Reactive polymer coatings: a general route to thiol-ene and thiol-yne click reactions.

Reactive polymer coatings were synthesized via chemical vapor deposition (CVD) polymerization process. These coatings decouple surface design from bulk properties of underlying materials and provide a facile and general route to support thiol-ene and thiol-yne reactions on a variety of substrate materials. Through the reported technique, surface functions can be activated through a simple design of thiol-terminated molecules such as polyethylene glycols (PEGs) or peptides (GRGDYC), and the according biological functions were demonstrated in controlled and low-fouling protein adsorptions as well as accurately manipulated cell attachments.

Multifunctional and Continuous Gradients of Biointerfaces Based on Dual Reverse Click Reactions.

Chemical or biological gradients that are composed of multifunctional and/or multidirectional guidance cues are of fundamental importance for prospective biomaterials and biointerfaces. As a proof of concept, a general modification approach for generating multifunctional and continuous gradients was realized via two controlled and reversed click reactions, namely, thermo-activated thiol-yne and copper-free alkyne and azide click reactions. The cell adhesion property of fibroblasts was guided in a gradient with an enhancement, showing that the PEG molecule and RGD peptide were countercurrently immobilized to form such reversed gradients (with negating of the cell adhesion property). Using the gradient modification protocol to also create countercurrent distributions of FGF-2 and BMP-2 gradients, the demonstration of not only multifunctional but also gradient biointerfacial properties was resolved in time latencies on one surface by showing the manipulation in gradients toward proliferation and osteogenic differentiation for adipose-derived stem cells.

Multifaceted and route-controlled "click" reactions based on vapor-deposited coatings.

"Click" reactions provide precise and reliable chemical transformations for the preparation of functional architectures for biomaterials and biointerfaces. The emergence of a multiple-click reaction strategy has paved the way for a multifunctional microenvironment with orthogonality and precise multitasking that mimics nature. We demonstrate a multifaceted and route-controlled click interface using vapor-deposited functionalized poly-para-xylylenes. Distinctly clickable moieties of ethynyl and maleimide were introduced into poly-para-xylylenes in one step via a chemical vapor deposition (CVD) copolymerization process. The advanced interface coating allows for a double-click route with concurrent copper(i)-catalyzed Huisgen 1,3-dipolar cycloaddition (CuAAC) and the thiol-maleimide click reaction. Additionally, double-click reactions can also be performed in a cascade manner by controlling the initiation route to enable the CuAAC and/or thiol-yne reaction using a mono-functional alkyne-functionalized poly-para-xylylene. The use of multifaceted coatings to create straightforward and orthogonal interface properties with respect to protein adsorption and cell attachment is demonstrated and characterized.

Vapor-based coatings for antibacterial and osteogenic functionalization and the immunological compatibility.

The immobilization of biofunctional molecules to biomaterial surfaces has enabled and expanded the versatility of currently available biomaterials to a wider range of applications. In addition, immobilized biomolecules offer modified surfaces that allow the use of smaller amounts of potentially harmful substances or prevent overdose, while the exhibited biological functions remain persistently effective. Surface concentrations of chlorhexidine (CHX) (1.40±0.08×10(-9)mol·cm(-2)) and bone morphogenetic protein 2 (BMP-2) (1.51±0.08×10(-11)mol·cm(-2)) immobilized molecules were determined in this study, and their specific biological functions in terms of antibacterial activity and osteogenesis potency, respectively, were demonstrated to be unambiguously effective. Immobilization exploits the use of vapor-based poly-p-xylylenes, which exhibit excellent biocompatibility and wide applicability for various substrate materials. This technique represents a practical and economical approach for the manufacture of certain industrial products. Furthermore, a minimal degree of macrophage activation was indicated on the modified surfaces via insignificant morphological changes and low levels of adverse inflammatory signals, including suppressed production of the pro-inflammatory cytokines IL-1ß and TNF-α as well as nitric oxide (NO). The results and the modification strategy illustrate a concept for designing prospective biomaterial surfaces such that the manipulation employed to elicit targeted biological responses does not compromise immunological compatibility.

Tunable coverage of immobilized biomolecules for biofunctional interface design.

The controlled coverage of immobilized biomolecules is introduced, illustrating a concept for designing biomaterial surfaces such that the extent of manipulation employed to elicit biological responses is controlled according to density changes in the underlying chemical motifs and the density of immobilized biomolecules.

Sustained immobilization of growth factor proteins based on functionalized parylenes.

Protein molecules immobilized on biomaterial surfaces are performed based on oriented conjugation or replaced mimicking peptides. The sustainable immobilization of growth factor proteins using functionalized parylene coatings is demonstrated in this study. Site-specific and nonspecific immobilization approaches are realized to conjugate bone morphogenetic protein (BMP-2). The binding affinities and conformational changes of BMP-2 are confirmed by QCM and SPR characterizations. Osteoinduction of stem cells is examined by ALP activity on the BMP-2 modified surfaces. Finally, immobilizations and equally sustained biological functions of vascular endothelial growth factor (VEGF) and a mimicking peptide of KLTWQELYQLKYKG (QK) are also examined and confirmed.