Water droplet excess free energy determined by cluster mitosis using guided molecular dynamics

Atmospheric aerosols play a vital role in affecting climate by influencing the properties and lifetimes of clouds and precipitation. Understanding the underlying microscopic mechanisms involved in the nucleation of aerosol droplets from the vapour phase is therefore of great interest. One key thermodynamic quantity in nucleation is the excess free energy of cluster formation relative to that of the saturated vapour. In our current study, the excess free energy is extracted for clusters of pure water modelled with the TIP4P/2005 intermolecular potential using a method based on nonequilibrium molecular dynamics and the Jarzynski relation. The change in free energy associated with the "mitosis" or division of a cluster of N water molecules into two N/2 sub-clusters is evaluated. This methodology is an extension of the disassembly procedure used recently to calculate the excess free energy of argon clusters [H. Y. Tang and I. J. Ford, Phys. Rev. E 91, 023308 (2015)]. Our findings are compared to the corresponding excess free energies obtained from classical nucleation theory (CNT) as well as internally consistent classical theory (ICCT). The values of the excess free energy that we obtain with the mitosis method are consistent with CNT for large cluster sizes but for the smallest clusters, the results tend towards ICCT; for intermediate sized clusters, we obtain values between the ICCT and CNT predictions. Furthermore, the curvature-dependent surface tension which can be obtained by regarding the clusters as spherical droplets of bulk density is found to be a monotonically increasing function of cluster size for the studied range. The data are compared to other values reported in the literature, agreeing qualitatively with some but disagreeing with the values determined by Joswiak et al. [J. Phys. Chem. Lett. 4, 4267 (2013)] using a biased mitosis approach; an assessment of the differences is the main motivation for our current study

Sedimentation, re-sedimentation and chronologies in archaeologically-important caves: problems and prospects

Excavations in the photic zones of caves have provided cornerstone archaeological sequences in many parts of the world. Before the appearance of modern dating techniques, cave deposits provided clear evidence for the antiquity, relative ages and co-occurrence of ancient human remains, material culture and fauna. Earlier generations of archaeologists had generally rather limited understanding of taphonomic and depositional processes, but the twentieth century saw considerable improvement in excavation and analytical techniques. The advent of modern dating and chronological methodologies offers very powerful tools for the analysis of cave fill deposits and this has resulted in the recognition of chronological incoherence in parts of some sites, with consequent re-evaluation of previous archaeological disputes. Obtaining multiple dates per context provides a means to assess the integrity and coherence of the archaeological and environmental records from cave fills. In the case of the Haua Fteah (Libya), this technique allowed the recognition of chronological coherence in low-energy depositional environments and limited recycling in high-energy contexts. We provide a conceptual model of the relationship between recycling, sedimentation rate and process energy. High-resolution investigation enables recognition of the complexity of the formation of cave sequences, thus an increasingly sophisticated understanding of human behaviour and environmental relationships in the past, and potentially gives a new life to old data

Sedimentation, re-sedimentation and chronologies in archaeologically-important caves: problems and prospects

Excavations in the photic zones of caves have provided cornerstone archaeological sequences in many parts of the world. Before the appearance of modern dating techniques, cave deposits provided clear evidence for the antiquity, relative ages and co-occurrence of ancient human remains, material culture and fauna. Earlier generations of archaeologists had generally rather limited understanding of taphonomic and depositional processes, but the twentieth century saw considerable improvement in excavation and analytical techniques. The advent of modern dating and chronological methodologies offers very powerful tools for the analysis of cave fill deposits and this has resulted in the recognition of chronological incoherence in parts of some sites, with consequent re-evaluation of previous archaeological disputes. Obtaining multiple dates per context provides a means to assess the integrity and coherence of the archaeological and environmental records from cave fills. In the case of the Haua Fteah (Libya), this technique allowed the recognition of chronological coherence in low-energy depositional environments and limited recycling in high-energy contexts. We provide a conceptual model of the relationship between recycling, sedimentation rate and process energy. High-resolution investigation enables recognition of the complexity of the formation of cave sequences, thus an increasingly sophisticated understanding of human behaviour and environmental relationships in the past, and potentially gives a new life to old data

Mollusk carbonate thermal behaviour and its implications in understanding prehistoric fire events in shell middens

Archaeological shell middens are particularly important for reconstructing prehistoric human subsistence strategies. However, very little is known about shellfish processing, especially when related to the use of fire for dietary and disposal purposes. To shed light on prehistoric food processing techniques, an experimental study was undertaken on modern gastropod shells (Phorcus lineatus). The shells were exposed to high temperatures (200-700 °C) to investigate subsequent mineralogy and macro- and microstructural changes. Afterwards, the three-pronged approach was applied to archaeological shells from Haua Fteah cave, Libya (Phorcus turbinatus) and from shell midden sites in the United Arab Emirates (Anadara uropigimelana and Terebralia palustris) to determine exposure temperatures. Results indicated that shells from the Haua Fteah were exposed to high temperatures (600 - 700 °C) during the Mesolithic period (c. 12.7 - 9 ka), whereas specimens from the Neolithic period (c. 8.5 - 5.4 ka) were mainly exposed to lower temperatures (300 - 500 °C). The thermally-induced changes in A. uropigimelana and T. palustris shells from the South East Arabian archaeological sites were similar to those seen in Phorcus spp. suggesting a broad applicability of the experimental results at an interspecific level. Although heat significantly altered the appearance and mineralogy of the shells, 14CAMS ages obtained on burnt shells fit within the expected age ranges for their associated archaeological contexts, indicating that robust radiocarbon ages may still be obtained from burnt shells. Our study indicates that the combination of microstructural and mineralogical observations can provide important information to infer shellfish processing strategies in prehistoric cultures and their change through time.Funding for this study was kindly provided by the EU within the framework (FP7) of the Marie Curie International Training Network ARAMACC (604802) to SM and by the Alexander von Humboldt Postdoctoral Fellowship (1151310) and McKenzie Postdoctoral Fellowship to AP. The Haua Fteah excavations were undertaken with the permission of the Libyan Department of Antiquities and with funding to GB from the Society for Libyan Studies and from the European Research Council (Advanced Investigator Grant 230421), whose support is also gratefully acknowledge

Surface thermodynamics of planar, cylindrical, and spherical vapour-liquid interfaces of water.

The test-area (TA) perturbation approach has been gaining popularity as a methodology for the direct computation of the interfacial tension in molecular simulation. Though originally implemented for planar interfaces, the TA approach has also been used to analyze the interfacial properties of curved liquid interfaces. Here, we provide an interpretation of the TA method taking the view that it corresponds to the change in free energy under a transformation of the spatial metric for an affine distortion. By expressing the change in configurational energy of a molecular configuration as a Taylor expansion in the distortion parameter, compact relations are derived for the interfacial tension and its energetic and entropic components for three different geometries: planar, cylindrical, and spherical fluid interfaces. While the tensions of the planar and cylindrical geometries are characterized by first-order changes in the energy, that of the spherical interface depends on second-order contributions. We show that a greater statistical uncertainty is to be expected when calculating the thermodynamic properties of a spherical interface than for the planar and cylindrical cases, and the evaluation of the separate entropic and energetic contributions poses a greater computational challenge than the tension itself. The methodology is employed to determine the vapour-liquid interfacial tension of TIP4P/2005 water at 293 K by molecular dynamics simulation for planar, cylindrical, and spherical geometries. A weak peak in the curvature dependence of the tension is observed in the case of cylindrical threads of condensed liquid at a radius of about 8 Å, below which the tension is found to decrease again. In the case of spherical drops, a marked decrease in the tension from the planar limit is found for radii below ∼ 15 Å; there is no indication of a maximum in the tension with increasing curvature. The vapour-liquid interfacial tension tends towards the planar limit for large system sizes for both the cylindrical and spherical cases. Estimates of the entropic and energetic contributions are also evaluated for the planar and cylindrical geometries and their magnitudes are in line with the expectations of our simple analysis

Land gastropod piercing during the Late Pleistocene and Early Holocene in the Haua Fteah, Libya

Land snail shell is a frequent constituent of archaeological sites, but it is rarely clear whether it represents food refuse, the remains of scavengers, or evidence for natural processes. Piercing of land snail shells enables the animal to be extracted from the shell and thus provides direct evidence for human consumption. We report pierced land snails from the Haua Fteah, Libya. The earliest pierced land snail shell in the Haua Fteah pre-dates the Last Interglacial, while the most recent is Late-Classical in age, but the largest quantities are in layers of Late-Glacial and earliest Holocene age, where they are associated with atypical microliths which may have been used to pierce shells to enable easy extraction of the animal

T Wave Alternans in high arrhythmic risk patients: Analysis in time and frequency domains: A pilot study

BACKGROUND: T wave alternans (TA) is a repolarisation phenomenon manifesting as a microvolt beat to beat change in the amplitude of the T wave and ST segment. TA has been shown to be a predictor of arrhythmic risk in unselected myocardial infarction populations. TA has not been used to differentiate risk within the ischaemic cardiomyopathy population. METHODS: The subjects investigated comprised, Group 1: 7 stable patients with remote (>20 months) extensive myocardial scarring and no arrhythmic events (NYHA 3 and 4). Group2: 9 post infarction patients with malignant arrhythmia and implantable defibrillator. During breath holding, 20 continuous QRST complexes from each patients X, Y and Z leads were digitally recorded. Time domain, resultant absolute difference vectors (ATA), were calculated for alternate resultant T wave sequences. Group differences between the magnitude and temporal distribution of mean ATAs and their spectral and cross-spectral analysis were compared. RESULTS: Group 1 v Group 2 mean ATAs were 10.7 (7.17) v 11.7 (8.48) respectively, not significant. Each group had a homogenous temporal distribution of ATAs. Both group's largest mean ATA frequency components were between 0 to 25 Hz, the largest ATA component being at the DC frequency. Cross spectral analysis showed no significant differences in group ATA frequency content. CONCLUSION: The frequency content and microvolt magnitude of T wave alternans was not significantly different in these two groups. The specificity of T wave alternans for differentiating arrhythmic risk in post infarction scarring and heart failure needs investigation

The cuttlefish Sepia officinalis (Sepiidae, Cephalopoda) constructs cuttlebone from a liquid-crystal precursor

Cuttlebone, the sophisticated buoyancy device of cuttlefish, is made of extensive superposed chambers that have a complex internal arrangement of calcified pillars and organic membranes. It has not been clear how this structure is assembled. We find that the membranes result from a myriad of minor membranes initially filling the whole chamber, made of nanofibres evenly oriented within each membrane and slightly rotated with respect to those of adjacent membranes, producing a helical arrangement. We propose that the organism secretes a chitin-protein complex, which self-organizes layer-by-layer as a cholesteric liquid crystal, whereas the pillars are made by viscous fingering. The liquid crystallization mechanism permits us to homologize the elements of the cuttlebone with those of other coleoids and with the nacreous septa and the shells of nautiloids. These results challenge our view of this ultra-light natural material possessing desirable mechanical, structural and biological properties, suggesting that two self-organizing physical principles suffice to understand its formation.Spanish Ministerio de Ciencia e Innovacion [CGL2010-20748-CO2-01, CGL2013-48247-P, FIS2013-48444-C2-2-P]; Andalusian Consejeria de Innovacion Ciencia y Tecnologia [RNM6433]; (Sepiatech, PROMAR program) of the Portuguese Ministerio da Agricultura e do Mar, Portugal [31.03.05.FEP.002]; Junta de Andalucia [RNM363]; FP7 COST Action of the European Community. [TD0903]info:eu-repo/semantics/publishedVersio

The Competition of Charge Remote and Charge Directed Fragmentation Mechanisms in Quaternary Ammonium Salt Derivatized Peptides—An Isotopic Exchange Study

Derivatization of peptides as quaternary ammonium salts (QAS) is a promising method for sensitive detection by electrospray ionization tandem mass spectrometry (Cydzik et al. J. Pept. Sci.2011, 17, 445–453). The peptides derivatized by QAS at their N-termini undergo fragmentation according to the two competing mechanisms – charge remote (ChR) and charge directed (ChD). The absence of mobile proton in the quaternary salt ion results in ChR dissociation of a peptide bond. However, Hofmann elimination of quaternary salt creates an ion with one mobile proton leading to the ChD fragmentation. The experiments on the quaternary ammonium salts with deuterated N-alkyl groups or amide NH bonds revealed that QAS derivatized peptides dissociate according to the mixed ChR-ChD mechanism. The isotopic labeling allows differentiation of fragments formed according to ChR and ChD mechanisms