalence regime.Comment: Typos in equations fixed. Reference list updated and corrected. Extende

Theory of mechanical unfolding of homopolymer globule: all-or-none transition in force-clamp mode vs phase coexistence in position-clamp mode

Equilibrium mechanical unfolding of a globule formed by long flexible homopolymer chain collapsed in a poor solvent and subjected to an extensional force f (force-clamp mode) or extensional deformation D (position-clamp mode) is studied theoretically. Our analysis, like all previous analysis of this problem, shows that the globule behaves essentially differently in two modes of extension. In the force-clamp mode, mechanical unfolding of the globule with increasing applied force occurs without intramolecular microphase segregation, and at certain threshold value of the pulling force the globule unfolds as a whole ("all-or-none" transition). The value of the threshold force and the corresponding jump in the distance between the chain ends increase with a deterioration of the solvent quality and/or with an increase in the degree of polymerization. In the position-clamp mode, the globule unfolding occurs via intramolecular microphase coexistence of globular and extended microphases followed by an abrupt unraveling transition. Reaction force in the microphase segregation regime demonstrates an "anomalous" decrease with increasing extension. Comparison of deformation curves in force and position-clamp modes demonstrates that at weak and strong extensions the curves for two modes coincide, differences are observed in the intermediate extension range. Another unfolding scenario is typical for short globules: in both modes of extension they unfold continuously, without jumps or intramolecular microphase coexistence, by passing a sequence of uniformly elongated configurations.Comment: 19 pages, 13 figures, 1 tabl

Crystal Structure Of 2-[(5′,6′,7′,8′-Tetrahydro-5′,5′ ,8′,8′-Tetramethyl)-2′-Naphthyl] -1-Ethyl-1H-Benzimidazole-5-Carboxylic Acid Ethyl Ester

Scopu

Lacustrine mineral facies and implications for estimation of palaeoenvironmental parameters: Neogene intervolcanic Pelitçik Basin (Galatean Volcanic Province), Turkey

The mineralogy of the Neogene lacustrine facies of Pelitcik basin was investigated for the purpose of deriving the palaeoenvironmental parameters of this intervolcanic basin. The laboratory studies indicate that dolomite and K-feldspar are the major non-clay minerals in the study area, where plagioclase, analcime, fibrous zeolite and quartz are the minor constituents. Dolomites are found to be non-stoichiometric in chemistry. The clay fraction of the lacustrine facies is composed mainly of dioctahedral smectites. The smectites are rich in Al-Fe indicating a detrital origin. Illite comprises a minor contribution to the clay fraction, where chlorite and kaolinite are found in trace amounts. Based on dolomite stoichiometry and the mineral paragenesis found in the Pelitcik basin, the depositional conditions are suggested to have been a shallow, quiet, perennial lacustrine environment with fresh to slightly saline and slightly alkaline water chemistry. In addition, based on geological and mineralogical constraints, it is suggested that the water chemistry fluctuated during the deposition of the Pazar formation and the lake began its evolution with a hydrologically closed system and completed its evolution with a hydrologically open system

Application of airborne LiDAR data and airborne multispectral imagery to structural mapping of the upper section of the Troodos ophiolite, Cyprus

Structural maps are traditionally produced by mapping features such as faults, folds, fabrics, fractures and joints in the field. However, large map areas and the spatially limited ground perspective of the field geologist can potentially increase the likelihood that not all structural features will be identified within a given area. The ability to recognise and map both local and regional structural features using high-resolution remote sensing data provides an opportunity to complement field-based mapping to help generate more comprehensive structural maps. Nonetheless, vegetation cover can adversely affect the extraction of structural information from remotely sensed data as it can mask the appearance of subtle spectral and geomorphological features that correspond to geological structures. This study investigates the utility of airborne Light Detection And Ranging (LiDAR) data and airborne multispectral imagery for detailed structural mapping in vegetated ophiolitic rocks and sedimentary cover of a section of the northern Troodos ophiolite, Cyprus. Visual enhancement techniques were applied to a 4-m airborne LiDAR digital terrain model and 4-m airborne multispectral imagery to assist the generation of structural lineament maps. Despite widespread vegetation cover, dykes and faults were recognisable as lineaments in both data sets, and the predominant strike trends of lineaments in all resulting maps were found to be in agreement with fieldbased structural data. Interestingly, prior to fieldwork, most lineaments were assumed to be faults, but were ground verified as dykes instead, emphasising the importance of ground-truthing. Dyke and fault trends documented in this study define a pervasive structural fabric in the upper Troodos ophiolite that reflects the original sea-floor spreading history in the Larnaca graben. This structural fabric has not previously been observed in such detail and is likely to be continuous in adjacent regions under sedimentary cover. This information may be useful to future exploration efforts in the region focused on identification of structurally controlled mineral and groundwater resources. Overall, our case study highlights the efficacy of airborne LiDAR data and airborne multispectral imagery for extracting detailed and accurate structural information in hard-rock terrain to help complement field-based mapping