Chanoong Lim

Nanomechanics of Poly(catecholamine) Coatings in Aqueous Solutions

Mussel-inspired self-polymerized catecholamine coatings have been widely utilized as a versatile coating strategy that can be applied to a variety of substrates. For the first time, nanomechanical measurements and an evaluation of the contribution of primary amine groups to poly(catecholamine) coatings have been conducted using a surface-forces apparatus. The adhesive strength between the poly(catecholamine) layers is 30-times higher than that of a poly(catechol) coating. The origin of the strong attraction between the poly(catecholamine) layers is probably due to surface salt displacement by the primary amine, π-π stacking (the quadrupole-quadrupole interaction of indolic crosslinks), and cation-π interactions (the monopole-quadrupole interaction between positively charged amine groups and the indolic crosslinks). The contribution of the primary amine group to the catecholamine coating is vital for the design and development of mussel-inspired catechol-based coating materials.

Strong adhesion and cohesion of chitosan in aqueous solutions.

Chitosan, a load-bearing biomacromolecule found in the exoskeletons of crustaceans and insects, is a promising biopolymer for the replacement of synthetic plastic compounds. Here, surface interactions mediated by chitosan in aqueous solutions, including the effects of pH and contact time, were investigated using a surface forces apparatus (SFA). Chitosan films showed an adhesion to mica for all tested pH ranges (3.0-8.5), achieving a maximum value at pH 3.0 after a contact time of 1 h (Wad ~ 6.4 mJ/m(2)). We also found weak or no cohesion between two opposing chitosan layers on mica in aqueous buffer until the critical contact time for maximum adhesion (chitosan-mica) was reached. Strong cohesion (Wco ~ 8.5 mJ/m(2)) between the films was measured with increasing contact times up to 1 h at pH 3.0, which is equivalent to ~60% of the strongest, previously reported, mussel underwater adhesion. Such time-dependent adhesion properties are most likely related to molecular or molecular group reorientations and interdigitations. At high pH (8.5), the solubility of chitosan changes drastically, causing the chitosan-chitosan (cohesion) interaction to be repulsive at all separation distances and contact times. The strong contact time and pH-dependent chitosan-chitosan cohesion and adhesion properties provide new insight into the development of chitosan-based load-bearing materials.

Mussel-Inspired Anchoring of Polymer Loops That Provide Superior Surface Lubrication and Antifouling Properties

We describe robustly anchored triblock copolymers that adopt loop conformations on surfaces and endow them with unprecedented lubricating and antifouling properties. The triblocks have two end blocks with catechol-anchoring groups and a looping poly(ethylene oxide) (PEO) midblock. The loops mediate strong steric repulsion between two mica surfaces. When sheared at constant speeds of ∼2.5 μm/s, the surfaces exhibit an extremely low friction coefficient of ∼0.002-0.004 without any signs of damage up to pressures of ∼2-3 MPa that are close to most biological bearing systems. Moreover, the polymer loops enhance inhibition of cell adhesion and proliferation compared to polymers in the random coil or brush conformations. These results demonstrate that strongly anchored polymer loops are effective for high lubrication and low cell adhesion and represent a promising candidate for the development of specialized high-performance biomedical coatings.

Dopamine-Mediated Sclerotization of Regenerated Chitin in Ionic Liquid

Chitin is a promising structural material for biomedical applications, due to its many advantageous properties and abundance in nature. However, its usage and development in the biomedical field have been stagnant, because of chitin’s poor mechanical properties in wet conditions and the difficulties in transforming it into an applicable form. To overcome these challenges, we created a novel biomimetic chitin composite. This regenerated chitin, prepared with ionic liquid, showed improved mechanical properties in wet conditions by mimicking insect cuticle and squid beak sclerotization, i.e., catechol-meditated cross-linking. By ionic liquid-based heat treatment, dopamine oxidation produced melanin-like compounds and dopamine-meditated cross-links without any solvent evaporation and oxidant utilization. The dopamine-meditated sclerotization increased the ultimate tensile strength (UTS) of the regenerated chitin by 2.52-fold, measured after six weeks of phosphate-buffered saline (PBS) submersion. In addition, the linear swelling ratio (LSR) of the chitin film was reduced by about 22%. This strategy raises a possibility of using regenerated chitin as an artificial hard tissue in wet conditions.

Contact time- and pH-dependent adhesion and cohesion of low molecular weight chitosan coated surfaces.

Low molecular weight chitosan (LMW chitosan, ∼5 kDa) potentially has many desirable biomedical applications such as anti-microbial, anti-tumor, and anti-diabetes. Unlike high molecular weight chitosan, LMW chitosan is easily dissolvable in aqueous solutions even at neutral and basic pH, but its dissolution mechanism is not well understood. Here, we measured adhesion and cohesion of molecularly thin LMW chitosan films in aqueous solutions in different buffer pHs (from 3.0 to 8.5) using a surface forces apparatus (SFA). Interestingly, significantly lower adhesion force was measured for LMW chitosan films compared to the high molecular weight chitosan (∼150 kDa) films. Not only the strength of adhesion is lower, but also the critical contact time where adhesion starts to increase with contact time is longer. The results from both the SFA and atomic force microscopy (AFM) indicate that, in physiological and basic conditions, the low cohesion of LMW chitosan due to the stiffness of the chain which cause strong electrostatic correlation energy penalty when they are aggregated. Here, we propose the reduction in cohesion for shorter chitosan (LMW chitosan) as an explanation of its high solubility of LMW chitosan in physiological pHs.

Chitosan and hydroxyapatite composite cross‐linked by dopamine has improved anisotropic hydroxyapatite growth and wet mechanical properties

Three of the major impediments to using hydroxyapatite (HAp)‐collagen composites for hard tissue repair are the difficulties in anisotropic growth of HAp, in functional collagen production, and in their cross‐linking. To solve these problems, we fabricated HAp‐based composites for hard tissue repair by using chitosan as a collagen matrix substitute, and dopamine as a replacement for aldehyde‐based cross‐linkers. In the presence of chitosan and dopamine, the HAp particles grew anisotropically in a needle shape with an aspect ratio of ∼4.4. The needle‐shaped HAp particles were dispersed well in the chitosan matrix, and dopamine‐mediated cross‐linking enhanced the stiffness and reduced swelling in the presence of water. The composite is too weak for use in hard tissue repair, but could be used for curing dentin sensitivity by blocking and remineralization on dentinal tubules, and in drug‐delivery applications.

Surface forces apparatus and its applications for nanomechanics of underwater adhesives

Successful adhesion on wet surfaces is one of the most important challenges in biomedical engineering. Marine fouling organisms exhibit effective adhesion for wet substrates, and the measurement of adhesion forces in wet conditions is the first step toward mimicking the smart strategies of the marine organisms. Surface forces apparatus (SFA) is one of the most powerful nanomechanical tools used to directly measure time- and distance-dependent interactions between biological macromolecules or biological surfaces in an aqueous medium at the molecular level. Recently, SFA has been adapted to probe the biomechanical nature of the underwater adhesive in marine organisms. This review describes some strategies of the marine fouling organisms for successful underwater adhesion determined using SFA.

Probing nanomechanical interaction at the interface between biological membrane and potentially toxic chemical

Various xenobiotics interact with biological membranes, and precise evaluations of the molecular interactions between them are essential to foresee the toxicity and bioavailability of existing or newly synthesized molecules. In this study, surface forces apparatus (SFA) measurement and Langmuir trough based tensiometry are performed to reveal nanomechanical interaction mechanisms between potential toxicants and biological membranes for ex vivo toxicity evaluation. As a toxicant, polyhexamethylene guanidine (PHMG) was selected because PHMG containing humidifier disinfectant and Vodka caused lots of victims in both S. Korea and Russia, respectively, due to the lack of holistic toxicity evaluation of PHMG. Here, we measured strong attraction (Wad ∼4.2 mJ/m2) between PHMG and head group of biological membranes while no detectable adhesion force between the head group and control molecules was measured. Moreover, significant changes in π-A isotherm of 1,2-Dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) monolayers were measured upon PHMG adsorption. These results indicate PHMG strongly binds to hydrophilic group of lipid membranes and alters the structural and phase behavior of them. More importantly, complementary utilization of SFA and Langmuir trough techniques are found to be useful to predict the potential toxicity of a chemical by evaluating the molecular interaction with biological membranes, the primary protective barrier for living organisms.