抗原变异可使得多种致病微生物易于逃避宿主免疫应答。表达在感染红细胞表面的恶性疟原虫红细胞表面蛋白1（PfPMP1）与感染红细胞、内皮细胞、树突状细胞以及胎盘的单个或多个受体作用，在黏附及免疫逃避中起关键的作用。每个单倍体基因组var基因家族编码约60种成员，通过启动转录不同的var基因变异体为抗原变异提供了分子基础。

疟原虫var基因转换速率变化导致抗原变异[英]／Paul H, Robert P, Christodoulou Z, et al//Proc Natl Acad Sci U S A

We report a method to form multifunctional polymer coatings through simple dip-coating of objects in an aqueous solution of dopamine. Inspired by the composition of adhesive proteins in mussels, we used dopamine self-polymerization to form thin, surface-adherent polydopamine films onto a wide range of inorganic and organic materials, including noble metals, oxides, polymers, semiconductors, and ceramics. Secondary reactions can be used to create a variety of ad-layers, including self-assembled monolayers through deposition of long-chain molecular building blocks, metal films by electroless metallization, and bioinert and bioactive surfaces via grafting of macromolecules.

/pdf/mussel-inspired-surface-chemistry-for-multifunctional-1noq7vcby7.pdf

Mussel-Inspired Surface Chemistry for Multifunctional Coatings

Polymer/layered silicate nanocomposites: a review from preparation to processing

Synthesis and surface engineering of iron oxide nanoparticles for biomedical applications

This review aims at reporting on very recent developments in syntheses, properties and (future) applications of polymer-layered silicate nanocomposites. This new type of materials, based on smectite clays usually rendered hydrophobic through ionic exchange of the sodium interlayer cation with an onium cation, may be prepared via various synthetic routes comprising exfoliation adsorption, in situ intercalative polymerization and melt intercalation. The whole range of polymer matrices is covered, i.e. thermoplastics, thermosets and elastomers. Two types of structure may be obtained, namely intercalated nanocomposites where the polymer chains are sandwiched in between silicate layers and exfoliated nanocomposites where the separated, individual silicate layers are more or less uniformly dispersed in the polymer matrix. This new family of materials exhibits enhanced properties at very low filler level, usually inferior to 5 wt.%, such as increased Young’s modulus and storage modulus, increase in thermal stability and gas barrier properties and good flame retardancy.

Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials

The glue proteins secreted by marine mussels bind strongly to virtually all inorganic and organic surfaces in aqueous environments in which most adhesives function poorly. Studies of these functionally unique proteins have revealed the presence of the unusual amino acid 3,4-dihydroxy-L-phenylalanine (dopa), which is formed by posttranslational modification of tyrosine. However, the detailed binding mechanisms of dopa remain unknown, and the chemical basis for mussels' ability to adhere to both inorganic and organic surfaces has never been fully explained. Herein, we report a single-molecule study of the substrate and oxidation-dependent adhesive properties of dopa. Atomic force microscopy (AFM) measurements of a single dopa residue contacting a wet metal oxide surface reveal a surprisingly high strength yet fully reversible, noncovalent interaction. The magnitude of the bond dissociation energy as well as the inability to observe this interaction with tyrosine suggests that dopa is critical to adhesion and that the binding mechanism is not hydrogen bond formation. Oxidation of dopa, as occurs during curing of the secreted mussel glue, dramatically reduces the strength of the interaction to metal oxide but results in high strength irreversible covalent bond formation to an organic surface. A new picture of the interfacial adhesive role of dopa emerges from these studies, in which dopa exploits a remarkable combination of high strength and chemical multifunctionality to accomplish adhesion to substrates of widely varying composition from organic to metallic.

https://www.pnas.org/content/pnas/103/35/12999.full.pdf

Single-molecule mechanics of mussel adhesion

The adhesive strategy of the gecko relies on foot pads composed of specialized keratinous foot-hairs called setae, which are subdivided into terminal spatulae of approximately 200 nm (ref. 1). Contact between the gecko foot and an opposing surface generates adhesive forces that are sufficient to allow the gecko to cling onto vertical and even inverted surfaces. Although strong, the adhesion is temporary, permitting rapid detachment and reattachment of the gecko foot during locomotion. Researchers have attempted to capture these properties of gecko adhesive in synthetic mimics with nanoscale surface features reminiscent of setae; however, maintenance of adhesive performance over many cycles has been elusive, and gecko adhesion is greatly diminished upon full immersion in water. Here we report a hybrid biologically inspired adhesive consisting of an array of nanofabricated polymer pillars coated with a thin layer of a synthetic polymer that mimics the wet adhesive proteins found in mussel holdfasts. Wet adhesion of the nanostructured polymer pillar arrays increased nearly 15-fold when coated with mussel-mimetic polymer. The system maintains its adhesive performance for over a thousand contact cycles in both dry and wet environments. This hybrid adhesive, which combines the salient design elements of both gecko and mussel adhesives, should be useful for reversible attachment to a variety of surfaces in any environment.

A reversible wet/dry adhesive inspired by mussels and geckos

Mussels attach to solid surfaces in the sea. Their adhesion must be rapid, strong, and tough, or else they will be dislodged and dashed to pieces by the next incoming wave. Given the dearth of synthetic adhesives for wet polar surfaces, much effort has been directed to characterizing and mimicking essential features of the adhesive chemistry practiced by mussels. Studies of these organisms have uncovered important adaptive strategies that help to circumvent the high dielectric and solvation properties of water that typically frustrate adhesion. In a chemical vein, the adhesive proteins of mussels are heavily decorated with Dopa, a catecholic functionality. Various synthetic polymers have been functionalized with catechols to provide diverse adhesive, sealant, coating, and anchoring properties, particularly for critical biomedical applications.

Mussel-Inspired Adhesives and Coatings

Immobilization of biomolecules onto surfaces is important in many of the biological and physical sciences, including cell and molecular biology, analytical chemistry, and in applied and interdisciplinary fields such as medical diagnostics, tissue engineering, and bioprocess engineering.[1-4] Strategies for biomolecule immobilization onto surfaces generally exploit either noncovalent or covalent reactions. Noncovalent methods allow reversible immobilization of biomolecules under specific conditions, and include physical adsorption and affinity immobilization. Some widely adapted examples are (strep)avidin-biotin, nitriloacetic acid (NTA)-histidine, and DNA-DNA interactions.[5-8] In contrast, covalent immobilization of molecules onto surfaces typically relies on conjugation reactions between ‘active’ functional groups, such as N-hydroxysuccinimide (NHS)[9] or maleimide,[10] and companion target moieties, such as amines and sulfhydryls. For reactions involving biomolecules performed in aqueous solvents, susceptibility of NHS, maleimide, and other activating groups to hydrolysis during storage and reaction can lead to low efficiency of surface bioconjugation.[11,12] In this study, we report a facile two-step aqueous approach to immobilization of biomolecules onto surfaces. The approach involves simple dip-coating of a biomimetic polymer thin film onto a substrate, followed by conjugation of biomolecules to the biomimetic polymer film. The method exploits the latent reactivity of the biomimetic polymer thin film towards nucleophiles, is unaffected by water, and allows for discrimination between nucleophiles on the basis of pKa.

Phillip B. Messersmith

Papers

Mussel-Inspired Surface Chemistry for Multifunctional Coatings

Single-molecule mechanics of mussel adhesion

A reversible wet/dry adhesive inspired by mussels and geckos

Mussel-Inspired Adhesives and Coatings

Facile Conjugation of Biomolecules onto Surfaces via Mussel Adhesive Protein Inspired Coatings