A stable gelatin gradient providing continuous increment of signaling for cell adhesion and proliferation was fabricated within 3D poly(L-lactic acid) (PLLA) scaffolds. The porous PLLA scaffold fabricated by NaCl particle leaching was vertically fixed on a glass vial. 1,6-Hexanediamine/propanol solution was continuously injected into the vial by a micropump to aminolyze the PLLA scaffold. As a result of reaction time difference, the introduced -NH2 groups increased continuously along with the longitude of the PLLA scaffold in the z-direction. After covalent immobilization of gelatin by glutaraldehyde coupling, the gelatin gradient scaffold was thus obtained. In vitro chondrocyte culture showed that the cells had higher viability and more extending morphology in the gelatin gradient scaffold than that in the uniform gelatin control.
Microarrays of spherical vessel-like colloids such as liposomes, polymerized vesicles and polyelec-trolyte capsules may find diverse applications in bioanalysis, biosensing, and combinatorial chemistry, for their capabilities in encapsulating chemical species such as drugs, biomolecules, probes, polymers and nanoparticles. This review reports the advances on methods for fabricating microarrays of the various hollow colloids. Related strategies are described in detail, including patterning techniques, surface modification methods, and tethering approaches such as oligonucleotide hybridization, receptor-ligand binding, covalent coupling and electrostatic interaction. The preliminary developments of functionalities of these arrays serving as sensor chips, microcarriers and microreactors are summarized as well.
A method for fabricating arrays of microcapsules covalently immobilized onto chemically patterned substrates was developed.The core-shell microparticles with poly(allylamine hydrochloride)(PAH) as the outermost layer were obtained by layer-by-layer (LbL) assembly,which were further treated with glutaraldehyde to endow the particles with abundant aldehyde groups on their surfaces.The particles were then covalently coupled to the chemically patterned regions with amino groups created by microcontact printing (μCP).After dissolution of the core particles,arrays of the hollow microcapsules with unchanged structures were obtained.These arrays could stand rigorous environmental conditions of higher ionic strength,and lower and higher pH values.Thus,the technique could be possibly applied to exploiting chips of microcontainers or microreactors in sensing technology.
Surface-grafted block copolymer brushes with continuous composition gradients containing poly(poly(ethylene glycol) monomethacrylate) (P(PEGMA)) and poly(N-isopropylacrylamide) (PNIPAAm) chains were fabricated by integration of the surface-initiated atom transfer radical polymerization (SI-ATRP) and continuous injection method. Three types of copolymer gradients were prepared: (1) a uniform P(PEGMA) layer was block copolymerized with a gradient PNIPAAm layer (PP1); (2) a gradient P(PEGMA) layer was block copolymerized with a uniform PNIPAAm layer (PP2); and (3) a gradient P(PEGMA) layer was inversely block copolymerized with a gradient PNIPAAm layer (PP3). The as-prepared gradients were characterized by ellipsometry, water contact angle and atomic force microscopy (AFM) to determine their alterations in thickness, surface wettability and morphology, confirming the gradient structures. In vitro culture of HepG2 cells was implemented on the gradient surfaces, revealing that the cells could adhere at 37 ℃ and be detached at 20 ℃. Introduction of the PEG chains as an underlying layer on the PNIPAAm grafting surfaces resulted in faster cell detachment compared with the PNIPAAm grafting surface.
The micro-molding technology has played an important role in fabrication of polymer micro-patterns and development of functional devices.In such a process,suitable solvent can swell or dissolve the polymer films to decrease their glass transition temperature(Tg) and viscosity and thereby improve flowing ability.Consequently,it is easy to obtain the 2D and 3D patterns with high fidelity by the solvent-assisted micro-molding.Compared with the high temperature molding,this technology overcomes some shortcomings such as shrinking after cooling,degradation at high temperature,difficulty in processing some functional materials having high Tg,etc.It can be applied to making patterns not only on polymer monolayers but also on polyelectrolyte multilayers.Moreover,the compression-induced patterns on the multilayers are chemically homogenous but physically heterogeneous.In this review,the controlling factors on the pattern quality are also discussed,including materials of the mold,solvent,pressure,temperature and pattern density.
