Dynamics of shear-induced orientation transitions in block copolymers

This review discusses liquid crystal phase formation by biopolymers in solution. Lyotropic mesophases have been observed for several classes of biopolymer including DNA, peptides, polymer/peptide conjugates, glycopolymers and proteoglycans. Nematic or chiral nematic (cholesteric) phases are the most commonly observed mesophases, in which the rod-like fibrils have only orientational order. Hexagonal columnar phases are observed for several systems (DNA, PBLG, polymer/peptide hybrids) at higher concentration. Lamellar (smectic) phases are reported less often, although there are examples such as the layer arrangement of amylopectin side chains in starch. Possible explanations for the observed structures are discussed. The biological role of liquid crystal phases for several of these systems is outlined. Commonly, they may serve as a template to align fibrils for defined structural roles when the biopolymer is extruded and dried, for instance in the production of silk by spiders or silkworms, or of chitin in arthropod shells. In other cases, liquid crystal phase formation may occur in vivo simply as a consequence of high concentration, for instance the high packing density of DNA within cell nuclei.

Small-angle x-ray scattering study of flow alignment of a thermotropic liquid crystal in the nematic and smectic phases

WThe capillary flow alignment of the thermotropic liquid crystal 4-n-octyl-4′-cyanobiphenyl in the nematic and smectic phases is investigated using time-resolved synchrotron small-angle x-ray scattering. Samples were cooled from the isotropic phase to erase prior orientation. Upon cooling through the nematic phase under Poiseuille flow in a circular capillary, a transition from the alignment of mesogens along the flow direction to the alignment of layers along the flow direction (mesogens perpendicular to flow) appears to occur continuously at the cooling rate applied. The transition is centered on a temperature at which the Leslie viscosity coefficient α3 changes sign. The configuration with layers aligned along the flow direction is also observed in the smectic phase. The transition in the nematic phase on cooling has previously been ascribed to an aligning-nonaligning or tumbling transition. At high flow rates there is evidence for tumbling around an average alignment of layers along the flow direction. At lower flow rates this orientation is more clearly defined. The layer alignment is ascribed to surface-induced ordering propagating into the bulk of the capillary, an observation supported by the parallel alignment of layers observed for a static sample at low temperatures in the nematic phase.

A two-dimensional X-ray scattering system for in-situ time-resolving studies of polymer structures subjected to controlled deformations

A two-dimensional X-ray scattering system developed around a CCD-based area detector is presented, both in terms of hardware employed and software designed and developed. An essential feature is the integration of hardware and software, detection and sample environment control which enables time-resolving in-situ wide-angle X-ray scattering measurements of global structural and orientational parameters of polymeric systems subjected to a variety of controlled external fields. The development and operation of a number of rheometers purpose-built for the application of such fields are described. Examples of the use of this system in monitoring degrees of shear-induced orientation in liquid-crystalline systems and crystallization of linear polymers subsequent to shear flow are presented.

Litomosoides sigmodontis: vaccine-induced immune responses against Wolbachia surface protein can enhance the survival of filarial nematodes during primary infection

Wolbachia are bacteria present within the tissues of most filarial nematodes. Filarial nematode survival is known to be affected by immune responses generated during filarial nematode infection and immune responses to Wolbachia can be found in different species harbouring filarial nematode infections, including humans. Using the rodent filarial model Litomosoides sigmodontis, we show that pre-exposure to wolbachia surface protein in a Th1 context (but not in a Th2-context) enhances worm survival on subsequent challenge. This study suggests that despite abundant evidence that pro-inflammatory reactions to the endosymbiont have detrimental effects on the both the nematode and mammalian host, they may under some circumstances be beneficial to the nematode.

Hydrogen bond-induced pair formation of glycine on the chiral Cu{531} surface

Enantio-specific interactions on intrinsically chiral or chirally modified surfaces can be identified experimentally via comparison of the adsorption geometries of similar nonchiral and chiral molecules. Information about the effects of substrate-related and in interactions on the adsorption geometry of glycine, the only natural nonchiral amino acid, is therefore important for identifying enantio-specific interactions of larger chiral amino acids. We have studied the long- and short-range adsorption geometry and bonding properties of glycine on the intrinsically chiral Cu{531} surface with low-energy electron diffraction, near-edge X-ray absorption One structure spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed desorption. For coverages between 0.15 and 0.33 ML (saturated chemisorbed layer) and temperatures between 300 and 430 K, glycine molecules adsorb in two different azimuthal orientations, which are associated with adsorption sites on the {110} and {311} microfacets of Cu{531}. Both types of adsorption sites allow a triangular footprint with surface bonds through the two oxygen atoms and the nitrogen atom. The occupation of the two adsorption sites is equal for all coverages, which can be explained by pair formation due to similar site-specific adsorption energies and the possibility of forming hydrogen bonds between molecules on adjacent {110} and {311} sites. This is not the ease for alanine and points toward higher site specificity in the case of alanine, which is eventually responsible for the enantiomeric differences observed for the alanine system.

Flow-induced dynamic surface tension effects at nanoscale

The aim of this study is to investigate flow-induced dynamic surface tension effects, similar to the well-known Marangoni phenomena, but solely generated by the nanoscale topography of the substrates. The flow-induced surface tension effects are examined on the basis of a sharp interface theory. It is demonstrated how nanoscale objects placed at the boundary of the flow domain result in the generation of substantial surface forces acting on the bulk flow.

WAXS studies of global molecular orientation induced in nematic liquid crystals by simple shear flow

Global molecular orientation function coefficients for the nematic liquid crystal 4-cyano 4'-nn -pentylbiphenyl (5CB) in shear flow are presented, being extracted from 2-dimensional Wide-Angle X-ray Scattering data. A linear increase in orientation parameter P2 is observed with a logarithmic increase in shear rate. It is proposed that this arises from an increased number of LC directors aligning to the shear axis. Upon cessation of shear flow, the anisotropy is seen to relax away completely, over a time scale which is inversely proportional to the previously applied shear rate.

Morphology induced spinodal decomposition at the surface of symmetric diblock copolymer films

Atomic force microscopy is used to study the ordering dynamics of symmetric diblock copolymer films. The films order to form a lamellar structure which results in a frustration when the film thickness is incommensurate with the lamellae. By probing the morphology of incommensurate films in the early ordering stages, we discover an intermediate phase of lamellae arranged perpendicular to the film surface. This morphology is accompanied by a continuous growth in amplitude of the film surface topography with a characteristic wavelength, indicative of a spinodal process. Using selfconsistent field theory, we show that the observation of perpendicular lamellae suggests an intermediate state with parallel lamellae at the substrate and perpendicular lamellae at the free surface. The calculations confirm that the intermediate state is unstable to thickness fluctuations, thereby driving the spinodal growth of surface structures.

Repulsion-induced surface-migration, by ballistics and bounce

The motion of adsorbate molecules across surfaces is fundamental to self-assembly, material growth, and heterogeneous catalysis. Recent Scanning Tunneling Microscopy studies have demonstrated the electron-induced long-range surface-migration of ethylene, benzene, and related molecules, moving tens of Angstroms across Si(100). We present a model of the previously unexplained long-range recoil of chemisorbed ethylene across the surface of silicon. The molecular dynamics reveal two key elements for directed long-range migration: first ‘ballistic’ motion that causes the molecule to leave the ab initio slab of the surface traveling 3–8 Å above it out of range of its roughness, and thereafter skipping-stone ‘bounces’ that transport it further to the observed long distances. Using a previously tested Impulsive Two-State model, we predict comparable long-range recoil of atomic chlorine following electron-induced dissociation of chlorophenyl chemisorbed at Cu(110)

Adsorption, orientation and thermal decomposition of copper(II) hexafluoroacetylacetonate on rutile TiO2(110)

We have investigated the adsorption and thermal decomposition of copper hexafluoroacetylacetonate (Cu-11(hfaC)(2)) on single crystal rutile TiO2(110). Low energy electron diffraction shows that room temperature saturation coverage of the Cu-II(hfac)(2) adsorbate forms an ordered (2 x 1) over-layer. X-ray and ultra-violet photoemission spectroscopy of the saturated surface were recorded as the sample was annealed in a sequential manner to reveal decomposition pathways. The results show that the molecule dissociatively adsorbs by detachment of one of the two ligands to form hfac and Cu-1(hfac) which chemisorb to the substrate at 298 K. These ligands only begin to decompose once the surface temperature exceeds 473 K where Cu core level shifts indicate metallisation. This reduction from Cu(I) to Cu(0) takes place in the absence of an external reducing agent and without disproportionation and is accompanied by the onset of decomposition of the hfac ligands. Finally, C K-edge near edge X-ray absorption fine structure experiments indicate that both the ligands adsorb aligned in the < 001 > direction and we propose a model in which the hfac ligands adsorb on the 5-fold coordinated Ti atoms and the Cu-1(hfac) moiety attaches to the bridging O atoms in a square planar geometry. The calculated tilt angle for these combined geometries is approximately 10 degrees to the surface normal.

Electronic structure of point defects in controlled self-doping of the TiO2 (110) surface: Combined photoemission spectroscopy and density functional theory study

Point defects in metal oxides such as TiO2 are key to their applications in numerous technologies. The investigation of thermally induced nonstoichiometry in TiO2 is complicated by the difficulties in preparing and determining a desired degree of nonstoichiometry. We study controlled self-doping of TiO2 by adsorption of 1/8 and 1/16 monolayer Ti at the (110) surface using a combination of experimental and computational approaches to unravel the details of the adsorption process and the oxidation state of Ti. Upon adsorption of Ti, x-ray and ultraviolet photoemission spectroscopy (XPS and UPS) show formation of reduced Ti. Comparison of pure density functional theory (DFT) with experiment shows that pure DFT provides an inconsistent description of the electronic structure. To surmount this difficulty, we apply DFT corrected for on-site Coulomb interaction (DFT+U) to describe reduced Ti ions. The optimal value of U is 3 eV, determined from comparison of the computed Ti 3d electronic density of states with the UPS data. DFT+U and UPS show the appearance of a Ti 3d adsorbate-induced state at 1.3 eV above the valence band and 1.0 eV below the conduction band. The computations show that the adsorbed Ti atom is oxidized to Ti2+ and a fivefold coordinated surface Ti atom is reduced to Ti3+, while the remaining electron is distributed among other surface Ti atoms. The UPS data are best fitted with reduced Ti2+ and Ti3+ ions. These results demonstrate that the complexity of doped metal oxides is best understood with a combination of experiment and appropriate computations.

How many facets are needed to represent the surface energy balance of an urban area?

We investigate the question of how many facets are needed to represent the energy balance of an urban area by developing simplified 3-, 2- and 1-facet versions of a 4-facet energy balance model of two-dimensional streets and buildings. The 3-facet model simplifies the 4-facet model by averaging over the canyon orientation, which results in similar net shortwave and longwave balances for both wall facets, but maintains the asymmetry in the heat fluxes within the street canyon. For the 2-facet model, on the assumption that the wall and road temperatures are equal, the road and wall facets can be combined mathematically into a single street-canyon facet with effective values of the heat transfer coefficient, albedo, emissivity and thermodynamic properties, without further approximation. The 1-facet model requires the additional assumption that the roof temperature is also equal to the road and wall temperatures. Idealised simulations show that the geometry and material properties of the walls and road lead to a large heat capacity of the combined street canyon, whereas the roof behaves like a flat surface with low heat capacity. This means that the magnitude of the diurnal temperature variation of the street-canyon facets are broadly similar and much smaller than the diurnal temperature variation of the roof facets. Consequently, the approximation that the street-canyon facets have similar temperatures is sound, and the road and walls can be combined into a single facet. The roof behaves very differently and a separate roof facet is required. Consequently, the 2-facet model performs similarly to the 4-facet model, while the 1-facet model does not. The models are compared with previously published observations collected in Mexico City. Although the 3- and 2-facet models perform better than the 1-facet model, the present models are unable to represent the phase of the sensible heat flux. This result is consistent with previous model comparisons, and we argue that this feature of the data cannot be produced by a single column model. We conclude that a 2-facet model is necessary, and for numerical weather prediction sufficient, to model an urban surface, and that this conclusion is robust and therefore applicable to more general geometries.

A review of the potential impacts of climate change on surface water quality

It is now accepted that some human-induced climate change is unavoidable. Potential impacts on water supply have received much attention, but relatively little is known about the concomitant changes in water quality. Projected changes in air temperature and rainfall could affect river flows and, hence, the mobility and dilution of contaminants. Increased water temperatures will affect chemical reaction kinetics and, combined with deteriorations in quality, freshwater ecological status. With increased flows there will be changes in stream power and, hence, sediment loads with the potential to alter the morphology of rivers and the transfer of sediments to lakes, thereby impacting freshwater habitats in both lake and stream systems. This paper reviews such impacts through the lens of UK surface water quality. Widely accepted climate change scenarios suggest more frequent droughts in summer, as well as flash-flooding, leading to uncontrolled discharges from urban areas to receiving water courses and estuaries. Invasion by alien species is highly likely, as is migration of species within the UK adapting to changing temperatures and flow regimes. Lower flows, reduced velocities and, hence, higher water residence times in rivers and lakes will enhance the potential for toxic algal blooms and reduce dissolved oxygen levels. Upland streams could experience increased dissolved organic carbon and colour levels, requiring action at water treatment plants to prevent toxic by-products entering public water supplies. Storms that terminate drought periods will flush nutrients from urban and rural areas or generate acid pulses in acidified upland catchments. Policy responses to climate change, such as the growth of bio-fuels or emission controls, will further impact freshwater quality.

A case study of the radiative forcing of persistent contrails evolving into contrail-induced cirrus

The radiative forcing due to a distinct pattern of persistent contrails that form into contrail-induced cirrus near and over the UK is investigated in detail for a single case study during March 2009. The development of the contrail-induced cirrus is tracked using a number of high-resolution polar orbiting and lower-resolution geostationary satellite instruments and is found to persist for a period of around 18 h, and at its peak, it covers over 50,000 km2. The shortwave (SW) and longwave (LW) radiative forcing of the contrail-induced cirrus is estimated using a combination of geostationary satellite instruments, numerical weather prediction models, and surface observation sites. As expected, the net radiative effect is a relatively small residual of the much stronger but opposing SW and LW effects, locally totaling around 10 W m−2 during daylight hours and 30 W m−2 during nighttime. A simple estimate indicates that this single localized event may have generated a global-mean radiative forcing of around 7% of recent estimates of the persistent contrail radiative forcing due to the entire global aircraft fleet on a diurnally averaged basis. A single aircraft operating in conditions favorable for persistent contrail formation appears to exert a contrail-induced radiative forcing some 5000 times greater (in W m−2 km−1) than recent estimates of the average persistent contrail radiative forcing from the entire civil aviation fleet. This study emphasizes the need to establish whether similar events are common or highly unusual for a confident assessment of the total climate effect of aviation to be made.

A case study of the radiative forcing of persistent contrails evolving into contrail-induced cirrus

The radiative forcing due to a distinct pattern of persistent contrails that form into contrail-induced cirrus near and over the UK is investigated in detail for a single case study during March 2009. The development of the contrail-induced cirrus is tracked using a number of high-resolution polar orbiting and lower-resolution geostationary satellite instruments and is found to persist for a period of around 18 h, and at its peak, it covers over 50,000 km2. The shortwave (SW) and longwave (LW) radiative forcing of the contrail-induced cirrus is estimated using a combination of geostationary satellite instruments, numerical weather prediction models, and surface observation sites. As expected, the net radiative effect is a relatively small residual of the much stronger but opposing SW and LW effects, locally totaling around 10 W m−2 during daylight hours and 30 W m−2 during nighttime. A simple estimate indicates that this single localized event may have generated a global-mean radiative forcing of around 7% of recent estimates of the persistent contrail radiative forcing due to the entire global aircraft fleet on a diurnally averaged basis. A single aircraft operating in conditions favorable for persistent contrail formation appears to exert a contrail-induced radiative forcing some 5000 times greater (in W m−2 km−1) than recent estimates of the average persistent contrail radiative forcing from the entire civil aviation fleet. This study emphasizes the need to establish whether similar events are common or highly unusual for a confident assessment of the total climate effect of aviation to be made.