The dominant role of the solvent-water interface in water droplet templating of polymers

We investigate the formation of microstructured polymer networks known as Breath Figure templated structures created by the presence of water vapour over evaporating polymer solutions. We use a highly controlled experimental approach to examine this dynamic and non-equilibrium process to uniquely compare pure solvent systems with polymer solutions and demonstrate using a combination of optical microscopy, focused ion-beam milling and SEM analysis that the porous polymer microstructure is completely controlled by the interfacial forces that exist between the water droplet and the solvent until a final drying dilation of the imprints. Water droplet contact angles are the same in the presence or absence of polymer and are independent of size for droplets above 5 μm. The polymer acts a spectator that serves to trap water droplets present at the air interface, and to transfer their shape into the polymer film. For the smallest pores, however, there are unexpected variations in the contact angle with pore size that are consistent with a possible contribution from line tension at these smaller dimensions. © The Royal Society of Chemistry.

Interfacial immobilization of monoclonal antibody and detection of human prostate-specific antigen.

Antibody orientation and its antigen binding efficiency at interface are of particular interest in many immunoassays and biosensor applications. In this paper, spectroscopic ellipsometry (SE), neutron reflection (NR), and dual polarization interferometry (DPI) have been used to investigate interfacial assembly of the antibody [mouse monoclonal anti-human prostate-specific antigen (anti-hPSA)] at the silicon oxide/water interface and subsequent antigen binding. It was found that the mass density of antibody adsorbed at the interface increased with solution concentration and adsorption time while the antigen binding efficiency showed a steady decline with increasing antibody amount at the interface over the concentration range studied. The amount of antigen bound to the interfacial immobilized antibody reached a maximum when the surface-adsorbed amount of antibody was around 1.5 mg/m(2). This phenomenon is well interpreted by the interfacial structural packing or crowding. NR revealed that the Y-shaped antibody laid flat on the interface at low surface mass density with a thickness around 40 Å, equivalent to the short axial length of the antibody molecule. The loose packing of the antibody within this range resulted in better antigen binding efficiency, while the subsequent increase of surface-adsorbed amount led to the crowding or overlapping of antibody fragments, hence reducing the antigen binding due to the steric hindrance. In situ studies of antigen binding by both NR and DPI demonstrated that the antigen inserted into the antibody layer rather than forming an additional layer on the top. Stability assaying revealed that the antibody immobilized at the silica surface remained stable and active over the monitoring period of 4 months. These results are useful in forming a general understanding of antibody interfacial behavior and particularly relevant to the control of their activity and stability in biosensor development.

Metal Retention Experiments for the Design of Soil-Mix Technology Permeable Reactive Barriers

Soil-mix technology is effective for the construction of permeable reactive barriers (PRBs) for in situ groundwater treatment. The objective of this study was to perform initial experiments for the design of soil-mix technology PRBs according to (i) sorption isotherm, (ii) reaction kinetics and (iii) mass balance of the contaminants. The four tested reactive systems were: (i) a granular zeolite (clinoptilolite-GZ), (ii) a granular organoclay (GO), (iii) a 1:1-mixture GZ and model sandy clayey soil and (iv) a 1:1:1-mixture of GZ, GO and model soil. The laboratory experiments consisted of batch tests (volume 900mL and sorbent mass 18g) with a multimetal solution of Pb, Cu, Zn, Cd and Ni. For the adsorption experiment, the initial concentrations ranged from 0.01 to 0.5mM (2.5 to 30mg/L). The maximum metal retention was measured in a batch test (300mg/L for each metal, volume 900mL, sorbent mass 90-4.5g). The reactive material efficiency order was found to be GZ>GZ-soil mix>GZ-soil-GO mix>GO. Langmuir isotherms modelled the adsorption, even in presence of a mixed cations solution. Adsorption was energetically favourable and spontaneous in all cases. Metals were removed according to the second order reaction kinetics; GZ and the 1:1-mix were very similar. The maximum retention capacity was 0.1-0.2mmol/g for Pb in the presence of clinoptilolite; for Cu, Zn, Cd and Ni, it was below 0.05mmol/g for the four reactive systems. Mixing granular zeolite, organoclay and model soil increased the chemisorption. Providing that GZ is reactive enough for the specific conditions, GZ can be mixed to obtain the required sorption. Granular clinoptilolite addition to soil is recommended for PRBs for metal contaminated groundwater. The laboratory experiments consisted of batch tests with a multimetal solution of Pb, Cu, Zn, Cd and Ni. The four reactive materials chosen were granular zeolite, clinoptilolite and model sandy clayey soil, granular organoclay and a mix of clinoptilolite, model soil and organoclay. The reactive material efficiency order was found to be granular clinoptilolite>clinoptilolite-soil mix>clinoptilolite-soil-organoclay mix>granular organoclay. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interfacial recognition of human prostate-specific antigen by immobilized monoclonal antibody: effects of solution conditions and surface chemistry.

The specific recognition between monoclonal antibody (anti-human prostate-specific antigen, anti-hPSA) and its antigen (human prostate-specific antigen, hPSA) has promising applications in prostate cancer diagnostics and other biosensor applications. However, because of steric constraints associated with interfacial packing and molecular orientations, the binding efficiency is often very low. In this study, spectroscopic ellipsometry and neutron reflection have been used to investigate how solution pH, salt concentration and surface chemistry affect antibody adsorption and subsequent antigen binding. The adsorbed amount of antibody was found to vary with pH and the maximum adsorption occurred between pH 5 and 6, close to the isoelectric point of the antibody. By contrast, the highest antigen binding efficiency occurred close to the neutral pH. Increasing the ionic strength reduced antibody adsorbed amount at the silica-water interface but had little effect on antigen binding. Further studies of antibody adsorption on hydrophobic C8 (octyltrimethoxysilane) surface and chemical attachment of antibody on (3-mercaptopropyl)trimethoxysilane/4-maleimidobutyric acid N-hydroxysuccinimide ester-modified surface have also been undertaken. It was found that on all surfaces studied, the antibody predominantly adopted the 'flat on' orientation, and antigen-binding capabilities were comparable. The results indicate that antibody immobilization via appropriate physical adsorption can replace elaborate interfacial molecular engineering involving complex covalent attachments.

Direct numerical simulation of turbulent flows over superhydrophobic surfaces with gas pockets using linearized boundary conditions

Superhydrophobic surfaces are shown to be effective for surface drag reduction under laminar regime by both experiments and simulations (see for example, Ou and Rothstein, Phys. Fluids 17:103606, 2005). However, such drag reduction for fully developed turbulent flow maintaining the Cassie-Baxter state remains an open problem due to high shear rates and flow unsteadiness of turbulent boundary layer. Our work aims to develop an understanding of mechanisms leading to interface breaking and loss of gas pockets due to interactions with turbulent boundary layers. We take advantage of direct numerical simulation of turbulence with slip and no-slip patterned boundary conditions mimicking the superhydrophobic surface. In addition, we capture the dynamics of gas-water interface, by deriving a proper linearized boundary condition taking into account the surface tension of the interface and kinematic matching of interface deformation and normal velocity conditions on the wall. We will show results from our simulations predicting the dynamical behavior of gas pocket interfaces over a wide range of dimensionless surface tensions.

Study of the turbulence in the air-side and water-side boundary layers in experimental laboratory wind induced surface waves

This study detailed the structure of turbulence in the air-side and water-side boundary layers in wind-induced surface waves. Inside the air boundary layer, the kurtosis is always greater than 3 (the value for normal distribution) for both horizontal and vertical velocity fluctuations. The skewness for the horizontal velocity is negative, but the skewness for the vertical velocity is always positive. On the water side, the kurtosis is always greater than 3, and the skewness is slightly negative for the horizontal velocity and slightly positive for the vertical velocity. The statistics of the angle between the instantaneous vertical fluctuation and the instantaneous horizontal velocity in the air is similar to those obtained over solid walls. Measurements in water show a large variance, and the peak is biased towards negative angles. In the quadrant analysis, the contribution of quadrants Q2 and Q4 is dominant on both the air side and the water side. The non-dimensional relative contributions and the concentration match fairly well near the interface. Sweeps in the air side (belonging to quadrant Q4) act directly on the interface and exert pressure fluctuations, which, in addition to the tangential stress and form drag, lead to the growth of the waves. The water drops detached from the crest and accelerated by the wind can play a major role in transferring momentum and in enhancing the turbulence level in the water side.On the air side, the Reynolds stress tensor's principal axes are not collinear with the strain rate tensor, and show an angle α σ≈=-20°to-25°. On the water side, the angle is α σ≈=-40°to-45°. The ratio between the maximum and the minimum principal stresses is σ a/σ b=3to4 on the air side, and σ a/σ b=1.5to3 on the water side. In this respect, the air-side flow behaves like a classical boundary layer on a solid wall, while the water-side flow resembles a wake. The frequency of bursting on the water side increases significantly along the flow, which can be attributed to micro-breaking effects - expected to be more frequent at larger fetches. © 2012 Elsevier B.V.