Biomimetic layers

Supported bilayers represent biomimetic layers which can be supported on a range of materials and adapted for the study of biointeractions (protein-protein, lipid-lipid) including molecular recognition, ion-channel transport and intramembrane interactions. This interface type can be separated into the so-called SLBs (supported lipid bilayers), HBMs (hybrid bilayer membranes) and t-BLMs (tethered bilayer membranes). 

As far as enzyme immobilization is concerned, the biocompatibility of support is another important requirement [120-123], as the biocompatible surface can reduce some non-biospecific enzyme-support interactions, create a specific microenvironment for the enzymes and thus provide substantial benefits to the enzyme activity [124], To increase the biocompatibility of the support, various surface modification protocols have often been used to introduce a biofriendly interface on the support surface, such as coating, adsorption, self-assembly and graft polymerization. Among these methods, it is relatively easy and effective to directly tether natural macromolecules on the support surface to form a biomimetic layer for enzyme immobilization. In fact, this protocol has been used in tissue engineering recently [125-127]. 

In this chapter we describe the basic principles involved in the controlled production and modification of two-dimensional protein crystals. These are synthesized in nature as the outermost cell surface layer (S-layer) of prokaryotic organisms and have been successfully applied as basic building blocks in a biomolecular construction kit. Most importantly, the constituent subunits of the S-layer lattices have the capability to recrystallize into iso-porous closed monolayers in suspension, at liquid-surface interfaces, on lipid films, on liposomes, and on solid supports (e.g., silicon wafers, metals, and polymers). The self-assembled monomolecular lattices have been utilized for the immobilization of functional biomolecules in an ordered fashion and for their controlled confinement in defined areas of nanometer dimension. Thus, S-layers fulfill key requirements for the development of new supramolecular materials and enable the design of a broad spectrum of nanoscale devices, as required in molecular nanotechnology, nanobiotechnology, and biomimetics [1-3]. 

Most important for many applications of S-layer lattices in molecular nanotechnology, biotechnology, and biomimetics was the observation that S-layer proteins are capable of reassembling into large coherent monolayers on solid supports (e.g., silicon wafers, polymers, metals) at the air/water interface and on Langmuir lipid films (Fig. 6) (see Sections V and VIII). 

In this context it is interesting to note that archaea, which possess S-layers as exclusive cell wall components outside the cytoplasmic membrane (Fig. 14), exist under extreme environmental conditions (e.g., high temperatures, hydrostatic pressure, and salt concentrations, low pH values). Thus, it is obvious one should study the effect of proteinaceous S-layer lattices on the fluidity, integrity, structure, and stability of lipid membranes. This section focuses on the generation and characterization of composite structures that mimic the supramolecular assembly of archaeal cell envelope structures composed of a cytoplasmic membrane and a closely associated S-layer. In this biomimetic structure, either a tetraether... 

FIG. 14 Schematic illustration of an archaeal cell envelope structure (a) composed of the cytoplasmic membrane with associated and integral membrane proteins and an S-layer lattice, integrated into the cytoplasmic membrane, (b) Using this supramolecular construction principle, biomimetic membranes can be generated. The cytoplasmic membrane is replaced by a phospholipid or tetraether hpid monolayer, and bacterial S-layer proteins are crystallized to form a coherent lattice on the lipid film. Subsequently, integral model membrane proteins can be reconstituted in the composite S-layer-supported lipid membrane. (Modified from Ref. 124.)... 

In order to enhance the stability of hposomes and to provide a biocompatible outermost surface shucture for controlled immobihzation (see Section IV), isolated monomeric and oligomeric S-layer protein from B. coagulans E38/vl [118,123,143], B. sphaericus CCM 2177, and the SbsB from B. stearothermophilus PV72/p2 [119] have been crystallized into the respective lattice type on positively charged liposomes composed of DPPC, HD A, and cholesterol. Such S-layer-coated hposomes are spherical biomimetic structures (Fig. 18) that resemble archaeal ceUs (Fig. 14) or virus envelopes. The crystallization of S-... 

Another important area of future development concerns copying the supramolecular principle of cell envelopes of archaea, which have evolved in the most extreme and hostile ecosystems. This biomimetic approach is expected to lead to new technologies for stabilizing fnnctional lipid membranes and their nse at the mesoscopic and macroscopic scales [200]. Along the same line, liposomes coated with S-layer lattices resemble archaeal cell envelopes or virns envelopes. Since liposomes have a broad application potential, particu-... 

A biomolecular system of glycoproteins derived from bacterial cell envelopes that spontaneously aggregates to form crystalline arrays in the mesoscopic range is reviewed in Chapter 9. The structure and features of these S-layers that can be applied in biotechnology, membrane biomimetics, sensors, and vaccine development are discussed. 

Bakke et al. (1982) have shown how montmorillonite catalyses chlorination and nitration of toluene nitration leads to 56 % para and 41 % ortho derivative compared to approximately 40 % para and 60 % ortho derivatives in the absence of the catalyst. Montmorillonite clays have an acidity comparable to nitric acid / sulphuric acid mixtures and the use of iron-exchanged material (Clayfen) gives a remarkable improvement in the para, ortho ratio in the nitration of phenols. The nitration of estrones, which is relevant in making various estrogenic drugs, can be improved in a remarkable way by using molecular engineered layer structures (MELS), while a reduction in the cost by a factor of six has been indicated. With a Clayfen type catalyst, it seems possible to manipulate the para, ortho ratio drastically for a variety of substrates and this should be useful in the manufacture of fine chemicals. In principle, such catalysts may approach biomimetic chemistry our ability to predict selectivity is very limited. 

M., Miyazaki, T., Tanihara, M., Sakaguchi, Y. and Konagaya, S. (2004) Coating of an apatite layer on polyamide films containing sulfonic groups by a biomimetic process. Biomaterials, 25, 4529 f534. 

Poly(oxyethylene)-Si02 ormosils have been prepared as an approach to the preparation of biologically active polymer-apatite composites. For this purpose, Yamamoto et al. [72] obtained these Class II hybrids from triethoxysilyl-terminated poly(oxyethylene) (PEG) and TEOS by using the in situ sol-gel process. After being subjected to the biomimetic process to form the bone-like apatite layer, it was found that a dense apatite layer could be prepared on the hybrid materials, indicating that the silanol groups provide effective sites for CHA nucleation and growth. 

A definite quantity of oxygen molecules accumulated on the surface of the biomimetic electrode (catalase reaction) must diffuse to the volume of the adhesive layer, toward the electrode surface. Hence, the specific requirements to the adhesive follow on the one hand, it must provide strong enough adhesion of a mimic to electrode on the other hand, it must possess low oxygen adsorption ability. 

Tan, W., Desai, T.A., Layer-by-layer microfluidics for biomimetic three-dimensional structures. Biomaterials 2004, 25, 1355-1364. 

Tang Z, Wang Y, Podsiadlo P et al (2006) Biomedical applications of layer-by-layer assembly from biomimetics to tissue engineering. Adv Mater 18 3203-3224... 

---