Spatio-temporal correlations in aqueous systems: computational studies of static and dynamic heterogeneity by 2D-IR spectroscopy

Local heterogeneity is ubiquitous in natural aqueous systems. It can be caused locally by external biomolecular subsystems like proteins, DNA, micelles and reverse micelles, nanoscopic materials etc., but can also be intrinsic to the thermodynamic nature of the aqueous solution itself (like binary mixtures or at the gas-liquid interface). The altered dynamics of water in the presence of such diverse surfaces has attracted considerable attention in recent years. As these interfaces are quite narrow, only a few molecular layers thick, they are hard to study by conventional methods. The recent development of two dimensional infra-red (2D-IR) spectroscopy allows us to estimate length and time scales of such dynamics fairly accurately. In this work, we present a series of interesting studies employing two dimensional infra-red spectroscopy (2D-IR) to investigate (i) the heterogeneous dynamics of water inside reverse micelles of varying sizes, (ii) supercritical water near the Widom line that is known to exhibit pronounced density fluctuations and also study (iii) the collective and local polarization fluctuation of water molecules in the presence of several different proteins. The spatio-temporal correlation of confined water molecules inside reverse micelles of varying sizes is well captured through the spectral diffusion of corresponding 2D-IR spectra. In the case of supercritical water also, we observe a strong signature of dynamic heterogeneity from the elongated nature of the 2D-IR spectra. In this case the relaxation is ultrafast. We find remarkable agreement between the different tools employed to study the relaxation of density heterogeneity. For aqueous protein solutions, we find that the calculated dielectric constant of the respective systems unanimously shows a noticeable increment compared to that of neat water. However, the `effective' dielectric constant for successive layers shows significant variation, with the layer adjacent to the protein having a much lower value. Relaxation is also slowest at the surface. We find that the dielectric constant achieves the bulk value at distances more than 3 nm from the surface of the protein.

滑坡型泥石流转化机理研究—以四川省达县青宁乡滑坡为例

Slide-debris flow is debris flow which is transformed from landslide consecutively in a short time, it comprises of two phases: First, Landslide starts to slide; Second, landslide changes to debris flow. Slide-debris flow which brings great property and life loss happens frequently at home and abroad. In order to forecast the happening possibility and scope of slide-debris flow, transfromation mechanism of Slide-debris flow must be studied. Research on transformation mechanism of slide-debris flow is intersectant science of landslide kinetics and debris flow starting theory, It is a fringe problem as well as front problem of geological hazard. This paper takes Qingning slide-debris flow in Da County, Sichuan Province for example and has studied the mechanism of its instability and transfromation into debris flow through indoor test (including usual soil test and ring shear test) and digital modeling method.The research gets the following conclusions. Qingning Landslide took place mainly because of confined water head arising from rainfall infiltration. Before Landslide occurring, it rained continuously for 22 days, accumulated precipitation arrived at 521.6mm.Investigation shows that strata of Qingning Landslide contains quaternary loose accumulation, slip soil and highly weathered bedrock, which is a good condition for formation of confined water in the slope. Further more, groundwater seepage in the slope body and corresponding slope safety factor before landslide occurring have been computed through finite element method. The result shows that because of infiltration of rainfall, confined water head in the slope arose sharply, accordingly, the safety factor of the slope declined quickly. The result also shows that force put on the slide body by the rock mass detached from Dazhaiyan mountain was the direct factor for landslide occurring. Qingning slide-debris transformation mode has been summarized, the process the landslide changed into debris flow is divided into three phases in the prospective of macroscopic geological condition: landslide occurring, transformation and debris flow. Landslide occurring phase is from slope’ local creeping slide to Landslide occurring; transformation phase contains slide body sliding on the slide bed after slide occurring and sliding on the slope after shearing opening; debris flow phase is that slide body breaks up completely and flows downward into the ditches. The transformation mechanism of Qingning slide-debris flow has been studied through indoor ring shear test of slip soil. The result shows that transformation mechanism contains two points: first, during slide body sliding on the slide bed and slope after shearing opening, shearing shrinkage, grain crushing and grain layering brought about declining of its volume and produced excess pore water pressure, and because producing velocity of excess pore water pressure is much greater than its dissipating velocity, shear strength of slide body decreased sharply because of accumulated pore water pressure. Second, grains crushing and grains layering during slide body sliding brought about thick liquefied layer at the bottom of the slidebody, liquefied layer contained high water content and its shear strength was very low, its thickness increased as the sliding displacement increasing. Liquefied layer makes slide body sliding fast and easily break down to debris flow. Excess pore water pressure and liquefied layer made shear strength of slidebody became very low, furthermore, water in the pit of slope joining in the slidebody was also a facter that made slidebody accelerate the transformation. Influence of slide body thickness and fine grains content to transformation of slide-debris flow has been studied through ring shear test. The result reaches two conclusions. First, thickness of slide body affects transformation of slide-debris flow by two ways, porewater pressure and effect of “soft base” increases as thickness of slide body increasing.so the thicker slide body is ,the easier transformation is. Second, actual dissipating velocity of porewater pressure should be considered when studying the influence of fine grains content to tranformation of slide-debris flow. There should be a critical content of fine grains which makes the difference of producing and dissipating velocity of water pore pressre greatest, this value is the best for slide-debris transformation. The whole process of slide-debris flow transformation is reproduced through discrete element method. Transformation mechanism of slide-debris flow is studied through monitoring various parameters including pore water pressure, grain crushing and grain layering in the slide body during the transformation. The result confirms and supplements the transformation mechanism of slide-debris flow got from ring shear test well.

Physico-chemical properties and component interactions in high solids food systems

The present study aimed to investigate interactions of components in the high solids systems during storage. The systems included (i) lactose–maltodextrin (MD) with various dextrose equivalents at different mixing ratios, (ii) whey protein isolate (WPI)–oil [olive oil (OO) or sunflower oil (SO)] at 75:25 ratio, and (iii) WPI–oil– {glucose (G)–fructose (F) 1:1 syrup [70% (w/w) total solids]} at a component ratio of 45:15:40. Crystallization of lactose was delayed and increasingly inhibited with increasing MD contents and higher DE values (small molecular size or low molecular weight), although all systems showed similar glass transition temperatures at each aw. The water sorption isotherms of non-crystalline lactose and lactose–MD (0.11 to 0.76 aw) could be derived from the sum of sorbed water contents of individual amorphous components. The GAB equation was fitted to data of all non-crystalline systems. The protein–oil and protein–oil–sugar materials showed maximum protein oxidation and disulfide bonding at 2 weeks of storage at 20 and 40°C. The WPI–OO showed denaturation and preaggregation of proteins during storage at both temperatures. The presence of G–F in WPI–oil increased Tonset and Tpeak of protein aggregation, and oxidative damage of the protein during storage, especially in systems with a higher level of unsaturated fatty acids. Lipid oxidation and glycation products in the systems containing sugar promoted oxidation of proteins, increased changes in protein conformation and aggregation of proteins, and resulted in insolubility of solids or increased hydrophobicity concomitantly with hardening of structure, covalent crosslinking of proteins, and formation of stable polymerized solids, especially after storage at 40°C. We found protein hydration transitions preceding denaturation transitions in all high protein systems and also the glass transition of confined water in protein systems using dynamic mechanical analysis.

Adhesion as a tool for in-built nanotechnology design in cementitious materials

Confined water, such as those molecules in nanolayers of 2-3 nm in length, plays an important role in the adhesion of hydrophilic materials, mainly in cementitious ones. In this study, the effects of water containing kosmotropic substances on adhesion, known for their ability of enhancing the hydrogen bond (H-bond) network of confined water, were evaluated using mechanical strength tests. Indeed, to link adhesion provided by water confined in nanolayers to a macro-response of the cementitious samples, such as the bending strength, requires the evaluation of local water H-bond network configuration in the presence of kosmotropes, considering their influences on the extent and the strength of H-bonds. Among the kosmotropes, trimethylamine and sucrose provided a 50% increase in bending strength compared to the reference samples, the latter just using water as an adhesive, whereas trehalose was responsible for reducing the bending strength to a value close to the samples without any adhesive. The results attained opened up perspectives regarding exploring the confined water behavior which naturally occurs throughout the hydration process in cement-based materials.

Análise de queilite actínica por espectroscopia micro FT-IR

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Molecular model for hydrated biological tissues

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The structure and dynamics of 2-dimensional fluids in swelling clays

The interlayer pores of swelling 2:1 clays provide an ideal 2-dimensional environment in which to study confined fluids. In this paper we discuss our understanding of the structure and dynamics of interlayer fluid species in expanded clays, based primarily on the outcome of recent molecular modelling and neutron scattering studies. Counterion solvation is compared with that measured in bulk solutions, and at a local level the cation-oxygen coordination is found to be remarkably similar in these two environments. However, for the monovalent ions the contribution to the first coordination shell from the clay surfaces increases with counterion radius. This gives rise to inner-sphere (surface) complexes in the case of potassium and caesium. In this context, the location of the negative clay surface charge (i.e. arising from octahedral or tetrahedral substitution) is also found to be of major importance. Divalent cations, such as calcium, eagerly solvate to form outer-sphere complexes. These complexes are able to pin adjacent clay layers together, and thereby prevent colloidal swelling. Confined water molecules form hydrogen bonds to each other and to the clays' surfaces. In this way their local environment relaxes to close to the bulk water structure within two molecular layers of the clay surface. Finally, we discuss the way in which the simple organic molecules methane, methanol and ethylene glycol behave in the interlayer region of hydrated clays. Quasi-elastic neutron scattering of isotopically labelled interlayer CH 3OD and (CH2OD)2 in deuterated clay allows us to measure the diffusion of the CH3- and CH2-groups in both clay and liquid environments. We find that in both the one-layer methanol solvates and the two-layer glycol solvates the diffusion of the most mobile organic molecules is close to that in the bulk solution.

Chemistry in Confined Spaces: High-Energy Conformer of a Piperidine Derivative is Favored Within a Water-Soluble Capsuleplex

Propyloxy-substituted piperidine in solution adopts a conformation in which its alkoxy group is equatorially positioned Surprisingly, two conformers of it that do not interconvert in the NMR time scale at room temperature have been found within an octa-acid capsule The serendipitous finding of the axial conformer of propyloxy-substituted piperidine within a supramolecular capsule highlights the value of confined spaces in physical organic chemistry.

Molecular probe dynamics reveals suppression of ice-like regions in strongly confined supercooled water

The structure of the hydrogen bond network is a key element for understanding water's thermodynamic and kinetic anomalies. While ambient water is strongly believed to be a uniform, continuous hydrogen-bonded liquid, there is growing consensus that supercooled water is better described in terms of distinct domains with either a low-density ice-like structure or a high-density disordered one. We evidenced two distinct rotational mobilities of probe molecules in interstitial supercooled water of polycrystalline ice Banerjee D, et al. (2009) ESR evidence for 2 coexisting liquid phases in deeply supercooled bulk water. Proc Natl Acad Sci USA 106: 11448-11453]. Here we show that, by increasing the confinement of interstitial water, the mobility of probe molecules, surprisingly, increases. We argue that loose confinement allows the presence of ice-like regions in supercooled water, whereas a tighter confinement yields the suppression of this ordered fraction and leads to higher fluidity. Compelling evidence of the presence of ice-like regions is provided by the probe orientational entropy barrier which is set, through hydrogen bonding, by the configuration of the surrounding water molecules and yields a direct measure of the configurational entropy of the same. We find that, under loose confinement of supercooled water, the entropy barrier surmounted by the slower probe fraction exceeds that of equilibrium water by the melting entropy of ice, whereas no increase of the barrier is observed under stronger confinement. The lower limit of metastability of supercooled water is discussed.

Highly oriented tunable wrinkling in polymer bilayer films confined with a soft mold induced by water vapor

The authors report the formation of highly oriented wrinkling on the surface of the bilayer [polystyrene (PS)/poly(vinyl pyrrolidone) (PVP)] confined by a polydimethylsiloxane (PDMS) mold in a water vapor environment. When PVP is subjected to water vapor, the polymer loses its mechanical rigidity and changes to a viscous state, which leads to a dramatic change in Young's modulus. This change generates the amount of strain in the bilayer to induce the wrinkling. With a shape-controlled mold, they can get the ordered wrinkles perfectly perpendicular or leaned 45 S to the channel orientation of the mold because the orientation of the resultant force changes with the process of water diffusion which drives the surface to form the wrinkling. Additionally, they can get much smaller wrinkles than the stripe spacing of PDMS mold about one order. The wrinkle period changes with the power index of about 0.5 for various values of the multiplication product of the film thicknesses of the two layers, namely, lambda similar to (h(PS)h(PVP))(1/2).

MOLECULAR DYNAMICS STUDIES OF SIMPLE MODEL FLUIDS AND WATER CONFINED IN CARBON NANOTUBE

Molecular Dynamics (MD) simulation is one of the most important computational techniques with broad applications in physics, chemistry, chemical engineering, materials design and biological science. Traditional computational chemistry refers to quantum calculations based on solving Schrodinger equations. Later developed Density Functional Theory (DFT) based on solving Kohn-Sham equations became the more popular ab initio calculation technique which could deal with ~1000 atoms by explicitly considering electron interactions. In contrast, MD simulation based on solving classical mechanics equations of motion is a totally different technique in the field of computational chemistry. Electron interactions were implicitly included in the empirical atom-based potential functions and the system size to be investigated can be extended to ~106 atoms. The thermodynamic properties of model fluids are mainly determined by macroscopic quantities, like temperature, pressure, density. The quantum effects on thermodynamic properties like melting point, surface tension are not dominant. In this work, we mainly investigated the melting point, surface tension (liquid-vapor and liquid-solid) of model fluids including Lennard-Jones model, Stockmayer model and a couple of water models (TIP4P/Ew, TIP5P/Ew) by means of MD simulation. In addition, some new structures of water confined in carbon nanotube were discovered and transport behaviors of water and ions through nano-channels were also revealed.

Determination of coastal ground and surface water processes and character by use of hydrochemistry and stable isotopes, Fraser Coast, Queensland

This study was part of an integrated project developed in response to concerns regarding current and future land practices affecting water quality within coastal catchments and adjacent marine environments. Two forested coastal catchments on the Fraser Coast, Australia, were chosen as examples of low-modification areas with similar geomorphological and land-use characteristics to many other coastal zones in southeast Queensland. For this component of the overall project, organic , physico-chemical (Eh, pH and DO), ionic (Fe2+, Fe3+), and isotopic (ä13CDIC, ä15NDIN ä34SSO4) data were used to characterise waters and identify sources and processes contributing to concentrations and form of dissolved Fe, C, N and S within the ground and surface waters of these coastal catchments. Three sites with elevated Fe concentrations are discussed in detail. These included a shallow pool with intermittent interaction with the surface water drainage system, a monitoring well within a semi-confined alluvial aquifer, and a monitoring well within the fresh/saline water mixing zone adjacent to an estuary. Conceptual models of processes occurring in these environments are presented. The primary factors influencing Fe transport were; microbial reduction of Fe3+ oxyhydroxides in groundwaters and in the hyporheic zone of surface drainage systems, organic input available for microbial reduction and Fe3+ complexation, bacterial activity for reduction and oxidation, iron curtain effects where saline/fresh water mixing occurs, and variation in redox conditions with depth in ground and surface water columns. Data indicated that groundwater seepage appears a more likely source of Fe to coastal waters (during periods of low rainfall) via tidal flux. The drainage system is ephemeral and contributes little discharge to marine waters. However, data collected during a high rainfall event indicated considerable Fe loads can be transported to the estuary mouth from the catchment.

A water-dielectric capacitor using hydrated graphene oxide film

Despite the widespread use of paper, plastic or ceramics in dielectric capacitors, water has not been commonly used as a dielectric due to its tendency to become conductive as it easily leaches ions from the environment. We show here that when water is confined between graphene oxide sheets, it can retain its insulating nature and behave as a dielectric. A hydrated graphene oxide film was used as a dielectric spacer to construct a prototype water-dielectric capacitor. The capacitance depends on the water content of the hydrated GO film as well as the voltage applied to the device. Our results show that the capacitance per unit area of the GO film is in the range of 100–800 mF cm �2, which is 5–40 times that of the double layer capacitance per surface area of activated carbon.

Absence of reptation in highly confined polymers

We present results of mechanical stress relaxation measurements on polymers confined at the air-water interface in the form of a monolayer. Systematic measurements allow, to our knowledge, for the first time, observation of the scaling of the stress relaxation time of the highly confined polymers as a function of both surface concentration and molecular weight. The observed scaling is found to be very close to that expected for motion of unentangled polymer solutions with hydrodynamic interactions. Our experimental observations thus clearly rule out the possibility of entanglement and hence reptation as a mode of relaxation in such highly confined polymeric systems.

Space allowances for confined livestock and their determination from allometric principles

The amount of space provided to animals governs important elements of their behaviour and, hence, is critical for their health and welfare. We review the use of allometric principles and equations to estimate the static space requirements of animals when standing and lying, and the space required for animals to feed, drink, stand-up and lie-down. We use the research literature relating to transportation and intensive housing of sheep and cattle to assess the validity of allometric equations for estimating space allowances. We investigated these areas because transportation and intensive housing provide points along a continuum in terms of the duration of confinement, (from hours to months) and spatial requirements are likely to increase with increasing duration of confinement, as animals will need to perform a greater behavioural repertoire for long-term survival, health and welfare. We find that, although there are theoretical reasons why allometric relationships to space allowances may vary slightly for different classes of stock, space allowances that have been demonstrated to have adverse effects on animal welfare during transportation correlated well with an inability to accommodate standing animals, as estimated from allometry. For intensive housing, we were able to detect a space allowance below which there were adverse effects on welfare. For short duration transportation during which animals remain standing, a space allowance per animal described by the allometric equation: area (m^2) = 0.020W^0.66, where W = liveweight (kg), would appear to be appropriate. Where it is desirable for all animals to lie simultaneously, then a minimum space allowance per animal described by the allometric equation: area (m^2) = 0.027W^0.66 appears to permit this, given that animals in a group time-share space. However, there are insufficient data to determine whether this allowance onboard a vehicle/vessel would enable animals to move and access food and water with ease. In intensive housing systems, a minimum space allowance per animal described by the allometric equation: area (m^2) = 0.033W^0.66 appears to be the threshold below which there are adverse effects on welfare. These suggested space allowances require verification with a range of species under different thermal conditions and, for transportation, under different conditions of vehicular/vessel stability. The minimum length of trough per animal (L in m) required for feeding and drinking can be determined from L = 0.064W^0.33, with the number of animals required to feed/drink simultaneously taken into account, together with any requirement to minimise competition. This also requires verification with a range of species. We conclude that allometric relationships are an appropriate basis for the formulation of space allowances for livestock.