Mussel-inspired Chemistry Research Articles

Mussel-Inspired Polymeric Coatings to Realize Functions from Single and Dual to Multiple Antimicrobial Mechanisms.

Numerous efforts to fabricate antimicrobial surfaces by simple yet universal protocols with high efficiency have attracted considerable interest but proved to be particularly challenging. Herein, we designed and fabricated a series of antimicrobial polymeric coatings with different functions from single to multiple mechanisms by selectively utilizing diethylene glycol diglycidyl ether (PEGDGE), polylysine, and poly[glycidylmethacrylate-co-3-(dimethyl(4-vinylbenzyl)ammonium)propyl sulfonate] (poly(GMA-co-DVBAPS)) via straightforward mussel-inspired codeposition techniques. Bactericidal polylysine endowed the modified surfaces with a high ability (∼90%) to kill attached bacteria, while PEGDGE components with unique surface hydration prevented bacterial adhesion, avoiding the initial biofilm formation. Moreover, excellent salt-responsive poly(GMA-co-DVBAPS) enabled reactant polymeric coatings to change chain conformations from shrinkable to stretchable state and subsequently release >90% attached bacteria when treated with NaCl solution, even after repeated cycles. Therefore, the obtained polymeric coatings, polydopamine/poly(GMA-co-DVBAPS) (PDA/PDV), polydopamine/polylysine/poly(GMA-co-DVBAPS) (PDA/l-PDV), and polydopamine/polylysine/poly(GMA-co-DVBAPS)/diethylene glycol diglycidyl ether (PDA/l-PDV-PEGDGE), controllably realized functions from single and dual to multiple antimicrobial mechanisms, as evidenced by long-term antifouling activity to bacteria, high bactericidal efficiency, and salt-responsive bacterial regeneration performance with several bacterial killing-release cycles. This study not only contributes to mussel-inspired chemistry for polymeric coatings with controllable functions but also provides a series of reliable and highly efficient antimicrobial surfaces for potential biomedical applications.

Anti-biofouling materials and surfaces based on mussel-inspired chemistry

The mussel-inspired chemistry has been widely applied to fabricate anti-biofouling materials and surfaces through various functionalization strategies.

Mussel-inspiredcapsules toward reaction-triggered cargo release

A reaction-triggered controlled release system based on enzyme-encased capsules is constructed through mussel-inspired chemistry, where the oxidation of glucose by glucose oxidase lowers the local pH value, causing the breakage of the CN bond in the capsule and the release of insulin.

Polymer brush growth by oxygen-initiated RAFT polymerization on various substrates

We developed a user-friendly method for growing polymer brushes on various substrates in the presence of air by O2-SI-RAFT polymerization and mussel-inspired surface chemistry. In particular, PHEMA brushes grew to 856 nm on the titanium substrate.

Nano-catalytic behavior of highly efficient and regenerable mussel-inspired Fe3O4@CFR@GO and Fe3O4@CFR@TiO2 magnetic nanospheres in the reduction of Evans blue dye

Fe3O4@catechol formaldehyde resin coated @Graphene Oxide nanocomposite (Fe3O4@CFR@GO) and Fe3O4@catechol formaldehyde resin coated @TiO2 (Fe3O4@CFR@TiO2) nanocomposite were fabricated by hydrothermal method. Particularly, catechol bunches on the highest layer of nanospheres to play a mussel-inspired chemistry to assist combined with graphene oxide (GO) to wrap the Fe3O4@ coated nanosphere. The prepared catalyst was proven to be very efficient with less than a minute and vey less dosage (15–17 mg) in the adsorptive degradation of Evans blue dye. The adsorptive degradation of Evans blue dye with Fe3O4@CFR@GO and Fe3O4@CFR@TiO2 nanocomposites are studied by several variables like the dye concentration, dosage, pH, contact time and temperature. It shows maximum adsorption capacity of 0.1435 mg/g (Fe3O4@CFR@GO) and 9.345 mg/g (Fe3O4@CFR@TiO2) nanocomposites. The equilibrium concentration and the adsorption capacity were evaluated using three different isothermal models. The kinetic study determined that Evans blue dye adsorption was in good analogy with the pseudo-first-order kinetic model.

Mussel-inspired preparation of temperature-responsive polymer brushes modified layered double hydroxides@Pd/carbon dots hybrid for catalytic applications

A novel type of multicomponent nanocomposite of LDH@PDA@PNIPAM@Pd/carbon dots (CDs) was successfully constructed for highly efficient heterogeneous catalytic reduction from two-dimensional layer double hydroxide (LDH) nanosheet functionalized with thermo-responsive PNIPAM polymer brushes based on the mussel-inspired chemistry. CDs were used as a reductant and stabilizer by in situ loading metal Pd onto LDH@PDA@PNIPAM. Compared with LDH@PDA@PNIPAM@Pd catalyst without CDs modification, the designed LDH@PDA@PNIPAM@Pd/CDs nanohybrid catalyst had better catalytic reduction ability for various dyes and nitrophenol thanks to the synergistic catalytic effect between metal active center and CDs, LDH and their high dispersion stability. Especially, a good catalytic reduction activity was demonstrated for methylene blue (MB) with a high TOF (545.2 min−1). Furthermore, the nanohybrid presented interesting thermo-responsive catalytic property due to the existence of PNIPAM polymer chains. In addition, the prepared catalyst also exhibited outstanding catalytic property for the Knoevenagel condensation reaction. Our study provides a new way for the composite preparation of organic-inorganic hybrid materials by polymer and inorganic materials, and shows great potential in the field of catalytic applications.

Mussel-inspired synthesis of magnetic carboxymethyl chitosan aerogel for removal cationic and anionic dyes from aqueous solution

A novel and facile method that magnetic carboxymethyl chitosan aerogel (Fe3O4@PDA/CMC) has been developed with the combination of mussel-inspired chemistry and Schiff base reaction to remove cation and anion dyes. The resulted aerogel were systematically characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscope (TEM), scanning electron microscope (SEM), X-ray diffraction (XRD), vibrating sample magnetometer (VSM), thermogravimetric analysis (TGA), N2 adsorption–desorption, and point of zero charge (pHpzc). Diverse factors affecting adsorption behavior such as pH, contact time, adsorbent dosage, initial concentration, ionic strength of dyes was investigated. The kinetic results show that the adsorption process can be well described by the pseudo-second-order. The Langmuir isotherm model can fit the equilibrium data well. The thermodynamic analyses show that the adsorption of cation and anion dyes onto Fe3O4@PDA/CMC aerogel is endothermic and spontaneous. In this study, the obtained Fe3O4@PDA/CMC aerogel is a simple, facile and environmentally friendly procedure which involves non-toxic organic solvent. The designed magnetic aerogel exhibited an excellent recyclability and removal efficiency after seven adsorption-desorption cycles.

Ultrastretchable, self-adhesive, strain-sensitive and self-healing GO@DA/Alginate/P(AAc-co-AAm) multifunctional hydrogels via mussel-inspired chemistry

For conductive hydrogels applied in biosensors, wearable devices and so forth, multifunctionality is an inevitable trend of development to meet various practical requirements and enhance human experience. Herein, inspired by nanocomposite, double-network (DN) and mussel chemistry, a new Graphene oxide@Dopamine/Alginate/Poly(acrylic acid-co-acrylamide) [GO@DA/Alginate/P(AAc-co-AAm)] hydrogel was fabricated through one-pot in-situ radical copolymerization. GO@DA nanofillers, prepared via GO confined DA polymerization, imparted the hydrogel with remarkable adhesiveness. Alginate/P(AAc-co-AAm) DN matrix, physically and chemically crosslinked by Fe3+ and N,N'-Methylenebisacrylamide, made hydrogels ultrastretchable, self-healing and biocompatible. With contents of DA and alginate accurately regulated, the tensile strength, elongation, adhesion strength and conductivity of the optimal hydrogel could reach 320.2 kPa, 1198 %, 36.9 kPa and 3.24 ± 0.12 S/m, respectively. What’s more notable was that the synergistic integration of repeatable adhesiveness, strain sensitivity, use stability, self-healing ability and biocompatibility provided such hydrogels with tremendous possibility of practical application for strain sensors.

Mussel-inspired functionalized LDH as covalent crosslinkers for constructing micro-crosslinking fluorenyl-containing polysulfone-based composite anion exchange membranes with enhanced properties

The low ionic conductivity and poor dimensional stability severely influence the application of anion exchange membranes (AEMs). Therefore, how to balance the problem of excessive swelling of polymer matrix caused by increasing ion conductivity becomes an important challenge. Herein, 3-(dimethylamino)-1- propylamine (DMAPA) and polyethyleneimine (PEI) were grafted to the surface of layered double hydroxide (LDH) through mussel-inspired chemistry. The sheet-like functionalized LDH (DLDH and PLDH) as both filler and crosslinker was incorporated into the quaternized fluorenyl-containing polyethersulfone (QPFSU) matrix to get a series of new composite anion exchange membranes (AEMs). The as-prepared micro-crosslinked AEMs were found to form more hydrophilic conductive ion clusters owing to the generation of new quaternary ammonium groups during the crosslinking reaction. The micro-crosslinked AEMs have better dimensional stability while having higher OH − conductivity. Especially the ion conductivity of CQPFSU-1%-PLDH membrane can reach 86.8 mS cm −1 at 80 °C with excellent dimensional and chemical stability (SR is 9.6% at 80 °C, 21.8% decrease in OH − conductivity at 60 °C in 1.0 M NaOH for 200 h). Overall, the micro-crosslinking method for functionalized LDH modified AEMs achieves a balance between ion conductivity and dimensional stability of AEMs. • 2D sheet-shaped functionalized LDH was prepared by mussel-inspired chemistry. • Micro-crosslinked QPFSU-based AEMs were prepared using functionalized LDH as crosslinkers and fillers. • Micro-crosslinked AEMs exhibited high ion conductivity and good dimensional stability. • Micro-crosslinking method achieves a balance between ion conductivity and dimensional stability of AEMs.

MoS2 decorated with ZrO2 nanoparticles through mussel-inspired chemistry of dopamine for reinforcing anticorrosion of epoxy coatings

Faced with severe corrosion of casing in oil wells, the epoxy coating was applied to prevent corrosion. Based on the mechanism that the filler eliminated the internal stress during the curing process of the coating and prevented the penetration of corrosive medium into the coating, a new filler was successfully prepared by the hydrothermal method. When the molar ratio of the precursor of ZrO2 to MoS2 was 1.2:1, MoS2 was uniformly modified with ZrO2 through mussel inspired chemistry of dopamine. Introducing fillers into epoxy coatings, specifically, a proper content of 0.8 wt.% filler can greatly improve the mechanical properties and corrosion resistance of the coatings. The coating maintained the excellent corrosion resistance for 16 h under high temperature (108 °C) and high pressure (pressurized with CO2 gas of 35 MPa), which would provide us a reliable anticorrosive coating for oil wells metal casing.

Superhydrophilic membranes produced by biomimetic mineralization for water treatment

Poly(vinylidene fluoride) (PVDF) membrane has been applied in the diverse water treatments, but its inherent hydrophobicity must be adjusted to reduce energy consumption. Herein, high hydrophobicity of PVDF membrane surface was transformed to superhydrophilicity by the combination of mussel-inspired chemistry and biomimetic mineralization. The deposited tannic acid (TA) and polyethylenimine (PEI) induced in situ biomimetic mineralization to form nanosphere and nanowire microstructures on the membrane surface. The highly efficient separation and outstanding antifouling properties were achieved for oil-in-water emulsion and dyeing wastewater treatment. The rejections of nano-ZrO2/PEI-TA/PVDF membranes to BSA, oil, Congo red and methyl blue reached as high as 99.3%, 98.8%, 96.8% and 93.5% (15-fold increment compared to that of pristine membrane), respectively. With rejections to BSA (95.0%), oil (93.9%), Congo red (86.6%) and methyl blue (83.2%), the permeate flux of nano-TiO2/PEI-TA/PVDF membranes reached as high as 1312.6 L/m2 h, showing nearly 7.6-fold increment compared with other reported values. This work developed a novel strategy to fabricate multifunctional separation membranes for environmental remediation. A superhydrophilic membrane with multiple hierarchical structures was fabricated through the combination of mussel-inspired chemistry and biomimetic mineralization to treat dyeing wastewater and oil emulsions highly efficiently.

Mussel-inspired fabrication of halloysite nanotube-based magnetic composites as catalysts for highly efficient degradation of organic dyes

In this work, heterogeneous catalysts based on halloysite nanotubes (HNTs) were fabricated through mussel-inspired chemistry that could be used in situ to generate Fe3O4 nanoparticles on HNTs. HNT-based magnetic composites (HNTs@PDA-MNPs) were examined as catalysts for the Fenton reaction. The characterization results demonstrated that Fe3O4 nanoparticles could be well-dispersed on HNTs with polydopamine (PDA) as the linkage. Various experimental parameters, such as the concentrations of HNTs@PDA-MNPs and H2O2, reaction temperature and solution pH, of the degradation efficiencies were investigated in detail. The results demonstrated that the degradation efficiencies of methylene blue were greater than 97% under optimized conditions. Moreover, HNTs@PDA-MNPs also exhibited excellent degradation efficiencies for other organic dyes (such as rhodamine B, methyl orange, and Congo red). Electron spin-resonance spectroscopy suggested that free radicals such as •OH and •O2− were generated during the Fenton reaction, which could destroy the structure of the organic dyes. Taken together, a biomimetic method based on the self-polymerization of dopamine and the in situ generation of Fe3O4 nanoparticles on HNTs is developed for the fabrication of HNTs@PDA-MNP composites, which exhibit excellent degradation efficiencies towards different organic dyes through the Fenton reaction. This method can also be extended for the preparation of other multifunctional composites with potential for different applications.

Superhydrophilic Coating with Antibacterial and Oil-Repellent Properties via NaIO4-Triggered Polydopamine/Sulfobetaine Methacrylate Polymerization.

Superhydrophilic coatings have been widely used for the surface modification of membranes or biomedical devices owing to their excellent antifouling properties. However, simplifying the modification processes of such materials remains challenging. In this study, we developed a simple and rapid one-step co-deposition process using an oxidant trigger to fabricate superhydrophilic surfaces based on dopamine chemistry with sulfobetaine methacrylate (SBMA). We studied the effect of different oxidants and SBMA concentrations on surface modification in detail using UV–VIS spectrophotometry, dynamic light scattering, atomic force microscopy, X-ray photoelectron spectroscopy, and surface plasmon resonance. We found that NaIO4 could trigger the rate of polymerization and the optimum ratio of dopamine to SBMA is 1:25 by weight. This makes the surface superhydrophilic (water contact angle < 10°) and antifouling. The superhydrophilic coating, when introduced to polyester membranes, showed great potential for oil/water separation. Our study provides a complete description of the simple and fast preparation of superhydrophilic coatings for surface modification based on mussel-inspired chemistry.

Surface/Interfacial design and tailoring of polymeric membranes for liquid-phase separation

Synthetic polymer membranes are widely used in many applications, including, among others, water purification, protein separation, and medicine. However, the use of existing polymer membranes faces major challenges, such as the trade-off between permeability and selectivity, membrane fouling, and poor mechanical strength. To address these problems the authors have focused their research on surface/interfacial tailoring and the structure-property relationship of polymer membranes used in liquid separation systems. Progress has been made as follows: (1) a methodology for membrane surface functionalization and nanofiltration (NF) membrane preparation based on mussel-inspired catecholic chemistry was proposed and established; (2) a class of mechanically robust and environmentally-responsive composite membranes with hydrogel pore-filled in rigid macroporous supports was designed and developed; (3) a methodology for surface tailoring and antifouling modification of polymer membranes based on amphiphilic copolymers was created and the scientific implications for amphiphilic polymer membranes elaborated; (4) an adsorption membrane with both filtration and adsorption functions was designed and developed to achieve rapid removal of trace micropollutants, including heavy metal ions, organic dyes, plasticizer, antibiotics, and others. This mini-review briefly summarizes this work.

Hydrogels as Durable Anti-Icing Coatings Inhibit and Delay Ice Nucleation

The accumulation of ice on surfaces brings dangerous and costly problems to our daily life. Thus, it would be desirable to design anti-icing coatings for various surfaces. We report a durable anti-icing coating based on mussel-inspired chemistry, which is enabled via fabricating a liquid water layer, achieved by modifying solid substrates with the highly water absorbing property of sodium alginate. Dopamine, the main component of the mussel adhesive protein, is introduced to anchor the sodium alginate in order to render the coating applicable to all types of solid surfaces. Simultaneously, it serves as the cross-linking agent for sodium alginate; thus, the cross-linking degree of the coatings could be easily varied. The non-freezable and freezable water in the coatings with different cross-link degrees all remain liquid-like at subzero conditions and synergistically fulfill the aim of decreasing the temperature of ice nucleation. These anti-icing coatings display excellent stability even under harsh conditions. Furthermore, these coatings can be applied to almost all types of solid surfaces and have great promise in practical applications.

Mussel-Inspired Magnetic Nanoflowers as an Effective Nanozyme and Antimicrobial Agent for Biosensing and Catalytic Reduction of Organic Dyes.

Mussel-inspired chemistry has been embodied as a method for acquiring multifunctional nanostructures. In this research, a novel mussel-inspired magnetic nanoflower was prepared through a mussel-inspired approach. Herein, magnetic PDA–Cu nanoflowers (NFs) were assembled via incorporating magnetic Fe3O4@SiO2–NH2 core/shell nanoparticles (NPs) into mussel-inspired polydopamine (PDA) and copper phosphate as the organic and inorganic portions, respectively. Accordingly, the flower-like morphology of MNPs PDA–Cu NFs was characterized by scanning electron microscopy (SEM) images. X-ray diffraction (XRD) analysis confirmed the crystalline structure of magnetic nanoparticles (MNPs) and copper phosphate. Vibrating sample magnetometer (VSM) data revealed the superparamagnetic behavior of MNPs (40.5 emu/g) and MNPs PDA–Cu NFs (35.4 emu/g). Catalytic reduction of MNPs PDA–Cu NFs was evaluated through degradation of methylene blue (MB). The reduction of MB pursued the Langmuir–Hinshelwood mechanism and first-order kinetics, in which the apparent reduction rate Kapp of MB was higher than 1.44 min–1 and the dye degradation ability was 100%. MNPs PDA–Cu NFs also showed outstanding recyclability and reduction efficiency, for at least six cycles. Furthermore, the prepared MNPs PDA–Cu NFs demonstrated a peroxidase-like catalytic activity for catalyzing 3,3′,5,5′-tetramethylbenzidine (TMB) to a blue oxidized TMB (oxTMB) solution in the presence of H2O2. Antimicrobial assays for MNPs PDA–Cu and PDA–Cu NFs were conducted on both Gram-negative and Gram-positive bacteria. Moreover, we demonstrated how the existence of magnetic nanoparticles in PDA–Cu NFs influences the inhibition of an increasing zone. Based on the results, mussel-inspired magnetic nanoflowers appear to have great potential applications, including those relevant to biological, catalysis, and environmental research.

Mussel-inspired preparation of MXene-PDA-Bi6O7 composites for efficient adsorptive removal of iodide ions

• The MXene-PDA-Bi 6 O 7 composites were synthesized through a bioinspired chemistry. • The MXene-PDA-Bi 6 O 7 composites were utilized as the adsorbents for removal of iodide ions. • The adsorption capacity of MXene-PDA-Bi 6 O 7 composites is higher than other related composites. • The bioinspired strategy is rather simple and universality. MXene has emerged as one of the most interesting two-dimensional (2D) nanomaterials, that has been widely explored for various applications, including environmental adsorption. However, the adsorption performance of unmodified MXene is poor and surface functionalization is necessary to endow new properties and improve the adsorption performance. In this work, we reported the fabrication of MXene based bismuth oxide (MXene-PDA-Bi 6 O 7 ) composites for the first time through the mussel-inspired chemistry, which relied on the self-polymerization of dopamine to form polydopamine (PDA) films on MXene for subsequent immobilization of Bi 6 O 7 nanoparticles. The utilization of MXene-PDA-Bi 6 O 7 composites for adsorptive removal of iodide ions and the adsorption parameters on adsorption behavior were examined in details. The surface morphology, chemical structure and chemical compositions of these samples were characterized by a series of techniques. The results demonstrated that the maximum adsorption capacity of MXene-PDA-Bi 6 O 7 towards iodide ions is 64.65 mg/g, which is obviously greater than that of unmodified MXene and MXene-PDA under identical adsorption conditions. In the fabrication strategy, the PDA could be facilely coated on the MXene and provide a platform for further immobilization of the Bi 6 O 7 nanoparticles. This method is simple, easy of operation and can be occurred under benign and mild experimental conditions. Moreover, this method could also be utilized for introduction of other functional components on the MXene and thus multifunctional MXene based composites with designed properties and functions could be fabricated. We believe that this work will open a new avenue for fabrication of functional MXene based composites for environmental treatment.

Superior lubrication performance of MoS2-Al2O3 composite nanofluid in strips hot rolling

Abstract The novel composite material MoS2-Al2O3 nanoparticles were synthesized via mussel-inspired chemistry of dopamine. Hot rolling lubrication performance of MoS2-Al2O3 in water-based fluid was evaluated using a two-high rolling mill. Results showed that the synthesized MoS2-Al2O3 nanofluid exhibited optimum hot rolling lubrication performance. The finish rolling thickness and rolled surface roughness reached lowest. Meanwhile the rolling force and oxide scale thickness of strips were respectively reduced by 26.9 % and 54.2 % compared with base-fluid lubricating condition. The ratio of Fe2O3 in oxide scale has lowered when rolled with nanofluids, owing to the antioxidation effect of nanoparticles during lubrication. MoS2 has partially oxidized to MoO3 and the excellent lubrication performance of MoS2-Al2O3 nanofluid resulted from the lubricating film formed by these three nanoparticles.

Fabrication of novel electrochemical immunosensor by mussel-inspired chemistry and surface-initiated PET-ATRP for the simultaneous detection of CEA and AFP

A functional electrochemical immunosensor was successfully designed for simultaneous and high sensitivity detection of carcinoembryonic antigen (CEA) and α-fetoprotein (AFP). This electrochemical immunosensor was mainly designed by surface-initiated poly(glycidyl methacrylate) (PGMA) from multi-walled carbon nanotubes (MWCNTs) with the methodology of mussel-inspired chemistry (polydopamine, PDA) and metal-free photoinduced electron transfer-atom transfer radical polymerization (PET-ATRP). Controlled PGMA was initiated from MWCNTs, in which Br-functional PDA-modified MWCNTs and eosin Y (EY) were used as initiator and photocatalyst, respectively. The epoxy group of PGMA is reacted with ethylenediamine (EDA) by a ring-opening reaction, the amino and hydroxyl groups in the polymer chain provide numerous effective binding sites for carboxyl groups of signal molecules and capture antibodies, realizing highly sensitive electrochemical detection. Under optimized conditions, the obtained hybrid nanoprobes (Aq/PGMA-g-MWCNTs and Fc/PGMA-g-MWCNTs) were used as efficient electrochemical immunosensor to simultaneously detect CEA and AFP. It is worth noting that the electrochemical immunosensor performed a wide detection range and a low detection limit of CEA (163 fg/mL ~ 163 ng/mL, 56.1 fg/mL) and AFP (100 fg/mL ~ 100 ng/mL, 32.8 fg/mL), respectively. This high sensitivity and selectivity detection platform has a potential application in the simultaneous detection of more tumor markers.

Magnetic Iron Oxide Nanoparticles Immobilized with Sugar-Containing Poly(ionic liquid) Brushes for Efficient Trapping and Killing of Bacteria.

Poly(ionic liquid)s (PILs) such as polymeric quaternary ammonium compounds (PQACs) are among the most widely used disinfectant agents due to their broad-spectrum antimicrobial activity. However, the high cytotoxicity and difficult reclamation of PQACs remain as challenges for practical water treatment. Herein, we present the synthesis of sugar-incorporated PQACs, which could efficiently decrease the cytotoxicity toward mammalian cells (mouse fibroblast cells, L929). On the basis of the mussel-inspired surface chemistry, the functional glycopolymers could then be immobilized onto the surface of magnetic iron oxide nanoparticles, which are successfully used for the trapping and killing of bacteria. The sugar-containing PILs have combined the lectin-recognition behavior of glycopolymers and the antibacterial activity of PQACs. Antibacterial experiments demonstrate the high-performance of cationic hybrid nanocomposites in killing pathogenic Escherichia coli (E. coli), up to 100% sterilization efficiency. The nanocomposites could be facilely recovered under external magnetic field, and a high sterilization efficiency of 94% could be retained during a five-circulation use. Such hybrid nanocomposites are highly efficient, expediently recyclable, and low-cytotoxicity disinfectant agents and may have potential application for water disinfection treatment.