Super-hydrophobicity fundamentals: implications to biofouling prevention

Abstract

The theory of wetting on super-hydrophobic surfaces is presented and discussed, within the general framework of equilibrium wetting and contact angles. Emphasis is put on the implications of super-hydrophobicity to the prevention of biofouling. Two main lines of thought are discussed, viz. i) “mirror imaging” of the Lotus effect, namely designing a surface that repels biological entities by being super-hydrophilic, and ii) designing a surface that minimises the water-wetted area when submerged in water (by keeping an air film between the water and the surface), so that the suspended biological entities have a low probability of encountering the solid surface.     

Wetting control through topography and surface hydrophilic/hydrophobic property changes by coarse grained simulation

Abstract

The changes of wetting state of water droplet on the solid surface featuring pillared structures are quantitatively studied by Coarse Grained simulation. Our results demonstrate that wetting state changes with the different topography (surface roughness), and it depends on the intrinsic hydrophilic/hydrophobic property of surface as well. Only if the contact angle of water droplet on the smooth surface is larger than 93.13°, the wetting state translates from the Wenzel state to the Cassie state on the rough surface with certain pillar height and width, and the contact angle climb up to the highest point and then remain almost unchanged with the increasing of pillar height and the same pillar distance. However, the wetting state does not change if the contact angle on the smooth surface is 85.1° or less, no matter what pillar structure the surface has. Additionally, the contact angles will remain almost unchanged if the pillar height is higher than a certain value. Our simulation results provide a quantitative understanding about the wetting state of water droplet on solid rough surfaces, and the results show the wetting state can be controlled by combining rough structure design and hydrophilic/hydrophobic property change of surfaces.     

Modeling Superhydrophobic Contact Angles and Wetting Transition

It is well known that surface roughness has a very important effect on superhydrophobicity.The Wenzel and Cassie-Baxtermodels,which correspond to the homogeneous and heterogeneous wetting respectively,are currently primary instructions fordesigning superhydrophobic surfaces.However,the particular drop shape that a drop exhibits might depend on how it is formed.A water drop can occupy multiple equilibrium states,which relate to different local minimal energy.In some cases,both equilibriumstates can even co-exist on a same substrate.Thus the apparent contact angles may vary and have different values.Wediscuss how the Wenzel and Cassie-Baxter equations determine the homogeneous and heterogeneous wetting theoretically.Contact angle analysis on hierarchical surface structure and contact angle hysteresis has been put specific attention.In particular,we study the energy barrier of transition from Cassie-Baxter state to Wenzel state,based on existing achievement by previousresearchers,to determine the possibility of the transition and how it can be interpreted.It has been demonstrated that surfaceroughness and geometry will influence the energy required for a drop to get into equilibrium,no matter it is homogeneous orheterogeneous wetting.     

Wetting characterisation of silicon (1,0,0) surface

Water droplets on bare silicon surfaces are studied to examine the wetting behaviour as a function of the surface energy and to parameterise water–silicon interactions in order to recover the hydrophobic behaviour measured by experiments. Two different wetting regimes characterised by a critical interaction strength value are observed. At a threshold value of the water–silicon interaction parameter, water molecules start penetrating into the first layer of silicon surface under thermally vibrating walls, resulting in two distinct wetting behaviours. Fixed (cold) silicon walls do not exhibit the two different wetting characteristics. Size effects are studied for nano-scale droplets, and line tension influence is observed depending on the surface wettability. Decrease in the droplet size increases the contact angle values for the low wetting cases, while contact angles decrease for smaller droplets on the high wetting surfaces. Considering the line tension effects and droplet size, ?_Si–O for water–silicon interactions to recover the hydrophobic behaviour of silicon surfaces is estimated to be 12.5% of the value predicted using the Lorentz–Berthelot mixing rule.     

不同类型生物土壤结皮覆盖下风沙土的入渗特征及模拟

干旱荒漠区广泛分布的生物土壤结皮(BSCs)对土壤水分入渗过程有重要影响。以古尔班通古特沙漠南缘的BSCs为研究对象,基于野外采样与室内模拟实验等方法,探究藓类、地衣和藻等3种类型BSCs覆盖下沙土的入渗特征。结果表明:与无结皮覆盖的风沙土对照,3种类型BSCs均显著降低了沙土初渗速率,藓类结皮、地衣结皮、藻结皮覆盖下初渗速率降低幅度依次为36.10%、46.42%、50.39%;藓类结皮、地衣结皮(P0.05)和藻结皮(P0.05)均明显降低了沙土稳渗速率,降低幅度依次为16.50%、33.98%和35.92%;3种类型BSCs均限制了湿润锋在沙土的推进过程,表现为:藓类结皮、地衣结皮、藻结皮的渗漏时间分别为裸沙对照的2.13、3.04和2.98倍;各类型BSCs均减小了沙土累积入渗量,阻碍了沙土水分入渗,与裸沙对照相比,藓类结皮、地衣结皮、藻结皮的1 h累积入渗量分别降低16.10%、28.56%和26.56%。在实验条件下,Kostiakov模型最适用于模拟不同类型BSCs覆盖下土壤水分入渗过程,Horton模型模拟效果次之。     

Effects of Methanol on Wettability of the Non-Smooth Surface on Butterfly Wing

The contact angles of distilled water and methanol solution on the wings of butterflies were determined by a visual contact angle measuring system. The scale structures of the wings were observed using scanning electron microscopy, The influence of the scale micro- and ultra-structure on the wettability was investigated. Results show that the contact angle of distilled water on the wing surfaces varies from 134.0° to 159.2°. High hydrophobicity is found in six species with contact angles greater than 150°. The wing surfaces of some species are not only hydrophobic but also resist the wetting by methanol solution with 55% concentration. Only two species in Parnassius can not resist the wetting because the micro-structure （spindle-like shape） and ultra-structure （pinnule-like shape） of the wing scales are remarkably different from that of other species. The concentration of methanol solution for the occurrence of spreading/wetting on the wing surfaces of different species varies from 70% to 95%. After wetting by methanol solution for 10 min, the distilled water contact angle on the wing surface increases by 0.8°-2.1°, showing the promotion of capacity against wetting by distilled water.     

Partial Sequence Analysis of the 5S to 18S rRNA Gene Region of the Maize Mitochondrial Genome

Measurements of the rate of imbibition by isolated cotyledons of soybean (Glycine max (L.) Merr cv Wayne) indicated that water uptake rates were slowed by low temperatures and by low initial moisture contents of the tissue. The role of water viscosity in the temperature effects on imbibition was examined, and a linear relation between imbibition rate and the reciprocal of viscosity was found only for seeds of very high initial moisture content. Adding solutes which lowered the surface tension, or increased the wetting ability of the water, yielded markedly increased rates of imbibition, especially for tissue of low initial moisture content. The data are interpreted as indicating a first component of water entry which is a wetting reaction influenced by the surface tension of the water, and a second component which resembles water flow through a porous matrix and is influenced by the water viscosity. We speculate that damage to soybeans during imbibition, such as in the case of chilling injury, may be particularly related to the initial wetting reaction rather than to the longer-term imbibitional rate.     

Surface Wettability and Chemistry of Ozone Perfusion Processed Porous Collagen Scaffold

Crosslinking treatment of collagen has often been used to improve the biological stability and mechanical properties of 3D porous collagen scaffolds. However, accompanying these improvements, the collagen fibril surface becomes hydrophobic nature resulting in a reduced surface wettability. The wetting of the collagen fibril by culture medium is reduced and it is difficult for the medium to diffuse into the 3D structure of a porous collagen scaffold. This paper reports a “perfusion processing” strategy using ozone to improve the surface wettability of chemical crosslinked collagen scaffolds. Surface wettability, surface composition and biological stability were analyzed to evaluate the effectiveness of this surface processing strategy. It was observed that ozone perfusion processing improved surface wettability for both exterior and interior surfaces of the porous 3D collagen scaffold. The improvement in wettability is attributed to the incorporation of oxygen-containing functional groups onto the surface of the collagen fibrils, as confirmed by X-ray Photoelectron Spectroscopy (XPS) analysis. This leads to a significant improvement in water taking capability without compromising the bulk biological stability and mechanical properties, and confirms that ozone perfusion processing is an effective tool to modify the wettability both for interior and exterior surfaces throughout the scaffold.     

The synthesis of primitive ‘living’ forms: Definitions,goals, strategies and evolution synthesizers

The arbitrariness of the definition of life is discussed in relation to both the archaic biological entities that preceded cells during the Molecular Evolution era, and the hypothetical, primitive, living entities that presumably can be synthesized in the laboratory. Several experimental approaches to the synthesis, detection, and characterization of living entities are discussed. The experimental approaches considered for the synthesis are the constructionist strategy, the whole-environment strategy, and the modular strategy, which is a combination of the first two. The whole-environment strategy is discussed in more detail and the establishment of an Evolution Synthesizer, based on this strategy, is proposed and rationalized. The guidelines for the detection and characterization of populations and processes of living entities include chemical and physical analyses, but are based mainly on the reproductive characterization of these entities. It is expected that the higher the evolutionary level of the living entities, the longer and more difficult it will be to synthesize them, but the easier it will be to detect them.     

Causal Regularities in the Biological World of Contingent Distributions

Former discussions of biological generalizations have focused on the question of whether there are universal laws of biology. These discussions typically analyzed generalizations out of their investigative and explanatory contexts and concluded that whatever biological generalizations are, they are not universal laws. The aim of this paper is to explain what biological generalizations are by shifting attention towards the contexts in which they are drawn. I argue that within the context of any particular biological explanation or investigation, biologists employ two types of generations. One type identifies causal regularities exhibited by particular kinds of biological entities. The other type identifies how these entities are distributed in the biological world.     

Microcalorimetric studies on the lyophilic properties of pectic substances

The exothermic effects observed on wetting pectins with water and aliphatic alcohols were studied using a microcalorimeter.The heat released on wetting 1 g pectin with water was found to be 171 ± 7·5 J g^?1. It was experimentally established that 1 g of dry pectin exothermically bonded up to 0·57 g of water.By using the Gibbs-Helmholtz-Young equation which relates the heat released by wetting to the area of the wetted surface, it was estimated that the surface accessible to water in 1 g of pectin was 1·46 × 10³ m² g^?1. The heat of hydration was independent of the degree of esterification of the pectin. The experimental results revealed that there were about six molecules of energetically bonded water per monomer unit of pectin.A specific interaction between methanol and the methoxyl groups of pectin was observed on wetting pectins with methanol and dependence was established between the released heat and the degree of esterification. No similar dependence was reported for the remaining aliphatic alcohols.     

Measurements of conformational changes during adhesion of lipid and protein (polylysine and S-layer) surfaces

The adhesion forces between various surfaces were measured using the "surface forces apparatus" technique. This technique allows for the thickness of surface layers and the adhesion force between them to be directly measured in controlled vapor or liquid environments. Three types of biological surfaces were prepared by depositing various lipid-protein monolayers (with thicknesses ranging from 1 to 4 nm) on the inert, molecularly smooth mica surface: (i) hydrophobic lipid monolayers; (ii) amphiphilic polyelectrolyte surfaces of adsorbed polylysine; and (iii) deposited bacterial S-layer proteins. The adhesion, swelling, and wetting properties of these surfaces was measured as a function of relative humidity and time. Initial adhesion is due mainly to the van der Waals forces arising from nonpolar (hydrophobic) contacts. Following adhesive contact, significant molecular rearrangements can occur which alter their hydrophobic-hydrophilic balance and increase their adhesion with time. Increased adhesion is generally enhanced by (i) increased relative humidity (or degree of hydration); (ii) increased contact time; and (iii) increased rates of separation. The results are likely to be applicable to the adhesion of many other biosurfaces, and show that the hydrophobicity of a lipid or protein surface is not an intrinsic property of that surface but depends on its environment (e.g., on whether it is in aqueous solution or exposed to the atmosphere), and on the relative humidity of the atmosphere. It also depends on whether the surface is in adhesive contact with another surface and-when considering dynamic (nonequilibrium) conditions-on the time and previous history of its interaction with that surface. (c) 1993 John Wiley & Sons, Inc.     

Domain formation by a Rhodococcus sp. biosurfactant trehalose lipid incorporated into phosphatidylcholine membranes

The study of the interaction of biosurfactants with biological membranes is of great interest in order to gain insight into the molecular mechanisms of their biological actions. In this work we report on the interaction of a bacterial trehalose lipid produced by Rhodococcus sp. with phosphatidylcholine membranes. Differential scanning calorimetry measurements show a good miscibility of the glycolipid in the gel state and immiscibility in the fluid state, suggesting domain formation. These domains have been visualized and characterized, for the first time, by scanning force microscopy. Incorporation of trehalose lipid into phosphatidylcholine membranes produces a small shift of the antisymmetric stretching band toward higher wavenumbers, as shown by FTIR, which indicates a weak increase in fluidity. The CO stretching band shows that incorporation of trehalose lipid increases the proportion of the dehydrated component in mixtures with the three phospholipids at temperatures below and above the gel to liquid-crystalline phase transition. This dehydration effect is also supported by data on the phospholipid PO stretching bands. Small-angle X-ray diffraction measurements show that in the samples containing trehalose lipid the interlamellar repeat distance is larger than in those of pure phospholipids. These results are discussed within the frame of trehalose lipid domain formation, trehalose lipid/phospholipid interactions and its relevance to membrane-related biological actions.     

Influence of epiphytic micro-organisms on leaf wettability: wetting of the upper leaf surface of Juglans regia and of model surfaces in relation to colonization by micro-organisms

Wetting of the upper leaf surface of Juglans regia L. and of model surfaces colonized by epiphytic micro-organisms was investigated by measuring contact angles of aqueous solutions buffered at different pH values. During June to October 1995, contact angles of aqueous solutions on the leaf surface of J. regia decreased by angles ranging from 12° (low pH values) to 25° at high pH values. At the end of this vegetation period, wetting was strongly dependent on pH showing significantly lower contact angles with alkaline solutions (pH 9·0) than with acidic solutions (pH 3·0). Contact angle titration measured angles on the leaf surface as a function of the pH of buffered aqueous solutions, covering a pH range from 3·0 to 11·0. Titration curves revealed inflection points around 7·5, indicating the existence of ionizable carboxylic groups at the interface of the phylloplane. Altered leaf-surface wetting properties observed on the intact leaf surface could be simulated in model experiments by measuring contact angles on artificial surfaces colonized by Pseudomonas fluorescens and by epiphytic micro-organisms isolated from the phylloplane of J. regia . Strong evidence is provided that interfacial carboxylic groups derive from epiphytic micro-organisms present on the phylloplane. Results suggest that the age-dependent increase in, and pH dependence of, wetting as leaves mature are related to the presence of epiphytic micro-organisms on the phylloplane. Ecological consequences of increased leaf-surface wetting, concerning the structure of the leaf surface as a microhabitat for epiphytic micro-organisms, are discussed.     

Querying quantitative logic models (Q2LM) to study intracellular signaling networks and cell-cytokine interactions

Mathematical models have substantially improved our ability to predict the response of a complex biological system to perturbation, but their use is typically limited by difficulties in specifying model topology and parameter values. Additionally, incorporating entities across different biological scales ranging from molecular to organismal in the same model is not trivial. Here, we present a framework called "querying quantitative logic models" (Q2LM) for building and asking questions of constrained fuzzy logic (cFL) models. cFL is a recently developed modeling formalism that uses logic gates to describe influences among entities, with transfer functions to describe quantitative dependencies. Q2LM does not rely on dedicated data to train the parameters of the transfer functions, and it permits straight-forward incorporation of entities at multiple biological scales. The Q2LM framework can be employed to ask questions such as: Which therapeutic perturbations accomplish a designated goal, and under what environmental conditions will these perturbations be effective? We demonstrate the utility of this framework for generating testable hypotheses in two examples: (i) a intracellular signaling network model; and (ii) a model for pharmacokinetics and pharmacodynamics of cell-cytokine interactions; in the latter, we validate hypotheses concerning molecular design of granulocyte colony stimulating factor.     

Synthetic approaches to the 2010 new drugs

New drugs are introduced to the market every year and each represents a privileged structure for its biological target. These new chemical entities (NCEs) provide insights into molecular recognition and also serve as leads for designing future new drugs. This review covers the synthesis of 15 NCEs that were launched anywhere in the world in 2010.     

Synthetic approaches to the 2011 new drugs

New drugs are introduced to the market every year and each represents a privileged structure for its biological target. These new chemical entities (NCEs) provide insights into molecular recognition and also serve as leads for designing future new drugs. This review covers the synthesis of 26 NCEs that were launched in the world in 2011.     

Simplicity and complexity in MIRROR universes

The scientific simplicity principle (OCCAM's razor) has always been strongly enforced by the available modelling tools. Moreover, the concept of simplicity itself is shaped by these (classical) tools. Computer models are less subject to simplicity constraints than other models are. It may be argued that complexity is the preeminent property for biological systems to study. In this paper we discuss our MIRROR modelling methodology in which (a concept of) simplicity is reconciled with biological complexity. Simplicity resides in the simple "TODO" ("do what there is to do") of the "individuals" (molecules, cells, organisms) which inhabit the model universe. The complexity appears in the multiple (levels of) individuals and the multiple levels of observable behavior of the universe. Examples are given of the development of complex, self-regulating social structures by simple interactions of individuals, and the adaptability of TODO based entities is compared to that of evolving entities. On the basis of these examples we sketch a slightly unconventional image of the evolution of complexity in biotic systems and discuss observations on the molecular record of biotic evolution which seem to fit this image.     

A critical approach to the definition of Darwinian units of selection

What are the biological units of selection? In fact, the notion of "unit of selection" (UOS) is blurred by ambiguity and controversy. To further evaluate the biological entities that are the objects of natural selection, three novel conceptual criteria (holism, minimalism, functionalism) are critically applied; they reveal, in addition to the self-evident case of the "individual," at least six distinct types of UOSs. These UOSs do not always have a defined structural organization; they can be parts of a living organism, a cohesive group of conspecifics, a multiunit entity, a totipotent cell, a DNA fragment, or a whole organism. UOS types diversify by amalgamation or parcelation processes of apparent entities. Therefore, previous attempts to characterize the UOSs solely on some morphological levels (gene, individual, group) without applying stringent criteria have failed to cope with the structural variations of natural phenomena and have led to the ambiguity of terms used.