Jun Huang

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.

Probing the Interaction between Air Bubble and Sphalerite Mineral Surface Using Atomic Force Microscope

The interaction between air bubbles and solid surfaces plays important roles in many engineering processes, such as mineral froth flotation. In this work, an atomic force microscope (AFM) bubble probe technique was employed, for the first time, to directly measure the interaction forces between an air bubble and sphalerite mineral surfaces of different hydrophobicity (i.e., sphalerite before/after conditioning treatment) under various hydrodynamic conditions. The direct force measurements demonstrate the critical role of the hydrodynamic force and surface forces in bubble-mineral interaction and attachment, which agree well with the theoretical calculations based on Reynolds lubrication theory and augmented Young-Laplace equation by including the effect of disjoining pressure. The hydrophobic disjoining pressure was found to be stronger for the bubble-water-conditioned sphalerite interaction with a larger hydrophobic decay length, which enables the bubble attachment on conditioned sphalerite at relatively higher bubble approaching velocities than that of unconditioned sphalerite. Increasing the salt concentration (i.e., NaCl, CaCl2) leads to weakened electrical double layer force and thereby facilitates the bubble-mineral attachment, which follows the classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory by including the effects of hydrophobic interaction. The results provide insights into the basic understanding of the interaction mechanism between bubbles and minerals at nanoscale in froth flotation processes, and the methodology on probing the interaction forces of air bubble and sphalerite surfaces in this work can be extended to many other mineral and particle systems.

Complexation and coacervation of like-charged polyelectrolytes inspired by mussels.

Significance Conventional coacervates can form on mixing oppositely charged polyelectrolytes in aqueous solutions, due to electrostatic attraction between the oppositely charged polymers. This report describes the first instance (to the best of our knowledge) of complexation and coacervation of two positively charged polyelectrolytes by overcoming longer-range electrostatic repulsion. The molecular force measurements and theoretical simulations demonstrate that the complexation of the like-charged coacervate is most likely driven by strong cation–π interactions inspired by marine mussel adhesives. This like-charged coacervation mechanism provides new insights into biological self-assembly processes and a new paradigm for engineering strong, reversible interactions between polymers underwater, which has various potential applications like encapsulation and dispersion of particles and cells. It is well known that polyelectrolyte complexes and coacervates can form on mixing oppositely charged polyelectrolytes in aqueous solutions, due to mainly electrostatic attraction between the oppositely charged polymers. Here, we report the first (to the best of our knowledge) complexation and coacervation of two positively charged polyelectrolytes, which provides a new paradigm for engineering strong, self-healing interactions between polyelectrolytes underwater and a new marine mussel-inspired underwater adhesion mechanism. Unlike the conventional complex coacervate, the like-charged coacervate is aggregated by strong short-range cation–π interactions by overcoming repulsive electrostatic interactions. The resultant phase of the like-charged coacervate comprises a thin and fragile polyelectrolyte framework and round and regular pores, implying a strong electrostatic correlation among the polyelectrolyte frameworks. The like-charged coacervate possesses a very low interfacial tension, which enables this highly positively charged coacervate to be applied to capture, carry, or encapsulate anionic biomolecules and particles with a broad range of applications.

In Vivo Residue‐Specific Dopa‐Incorporated Engineered Mussel Bioglue with Enhanced Adhesion and Water Resistance

Misaminoacylation of 3,4-dihydroxyphenylalanine (Dopa) molecules to tRNA(Tyr) by endogenous tyrosyl-tRNA synthetase allowed the quantitative replacement of tyrosine residues with a yield of over 90u2009% by an inu2005vivo residue-specific incorporation strategy, to create, for the first time, engineered mussel adhesive proteins (MAPs) in Escherichia coli with a very high Dopa content, close to that of natural MAPs. The Dopa-incorporated MAPs exhibited a superior surface adhesion and water resistance ability by assistance of Dopa-mediated interactions including the oxidative Dopa cross-linking, and furthermore, showed underwater adhesive properties comparable to those of natural MAPs. These results propose promising use of Dopa-incorporated engineered MAPs as bioglues or adhesive hydrogels for practical underwater applications.

Poly(acrylic acid) functionalized magnetic graphene oxide nanocomposite for removal of methylene blue

A polyacrylic acid (PAA) functionalized magnetic Fe3O4 nanoparticle-graphene oxide nanocomposite (PAA/MGO) was synthesized by a facile method. The structure and surface properties of MGO and PAA/MGO composites were characterized by infrared (IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HRTEM), thermogravimetric analysis (TGA) and zeta potential measurements. The adsorption of a model dye pollutant, methylene blue (MB), on MGO and PAA/MGO was investigated in batch tests. The functionalization of PAA to MGO significantly enhances the maximum adsorption capacity of MB (at pH = 7) from ∼70 mg g−1 (on MGO) to ∼291 mg g−1 (PAA/MGO). The adsorption of MB on MGO and PAA/MGO was mainly driven by the electrostatic attraction between positively charged MB molecules and negatively charged nanocomposite surfaces, and the higher adsorption capacity of PAA/MGO is mainly attributed to the functionalization of PAA and its higher content of charged carboxyl groups than MGO. The adsorption capacity of MB on both MGO and PAA/MGO adsorbents also increases with increasing solution pH from 3 to 11, due to enhanced electrostatic attraction at high pH conditions. The limited adsorption capacity of MB on MGO and PAA/MGO at pH 3, when electrostatic attraction is almost negligible, indicates that π–π interaction between the GO surface and MB also plays a role in the adsorption process. The PAA/MGO shows a rapid adsorption rate and high adsorption capacity of MB with magnetic properties for easy separation and excellent recyclability, which endows the nanocomposite with great potential for the removal of cationic organic pollutants in wastewater treatment.

Recent experimental advances on hydrophobic interactions at solid/water and fluid/water interfaces.

Hydrophobic effects play important roles in a wide range of natural phenomena and engineering processes such as coalescence of oil droplets in water, air flotation of mineral particles, and folding and assembly of proteins and biomembranes. In this work, the authors highlight recent experimental attempts to reveal the physical origin of hydrophobic effects by directly quantifying the hydrophobic interaction on both solid/water and fluid/water interfaces using state-of-art nanomechanical techniques such as surface forces apparatus and atomic force microscopy (AFM). For solid hydrophobic surfaces of different hydrophobicity, the range of hydrophobic interaction was reported to vary from ∼10 to >100u2009nm. With various characterization techniques, the very long-ranged attraction (>100u2009nm) has been demonstrated to be mainly attributed to nonhydrophobic interaction mechanisms such as pre-existing nanobubbles and molecular rearrangement. By ruling out these factors, intrinsic hydrophobic interaction was measured to follow an exponential law with decay length of 1-2u2009nm with effective range less than 20u2009nm. On the other hand, hydrophobic interaction measured at fluid interfaces using AFM droplet/bubble probe technique was found to decay with a much shorter length of ∼0.3u2009nm. This discrepancy of measured decay lengths is proposed to be attributed to inherent physical distinction between solid and fluid interfaces, which impacts the structure of interface-adjacent water molecules. Direct measurement of hydrophobic interaction on a broader range of interfaces and characterization of interfacial water molecular structure using spectroscopic techniques are anticipated to help unravel the origin of this rigidity-related mismatch of hydrophobic interaction and hold promise to uncover the physical nature of hydrophobic effects. With improved understanding of hydrophobic interaction, intrinsic interaction mechanisms of many biological and chemical pathways can be better elucidated, and novel devices/processes can be developed with capacity to modulate and control the hydrophobic effects from the molecular to the macroscopic scale.

Understanding nanorheology and surface forces of confined thin films

Understanding the nanorheology and associated intermolecular/surface forces of fluids in confined geometries or porous media is of both fundamental and practical importance, providing significant insights into various applications such as lubrication and micro/nanoelectromechanical systems. In this work, we briefly reviewed the fundamentals of nanoreheolgy, advances in experimental techniques and theoretical simulation methods, as well as important progress in the nanorheology of confined thin films. The advent of advanced experimental techniques such as surface forces apparatus (SFA), X-ray surface forces apparatus (XSFA) and atomic force microscope (AFM) and computational methods such as molecular dynamics simulations provides powerful tools to study a wide range of rheological phenomena at molecular level and nano scale. One of the most challenging issues unresolved is to elucidate the relationship between the rheological properties and structural evolution of the confined fluid films and particles suspensions. Some of the emerging research areas in the nanorheology field include, but are not limited to, the development of more advanced characterization techniques, design of multifunctional rheological fluids, bio-related nanorheology, and polymer brushes.

A two-step flocculation process on oil sands tailings treatment using oppositely charged polymer flocculants

Water management and treatment of mineral tailings and oil sands tailings are becoming critical challenges for the sustainable development of natural resources. Polymeric flocculants have been widely employed to facilitate the flocculation and settling of suspended fine solid particles in tailings, resulting in the separation of released water and solid sediments. In this study, a new flocculation process was developed for the treatment of oil sands tailings by using two oppositely charged polymers, i.e. an anionic polyacrylamide and a natural cationic biopolymer, chitosan. The new process was able to not only improve the clarity of supernatant after settling but also achieve a high settling efficiency. Treatment of the oil sands tailings using pure anionic polyacrylamide showed relatively high initial settling rate (ISR) of ~10.3m/h but with poor supernatant clarity (>1000NTU); while the treatment using pure cationic polymer resulted in clear supernatant (turbidity as low as 22NTU) but relatively low ISR of >2m/h. In the new flocculation process, the addition of anionic polyacrylamide to the tailings was followed by a cationic polymer, which showed both a high ISR (~7.7m/h) and a low turbidity (71NTU) of the supernatant. The flocculation mechanism was further investigated via the measurements of floc size, zeta potential and surface forces. The new flocculation process was revealed to include two steps: (1) bridging of fine solids by anionic polyacrylamide, and (2) further aggregation and flocculation mediated by charge neutralisation of the cationic polymer, which significantly eliminated the fine solids in the supernatants as well as increases floc size. Our results provide insights into the basic understanding of the interactions between polymer flocculants and solid particles in tailings treatment, as well as the development of novel tailings treatment technologies.

Sugary interfaces mitigate contact damage where stiff meets soft

The byssal threads of the fan shell Atrina pectinata are non-living functional materials intimately associated with living tissue, which provide an intriguing paradigm of bionic interface for robust load-bearing device. An interfacial load-bearing protein (A. pectinata foot protein-1, apfp-1) with L-3,4-dihydroxyphenylalanine (DOPA)-containing and mannose-binding domains has been characterized from Atrinas foot. apfp-1 was localized at the interface between stiff byssus and the soft tissue by immunochemical staining and confocal Raman imaging, implying that apfp-1 is an interfacial linker between the byssus and soft tissue, that is, the DOPA-containing domain interacts with itself and other byssal proteins via Fe3+–DOPA complexes, and the mannose-binding domain interacts with the soft tissue and cell membranes. Both DOPA- and sugar-mediated bindings are reversible and robust under wet conditions. This work shows the combination of DOPA and sugar chemistry at asymmetric interfaces is unprecedented and highly relevant to bionic interface design for tissue engineering and bionic devices.

A novel PKD2L1 C-terminal domain critical for trimerization and channel function

As a transient receptor potential (TRP) superfamily member, polycystic kidney disease 2-like-1 (PKD2L1) is also called TRPP3 and has similar membrane topology as voltage-gated cation channels. PKD2L1 is involved in hedgehog signaling, intestinal development, and sour tasting. PKD2L1 and PKD1L3 form heterotetramers with 3:1 stoichiometry. C-terminal coiled-coil-2 (CC2) domain (G699-W743) of PKD2L1 was reported to be important for its trimerization but independent studies showed that CC2 does not affect PKD2L1 channel function. It thus remains unclear how PKD2L1 proteins oligomerize into a functional channel. By SDS-PAGE, blue native PAGE and mutagenesis we here identified a novel C-terminal domain called C1 (K575-T622) involved in stronger homotrimerization than the non-overlapping CC2, and found that the PKD2L1 N-terminus is critical for dimerization. By electrophysiology and Xenopus oocyte expression, we found that C1, but not CC2, is critical for PKD2L1 channel function. Our co-immunoprecipitation and dynamic light scattering experiments further supported involvement of C1 in trimerization. Further, C1 acted as a blocking peptide that inhibits PKD2L1 trimerization as well as PKD2L1 and PKD2L1/PKD1L3 channel function. Thus, our study identified C1 as the first PKD2L1 domain essential for both PKD2L1 trimerization and channel function, and suggest that PKD2L1 and PKD2L1/PKD1L3 channels share the PKD2L1 trimerization process.