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.

Nitrogen dynamics in large shallow eutrophic Lake Chaohu, China

Temporal and spatial dynamics of nitrogen in lake and interstitial water were studied monthly in a large shallow, eutrophic lake in subtropical China from October 2002 to September 2003. The distribution of nitrogen was consistent with the idea that high nitrogen concentrations in the western part of the lake resulted from high levels of the nutrients from the surrounding cities through sewage-drainage systems. Nitrate was the predominant form of nitrogen in the overlying water, while ammonium was predominant in the interstitial water, indicating that strong oxidative nutrient regeneration occurred near the sediment-water interface. Nitrate could be an important dissolved inorganic matter source for phytoplankton, which in turn influenced the seasonal variations of nitrate concentrations in lake water. Significant positive correlation between ammonium fluxes and water temperature was observed and could probably be attributed to the intensified ammonification and nitrate reduction with increased temperature. Positive correlation between ammonium fluxes and algae biomass and Chl a concentrations may indicate that phytoplankton was an important factor driving ammonium fluxes in our study lake, and vice versa that higher fluxes of ammonium supported a higher biomass of the phytoplankton.

Biological mechanisms driving the seasonal changes in the internal loading of phosphorus in shallow lakes

Because of the obvious importance of P as a nutrient that often accelerates growth of phytoplankton (including toxic cyanobacteria) and therefore worsens water quality, much interest has been devoted to P exchange across the sediment-water interface. Generally, the release mode of P from the sediment differed greatly between shallow and deep lakes, and much of the effort has been focused on iron and oxygen, and also on the relevant environmental factors, for example, turbulence and decomposition, but a large part of the P variation in shallow lakes remains unexplained. This paper reviews experimental and field studies on the mechanisms of P release from the sediment in the shallow temperate (in Europe) and subtropical (in the middle and lower reaches of the Yangtze River in China) lakes, and it is suggested that pH rather than DO might be more important in driving the seasonal dynamics of internal P loading in these shallow lakes, i.e., intense photosynthesis of phytoplankton increases pH of the lake water and thus may increase pH of the surface sediment, leading to enhanced release of P (especially iron-bound P) from the sediment. Based on the selective pump of P (but not N) from the sediment by algal blooms, it is concluded that photosynthesis which is closely related to eutrophication level is the driving force for the seasonal variation of internal P loading in shallow lakes. This is a new finding. Additionally, the selective pump of P from the sediment by algal blooms not only explains satisfactorily why both TP and PO4-P in the hypereutrophic Lake Donghu declined significantly since the mid-1980s when heavy cyanobacterial blooms were eliminated by the nontraditional biomanipulation (massive stocking of the filter-feeding silver and bighead carps), but also explains why TP in European lakes decreased remarkably in the spring clear-water phase with less phytoplankton during the seasonal succession of aquatic communities or when phytoplankton biomass was decreased by traditional biomanipulation. Compared with deep lakes, wax and wane of phytoplankton due to alternations in the ecosystem structure is also able to exert significant influences on the P exchange at the sediment-water interface in shallow lakes. In other words, biological activities are also able to drive P release from sediments, and such a static P release process is especially more prominent in eutrophic shallow lakes with dense phytoplankton.

Facile fabrication of gold nanoparticle arrays for efficient surface-enhanced Raman scattering

An effective and facile method for the fabrication of a surface-enhanced Raman scattering (SERS)-active film with closely packed gold nanoparticle (AuNP) arrays is proposed by self-assembly of different sizes ( 16, 25, 40 and 70 nm) of AuNPs at a toluene/water interface with ethanol as the inducer. The as-prepared AuNP arrays exhibit efficient Raman scattering enhancement, and the enhancement factors estimated using p-aminothiophenol as a probe molecule range from 10(5) to 10(7).

Facile fabrication of large area of aggregated gold nanorods film for efficient surface-enhanced Raman scattering

An effective and facile method for fabrication of large area of aggregated gold nanorods (AuNRs) film was proposed by self-assembly of AuNRs at a toluene/water interface for the first time. It was found that large area of aggregated AuNRs film could be formed at the interface of toluene and water due to the interfacial tension between the two phases. The obtained large area of aggregated AuNRs film exhibits strong surface-enhanced Raman scattering (SERS) activity with 4-aminothiophenol (4-ATP) and 2-aminothiophenol (2-ATP) as the probe molecules based on the strong electromagnetic coupling effect between the very adjacent AuNRs.

Rapid fabrication of Au nanoparticle films with the aid of centrifugal force

In this work, rapid fabrication of Au nanoparticle (Au NP) films has been simply achieved by alternate adsorption of citrate-stabilized Au NPs and poly(diallyldimethylammonium chloride) with the aid of centrifugal force. In contrast to conventional electrostatic assembly, we carried out the assembly process in a centrifuge with a rotating speed of 4000 rpm, where centrifugal force can be imposed on Au NPs. Scanning electron microscopy and cyclic voltammetry were employed to characterize the assembly procedure and the thus-prepared thin solid films. Our results demonstrate that centrifugal force can promote the assembly of Au NPs and therefore enable the rapid fabrication of functional Au NP films.

Phase separation of PS/PVME blend films induced by capillary force

The phase behavior of a miscible PS/PVME (80/20, w/w) blend film in a confined geometry has been investigated at the annealing temperature much lower than the low critical solution temperature (LCST) of the blend. When the annealing temperature (52degreesC) is near the glass transition temperature of the blend (51.2degreesC), PVME-rich phase at the air-film surface under a microchannel forms smaller protrusion. When the annealing temperature is increased to 70degreesC, the protruding stripes, which are almost developed, are mainly composed of the mobile PVME-rich phase. These results reveal that the capillary force lead to the enrichment of PVME-rich phase at the air-polymer interface of a PDMS microchannel, that is, the capillary force lithography (CFL) can induce the phase separation of PS/PVME blend films.

In situ electrochemical scanning tunneling microscopy investigation of renewing graphite surface accompanied by electrochemical reaction

In situ electrochemical scanning tunneling microscopy (ECSTM) has been employed to follow the renewal process of a graphite electrode accompanied by flavin adenine dinucleotide (FAD) electrochemical reaction which involves adsorption of the reduced form (FADH(2)) and desorption of the oxidized form (FAD). The renewal process initiates from steps or kinks on the electrode surface, which provide high active sites for adsorption. This renewal depends on the working electrode potential, especially in the range near the FAD redox potential. Our experiment suggests that delamination of the graphite surface is caused by interaction between the substrate and adsorbed molecules. A simple model is proposed to explain this phenomenon.

Wave breaking on turbulent energy budget in the ocean surface mixed layer

As an important physical process at the air-sea interface, wave movement and breaking have a significant effect on the ocean surface mixed layer (OSML). When breaking waves occur at the ocean surface, turbulent kinetic energy (TKE) is input downwards, and a sublayer is formed near the surface and turbulence vertical mixing is intensively enhanced. A one-dimensional ocean model including the Mellor-Yamada level 2.5 turbulence closure equations was employed in our research on variations in turbulent energy budget within OSML. The influence of wave breaking could be introduced into the model by modifying an existing surface boundary condition of the TKE equation and specifying its input. The vertical diffusion and dissipation of TKE were effectively enhanced in the sublayer when wave breaking was considered. Turbulent energy dissipated in the sublayer was about 92.0% of the total depth-integrated dissipated TKE, which is twice higher than that of non-wave breaking. The shear production of TKE decreased by 3.5% because the mean flow fields tended to be uniform due to wave-enhanced turbulent mixing. As a result, a new local equilibrium between diffusion and dissipation of TKE was reached in the wave-enhanced layer. Below the sublayer, the local equilibrium between shear production and dissipation of TKE agreed with the conclusion drawn from the classical law-of-the-wall (Craig and Banner, 1994).

Characteristics of nitrogen forms in the surface sediments of southwestern Nansha Trough, South China Sea

The area of the southwestern Nansha Trough is one of the most productive areas of the southern South China Sea. It is a typical semi-deep sea area of transition from shoal to abyssal zone. To understand distributions and roles of nitrogen forms involved in biogeochemical cycling in this area, contents of nitrogen in four extractable forms: nitrogen in ion exchangeable form (IEF-N), nitrogen in weak acid extractable form (WAEF-N), nitrogen in strong alkali extractable form (SAEF-N) and nitrogen in strong oxidation extractable form (SOEF-N), as well as in total nitrogen content (TN) in surface sediments were determined from samples collected from the cruise in April-May 1999. The study area was divided into three regions (A, B and C) in terms of clay sediment (< 4 mu m) content at < 40%, 40%-60% and > 60%, respectively. Generally, region C was the richest in the nitrogen of all forms and region A the poorest, indicating that the finer the grain size is, the richer the contents of various nitrogen are. The burial efficiency of total nitrogen in surface sediments was 28.79%, indicating that more than 70% of nitrogen had been released and participated in biogeochemical recycling through sediment-water interface.

Assessment of metal contamination in surface sediments of Jiaozhou Bay, Qingdao, China

An assessment of metal contamination in surface sediments of the Jiaozhou Bay, Qingdao, one of the rapidly developing coastal economic zones in China, is provided. Sediments were collected from 10 stations and a total of 15 heavy metals were analyzed. Concentrations of metals show significant variability and range from 210 to 620 ppm for Ti, 2.7 to 23 ppm for Ni, 4.2 to 28 ppm for Cu, 5.2 to 18 ppm for Pb, 12 to 58 ppm for Zn, 0.03 to 0.11 ppm for Cd, 5 to 51 ppm for Cr, 1.5 to 9.9 ppm for Co, 5.3 to 19 ppm for As, 12 to 32 ppm for Se, and 19 to 97 ppm for Sr. Based on concentration relationships and enrichment factor (EF) analyses, the results indicate that sediment grain size and organic matter played important roles in controlling the distribution of the heavy metals in surface sediments of the Jiaozhou Bay. The study shows that the sediment of the Jiaozhou Bay has been contaminated by heavy metals to various degrees, with prominent arsenic contributing the most to the contamination. The analysis suggests that the major sources of metal contamination in the Jiaozhou Bay are land-based anthropogenic ones, such as discharge of industrial waste water and municipal sewage and run-off. Notably, the elevated heavy metal concentrations of the Jiaozhou Bay sediments could have a significant impact on the bay's ecosystem. With the rapid economic development and urbanization around the Jiaozhou Bay, coastal management and pollution control should focus on these contaminant sources, as well as provide ongoing monitoring studies of heavy metal contamination within the bay.

Biodeposition and Biogeochemical Processes in Shallow, Mesohaline Sediments of Chesapeake Bay

Stocks of the eastern oyster, Crassostrea virginica, have been declining in Chesapeake Bay since the late 19th century, and current strategies involve restoring culture of Crassostrea virginica on-bottom and in devices suspended within the water column. Sub-tidal suspension culture of Crassostrea virginica in Chesapeake Bay occurs mostly in sheltered inlets and tidal creeks and, thereby, has the potential to influence shallow water biogeochemical processes. To assess the influence of Crassostrea virginica biodeposits and benthic microalgae on sediment nitrogen and phosphorus exchange, field studies with Crassostrea virginica held in aquaculture floats and laboratory experiments were conducted. Enhanced organic nitrogen deposition from Crassostrea virginica biodeposits led to gradual increases in surface sediment nitrogen and pore water ammonium concentrations; however, modifications to pore water concentrations were not always expressed at the sediment-water interface. Benthic microalgae often modulated the influence of biodeposits on sediment nitrogen exchange but, as observed in laboratory experiments, the supply of nitrogen from Crassostrea virginica biodeposits may exceed their biological demand. Organic carbon from biodeposits had varying influences on aerobic respiration but consistently stimulated anaerobic metabolism. Shifts in net phosphorus exchange were driven by this anaerobic remineralization and concentrations of iron and manganese oxy(hydr)oxides, with transitions in fluxes coinciding with changes in benthic photosynthesis and oxidation of surface sediments. Manganese and iron oxy(hydr)oxides from biodeposits supported incorporation of added phosphorus and prevented exchange at the sediment-water interface in the absence of iron-sulfide mineral formation. Differences in the response of shallow water sediments to Crassostrea virginica biodeposits were due to the quality and quantity of biodeposits supplied, as well as the spatial and temporal variability within these sediments. Initial conditions and corresponding reference sediments illustrated the potential for sediment biogeochemistry and nutrient exchange from tidal creek sediments to vary spatially and temporally on relatively small scales. Factors influencing variability within tidal creek sediments were related to shifts in riverine freshwater inputs, macroalgal blooms, nutrient concentrations in overlying waters, and bioirrigation from the clam, Macoma balthica.