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Global climate change is heavily affected by an increase in CO2. As one of several efforts to cope with this, research on poplar, a representative, fast growing, and model organism in plants, is actively underway. The effects of elevated atmospheric CO2 on the metabolism, growth, and transcriptome of poplar were investigated to predict productivity in an environment where CO2 concentrations are increasing. Poplar trees were grown at ambient (400 ppm) or elevated CO2 concentrations (1.4× ambient, 560 ppm, and 1.8× ambient, 720 ppm) for 16 weeks in open-top chambers (OTCs). We analyzed the differences in the transcriptomes of Populusalba × Populus glandulosa clone “Clivus” and Populus euramericana clone “I-476” using high-throughput sequencing techniques and elucidated the functions of the differentially expressed genes (DEGs) using various functional annotation methods. About 272,355 contigs and 207,063 unigenes were obtained from transcriptome assembly with the Trinity assembly package. Common DEGs were identified which were consistently regulated in both the elevated CO2 concentrations. In Clivus 29, common DEGs were found, and most of these correspond to cell wall proteins, especially hydroxyproline-rich glycoproteins (HRGP), or related to fatty acid metabolism. Concomitantly, in I-476, 25 were identified, and they were related to heat shock protein (HSP) chaperone family, photosynthesis, nitrogen metabolism, and carbon metabolism. In addition, carbohydrate contents, including starch and total soluble sugar, were significantly increased in response to elevated CO2. These data should be useful for future gene discovery, molecular studies, and tree improvement strategies for the upcoming increased-CO2 environments.

Antimicrobial peptides (AMPs) are the frontline innate defense system evolutionarily preserved in insects to combat invading pathogens. These AMPs could serve as an alternative to classical antibiotics to overcome the burden of treating multidrug resistant bacteria. Psacotheasin, a knottin type AMP was isolated from Psacothea hilaris and shown to exhibit antimicrobial activity, especially against fungi through apoptosis mediated cell death. In this study, we aimed to identify novel probable AMPs from Psacothea hilaris, the yellow spotted longicorn beetle. The beetle was immunized with the two bacterial strains (E. coli and S. aureus), and the yeast strain C. albicans. After immunization, total RNA was isolated and sequenced in Illumina platform. Then, beetle transcriptome was de novo assembled and searched for putative AMPs with the known physiochemical features of the AMPs. A selection of AMP candidates were synthesized and tested for antimicrobial activity. Four peptides showed stronger activity against E. coli than the control AMP, melittin while one peptide showed similar activity against S. aureus. Moreover, four peptides and two peptides showed antifungal activity stronger than and similar to melittin, respectively. Collectively one peptide showed both antibacterial and antifungal activity superior to melittin, thus, it provides a potent antimicrobial peptide. All the peptides showed no hemolysis in all the tested concentrations. These results suggest that in silico mining of insects&rsquo, transcriptome could be a promising tool to obtain and optimize novel AMPs for human needs.

Lignin is an aromatic-rich biomass polymer that is cheap, abundant, and sustainable. However, its application in the solid electrolyte field is rare due to challenges in well-defined polymer synthesis. Herein, the synthesis of lignin-graft-poly(ethylene glycol) (PEG) and its conductivity test for a solid electrolyte application are demonstrated. The main steps of synthesis include functionalization of natural lignin's hydroxyl to alkene, followed by graft-copolymerization of PEG thiol to the lignin via photoredox thiol-ene reaction. Two lignin-graft-PEGs are prepared having 22 wt% lignin (lignin-graft-PEG 550) and 34 wt% lignin (lignin-graft-PEG 2000). Then, new polymer electrolytes for conductivity tests are prepared via addition of lithium bis-trifluoromethanesulfonimide. The polymer graft electrolytes exhibit ionic conductivity up to 1.4 × 10-4 S cm-1 at 35 °C. The presence of lignin moderately impacts conductivity at elevated temperature compared to homopolymer PEG. Furthermore, the ionic conductivity of lignin-graft-PEG at ambient temperature is significantly higher than homopolymer PEG precedents.

A glucose-based bioadhesive, poly(2-methacrylamido glucopyranose-co-N-methacryloyl-3,4-dihydroxyl-L-phenylalanine-co-8-azidooctyl methacrylate) [poly(MG-co-MDOPA-co-AOM)], has been synthesized by thermally-initiated free radical polymerization. The new bioadhesive is composed of three modules: a hydrophilic glycopolymer segment, a mussel-inspired catechol segment, and a crosslinking azide segment. Poly(ethylene glycol) (PEG)-based crosslinker, (1R,8S,9s)-bicyclo[6.1.0]non-4-yn-9-ylmethyl PEG (BCN-PEG) was synthesized separately. Bulk adhesion properties of the terpolymer were enhanced by covalent bond forming crosslinking via strain-promoted azide–alkyne cycloaddition (SPAAC). The occurrence of SPAAC was confirmed by 1H NMR and FT-IR. After moistening the adhesive and the crosslinker, BCN-PEG with water, adhesion properties were examined by a lap shear strength test on porcine skins. The control of adhesion was studied under various crosslinker concentrations, crosslinking durations, and crosslinker lengths. Even without crosslinking, the new terpolymer adhesive demonstrated 20-fold higher adhesion strength (115 kPa) compared to a commercial rubber cement (5.8 kPa). The most significant factor to control for adhesion was crosslinker length. BCN-PEG was prepared with 134 and 43 repeating units of PEG. Crosslinking with the long crosslinker, BCN-PEG (PEG repeating units: 134), did not enhance adhesion strength meaningfully. However, crosslinking the short crosslinker BCN-PEG (repeating units: 43) showed significant improvement in work of adhesion (150% higher than uncrosslinked). The overall revealed features of strong adhesion on biological surfaces, structural similarity to natural carbohydrate, water compatibility, controllability of adhesion strength, and non-toxic adhesion enhancement principle via SPAAC crosslinking, suggest that the new glucose-based bioadhesive can be successfully used for biomedical applications.

The current use of lignin as a raw material is very limited and focused only on cheap and poorly defined nonfunctional materials mainly due to challenges in synthetic modification of lignin. Herein, we report a new low energy and environmentally friendly lignin modification method induced by visible blue light. The key modification reaction is a photoredox catalyzed thiol–ene reaction. The lignin was modified to possess alkenes for the thiol–ene reaction. Three photochemical reagents—Ru(bpy)3Cl2, Eosin Y, and 2,2-dimethoxy-2-phenylacetophenone—were tested to determine the best thiol–ene modification method. The thiol–ene reaction between lignin–alkene and 1-decanethiol revealed that Ru(bpy)3Cl2 was the most efficient, resulting in conversions of 97% with 2.5 mol % catalyst loading. The Ru(bpy)3Cl2 was further investigated with diverse thiol compounds. All tested thiol–ene reactions showed excellent efficiencies, with conversions of 93–97% under low-energy 3W blue LED light. In particular, thiol terminal p...

Lignin is an important source of synthetic materials because of its abundance in nature, low cost, stable supply, and no competition to the human food supply. Lignin, a cross-linked phenolic polymer, contains a large number of aromatic groups that can be used as a substitute for petroleum-based aromatic fine chemicals. However, modification of lignin is necessary for its application in advanced materials due to its chemically inert nature and structural complexity. Polymeric modification of lignin via graft copolymerization represents an important avenue for modification because this method forms stable covalent bond linkages between lignin and synthetic functional polymers. In this review, we discuss recent synthetic strategies toward polymeric modification of lignin using graft copolymerization and the special properties and applications of the produced lignin copolymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3515–3528

A general method, focusing upon olefin metathesis, was developed for the recovery of homogeneous olefin metathesis catalysts from crude reaction solutions. This method utilizes the supramolecular host–guest interaction between an azobenzene-modified N-heterocyclic carbene ligand and a silica-grafted β-cyclodextrin to remove homogeneous catalyst in a heterogeneous manner, allowing for the recovery of more than 97% of ruthenium in solution. The robust and simple nature of the guest molecule allows for the application of this method to a wide range of homogeneous catalysts. This study reports the synthesis and characterization of the said precatalyst and host compound as well as proof-of-concept recovery trials for a number of common substrates, with the residual ruthenium content of reaction mixtures evaluated by inductively coupled plasma mass spectrometry.

A bioinspired, modular terpolymer adhesive, poly(N-methacryloyl-3,4-dihydroxyl-l-phenylalanine-co-9-(acryloyloxy)butyl anthracene-9-carboxylate-co-acrylic acid), has been synthesized containing three different functionalities: a photo-cross-linking segment, a wet interfacial adhesion segment, and a water-soluble segment. The synthesized adhesive polymer is the first example of a single-phase, photo-cross-linkable adhesive which does not require additional photoinitiator or other cross-linking agents. The terpolymer demonstrates strong adhesion when it swells in water and/or ethanol. The terpolymer is composed of three repeating units: N-methacryloyl-3,4-dihydroxyl-l-phenylalanine (MDOPA), which has been known to generate strong adhesion under wet conditions, poly(acrylic acid), which has been known to increase water solubility of polymers, and a photo-cross-linking segment consisting of an anthracene-based monomer used for enhancement of cohesion properties via UV irradiation (352 nm). A photomediated [4 + 4] cycloaddition reaction of anthracene results in the cross-linking of individual polymer chains after interfacial adhesion between substrates and adhesive polymers. Chemically, the covalent photo-cross-linking was confirmed by UV-vis

We report the synthesis of a highly-functional macromonomer, and subsequent crosslinkable poly(ethylene glycol) (PEG)-based bottlebrush polymers prepared via graft-through ring-opening metathesis polymerization (ROMP). This work makes two important additions to the repertoire of bottlebrush polymers: (1) the first example of a catechol-derived brush adhesive relying on an internal ketone for post-polymerization modification; and (2) the post-polymerization modification is utilized to greatly affect the mechanical properties of the bulk material through oxime functionalization and subsequent metal-free click chemistry beginning from the innocuous, and easily introduced, internal ketone. This form of oxime ligation was demonstrated with a series of oxyamines, with degrees of functionalization on the range of 18–100%, while introducing further functionality in the form of azide groups, which were rapidly converted to corresponding triazoles via metal-free click chemistry using the crosslinker (1R, 8S, 9S)-bicyclo[6.1.0]non-4-yn-9-ylmethyl (BCN) bisfunctionalized PEG (Mn = ∼6000 g mol−1). Under these conditions, the transformation from soluble polymer solution to soft hydrogel occurs within minutes. The polymer described herein stands testament to the ability of modularly-designed macromonomers to dictate the structure and properties of downstream materials in a predicable fashion.

Glycopolymers are an important class of biomaterials which include carbohydrate moieties in their polymer structure. In addition to biological research on the interactions of glycopolymers with lectin-carbonate, glycopolymers have recently been used as a new synthetic biomaterial for direct therapeutic methods, medical adhesives, and biosensors. Thus, a comprehensive understanding of new advances in glycopolymer research is essential for the next level of biomaterial studies. This review article highlights commonly used glycopolymer synthesis methods and biomedical applications thereof. Glycopolymers can be synthesized by modern polymerization methods that can control the molecular weight, molecular weight distribution, chemical functionality, and polymer architecture. The polymerizations include free radical polymerization, atom transfer radical polymerization, reversible addition-fragmentation chain-transfer polymerization, and nitroxide-mediated polymerization. Because the carbohydrate-lectin interactions with glycopolymers are involved in many biological processes, carbohydrates containing glycopolymers are used in (1) fundamental studies to understand the specificity and strength of biological binding, (2) controllable interactions to prevent microorganism adhesion to human cells, (3) large scale bulk adhesives for medical applications, (4) biocompatible therapeutic nanoparticles, (5) direct drug delivery vehicles, and (6) precise quantitative measurement of biosensor materials that can detect physiological signals.

Lignin can be an important source of synthetic commodity materials owing to its abundance in nature and low production cost. The current use of lignin as a raw material, however, is very limited and focused only on cheap and poorly defined nonfunctional materials. Herein we report a new lignin-containing functional polymer, lignin-graft-poly(5-acetylaminopentyl acrylate) (lignin-graft-PAA), which has been prepared by the covalent linkage of chemically modified lignin with PAA, which is an end-group functionalized polymer. This work makes two significant advances in the study of lignin-containing polymers: (1) lignin-graft-PAA is the first example of lignin being modified by a polymer with sophisticated structure, and (2) lignin-graft-PAA shows a special performance, autonomic self-healing properties, which have not yet been seen in lignin-containing polymers. The key synthetic step in this process utilizes a copper-catalyzed azide–alkyne cycloaddition or “click” reaction in order to join together the lign...

A study of reaction kinetics and removal efficiency of a family of ruthenium (Ru)-based olefin metathesis catalysts containing ethylene-glycol-oligomer-tethered N-heterocyclic carbene (NHC) ligands has been carried out, with a focus on variation of ethylene glycol oligomer length. The length of ethylene glycol oligomer was precisely defined by sequential addition of repeating units. Due to the dual solubility of ethylene glycol oligomer, the produced catalyst was highly soluble in both aqueous and organic solvents (dichloromethane). In aqueous solution, the polarity increase with longer ethylene glycol oligomers enhanced the reactivity in homogeneous solution. The length of ethylene glycol oligomer did not significantly affect olefin metathesis rate in organic solution. Yet the removal efficiency of catalyst strongly relies on the length of ethylene glycol oligomer. A longer ethylene glycol oligomer demonstrated better catalyst removal efficiency. The tested catalyst removal method was aqueous extraction from organic solution using its higher water solubility property compared to its lower organic solvent (dichloromethane) solubility property. The results obtained from the aqueous extraction catalyst removal method demonstrated similar and/or better removal rates compared to previously reported host-guest catalyst removal methods.

A highly removable N-heterocyclic carbene ligand for a transition-metal catalyst in aqueous media via host–guest interactions has been developed. Water-soluble adamantyl tethered ethylene glycol in the ligand leads a hydrophobic inclusion into the cavity of β-cyclodextrin. Ruthenium (Ru) olefin metathesis catalyst with this ligand demonstrated excellent performance in various metathesis reactions in water as well as in CH2Cl2, and removal of residual Ru was performed via filtration utilizing a host–guest interaction and extraction.

Nanocomposites based on synthetic polymers grafted from kraft lignin with average particle size of 5 nm were synthesized using atom transfer radical polymerization (ATRP). Lignin macroinitiators were prepared, and polystyrene and poly(methyl methacrylate) were polymerized with target degree of polymerization of 450 resulting in materials having lignin mass fractions of 4.5%, 8.3%, and 22.1% for the poly(methyl methacrylate) samples and 3.2%, 7.1%, and 19.6% for the polystyrene samples. Tensile testing showed a decreased modulus but enhanced toughness of all nanocomposites compared to homopolymers, and the poly(methyl methacrylate)-grafted samples had nearly twice the ultimate elongation as the polystyrene grafts at high graft density. Both types of grafted nanocomposites had toughness values that were greater than 10-times that of the corresponding kraft-lignin/polymer blend system, indicating the potential of ATRP as the basis for the ‘one component’ composite approach towards more sustainable polymeric materials. Dynamical mechanical analysis was used to measure softening temperatures, and both the polystyrene-grafted and poly(methyl methacrylate)-grafted nanocomposites had a peak in the loss modulus that was higher than the corresponding homopolymer, consistent with strong polymer–lignin interactions. Lignin grafted with thermoplastic polymers could be an important material based on an inexpensive, renewable feedstock that offers unique mechanical properties compared with many other nanocomposites based on inorganic nanoparticles. Our results indicate that ATRP is well suited for preparing lignin-based thermoplastics and could be the basis for hybrid materials that make effective use of this important renewable resource.

There is a need for renewable resources as a raw material for commodity polymers. Lignin is one of the most important natural biopolymers from renewable resources due to its sufficient supply, robust material properties and the fact that its use does not compete with the food supply. Lignin has been investigated since the late 19th century, but its applications are limited due to poor processability, low reactivity and intrinsic heterogeneity depending on the plant source and isolation methods used. Current strategies for using lignin in modern materials center on integrating it with other natural or synthetic polymers. This review article introduces the technological importance of lignin and focuses on copolymers and blends based on lignin in a broad range of applications.

A new three-component bio-inspired adhesive was synthesized that is a terpolymer composed of a water-soluble segment, an interfacial adhesion segment, and a cross-linking segment. Strong wet adhesion properties are obtained utilizing a 3,4-dihydroxy-l-phenylalanine (DOPA) moiety. Poly(acrylic acid) provides high water solubility due to strong ionic interactions with water. An acrylic acid N-hydroxysuccinimide ester (NHS) was included in the adhesive polymer to allow rapid cross-linking with thiol-terminated, 3-armed poly(ethylene glycol) cross-linking agents. The thiol terminal poly(ethylene glycol) was designed to be bulky to avoid possible penetration of molecules to the cell and tissue. The NHS and thiol groups react within 30 s to form covalent bonds. This design allows for rapid optimization of properties for specific applications. Lap shear strength tests on wet porcine skin demonstrated a 190% increased value in adhesion strength for adhesives having the DOPA moiety. After cross-linking, adhesion was enhanced by 450% over poly(acrylic acid-co-acrylic acid NHS) and was 240% higher than un-cross-linked poly(acrylic acid-co-acrylic acid NHS-co-N-methacryloyl-3,4-dihydroxyl-l-phenylalanine). Rheology studies show adhesive viscosity drops significantly at high shear rates, demonstrating its potential to be injected via syringe. The cross-linked adhesive displayed much stronger mechanical properties and higher elastic and viscous moduli than an un-cross-linked adhesive model. Furthermore, the cross-linked adhesive has enhanced moduli near body temperature (38 °C) as compared to room temperature (23 °C), increasing the applications as a biomedical adhesive.

Lignin is the most important aromatic polymer from renewable resources due to its natural abundance, robust material properties, and the fact that its use does not directly compete with the food supply. Lignin has been investigated since the late nineteenth century, but it finds limited application due to poor processability, low reactivity, and intrinsic heterogeneity depending on the plant source and isolation methods used. Current strategies for using lignin in modern materials center on integrating it with other natural or synthetic polymers. This chapter introduces diverse types of lignin according to its extraction methods from raw biomass and focuses on commercial-grade mass production technologies of lignin and the effects of these processes on its chemical characteristics.

Chemical modification strategies to improve the mechanical properties of lignin-based polyurethanes are presented. We hypothesized that treatment of lignin with Lewis acids would increase the concentration of hydroxyl groups available to react with diisocyanate monomers. Under the conditions used, hydrogen bromide-catalyzed modification resulted in a 28% increase in hydroxyl group content. Associated increases in hydrophilicity of solvent-cast thin films were also recorded as evidenced by decreases in water contact angle. Polyurethanes were then prepared by first preparing a prepolymer based on mixtures of toluene-2,4-diisocyanate (TDI) and unmodified or modified lignin, then polymerization was completed through addition of polyethylene glycol (PEG), resulting in mass ratios of TDI:lignin:PEG of 43:17:40 in the compositions investigated here. The mixture of TDI and unmodified lignin resulted in a lignin powder at the bottom of the liquid, suggesting it did not react directly with TDI. However, a homogeneous solution resulted when TDI and the hydrogen bromide-treated lignin were mixed, suggesting demethylation indeed increased reactivity and resulted in better integration of lignin into the urethane network. Significant improvements in mechanical properties of modified lignin polyurethanes were observed, with a 6.5-fold increase in modulus, which were attributed to better integration of the modified lignin into the covalent polymer network due to the higher concentration of hydroxyl groups. This research indicates that chemical modification strategies can lead to significant improvements in the properties of lignin-based polymeric materials using a higher fraction of an inexpensive lignin monomer from renewable resources and a lower fraction an expensive, petroleum-derived isocyanate monomer to achieve the required material properties.

Hydroxy-functionalized isotactic poly(1-butene) was synthesized using transition metal-catalyzed regioselective C-H borylation at the side chain of the commercial polyolefin and subsequent oxidation of the boronic ester functionality. Functionalization up to ∼ 19 mol % of the termini of the ethyl side chain occurred without significant side reactions that could alter the polymer chain length. Esterification of the hydroxy group in the polymer with 2-bromoisobutyl bromide generated a side chain-functionalized polyolefin macroinitiator. Atom transfer radical polymerization of tert-butyl acrylate from the macroinitiator produced a high molecular-weight graft copolymer of the polyolefin, isotactic poly(1-butene)-graft-poly(tert-butyl acrylate) (PB-g-PtBA). Finally, the hydrolysis of the tert-butoxy ester group of PB-g-PtBA created an amphiphilic polyolefin, isotactic poly(1-butene)-graft-poly(acrylic acid), which contained a short carboxylic acid-functionalized polymer block at the side chain.

We present a study on the effects of cross-linking on the adhesive properties of bio-inspired 3,4-dihydroxyphenylalanine (DOPA). DOPA has a unique catechol moiety found in adhesive proteins in marine organisms, such as mussels and polychaete, which results in strong adhesion in aquatic conditions. Incorporation of this functional group in synthetic polymers provides the basis for pressure-sensitive adhesives for use in a broad range of environments. A series of cross-linked DOPA-containing polymers were prepared by adding divinyl cross-linking agent ethylene glycol dimethacrylate (EGDMA) to monomer mixtures of dopamine methacrylamide (DMA) and 2-methoxyethyl acrylate (MEA). Samples were prepared using a solvent-free microwave-assisted polymerization reaction and compared to a similar series of cross-linked MEA materials. Cross-linking with EGDMA tunes the viscoelastic properties of the adhesive material and has the advantage of not reacting with the catechol group that is responsible for the excellent adhesive performance of this material. Adhesion strength was measured by uniaxial indentation tests, which indicated that 0.001 mol % of EGDMA-cross-linked copolymer showed the highest work of adhesion in dry conditions, but non-cross-linked DMA was the highest in wet conditions. The results suggest that there is an optimal cross-linking degree that displays the highest adhesion by balancing viscous and elastic behaviors of the polymer but this appears to depend on the conditions. This concentration of cross-linker is well below the theoretical percolation threshold, and we propose that subtle changes in polymer viscoelastic properties can result in significant improvements in adhesion of DOPA-based materials. The properties of lightly cross-linked poly(DMA-co-MEA) were investigated by measurement of the frequency dependence of the storage modulus (G') and loss modulus (G''). The frequency-dependence of G' and magnitude of G'' showed gradual decreases with the fraction of EGDMA. Loosely cross-linked DMA copolymers, containing 0% and 0.001 mol % of EGDMA-cross-linked copolymers, displayed rheological behavior appropriate for pressure-sensitive adhesives characterized by a higher G' at high frequencies and lower G' at low frequencies. Our results indicate that dimethacrylate cross-linking of DMA copolymers can be used to enhance the adhesive properties of this unique material.

The challenge of having a medical device robustly and reversibly adhere to a tissue in a minimally-invasive way during a clinical procedure is significant and has yet to be solved. Materials that could perform this adhesion would be valuable for use in a wide array of devices, including wired and wireless endoscopes for gastrointestinal interventions; cardiovascular devices such as mobile robots that transverse the heart surface or fixation devices for open heart surgery; and for adhering craniectomy devices to the skull during decompressive treatment. Fibrillar patterned adhesives inspired by the micro- and nano-scale structures on the feet of geckos have been widely studied and synthesized and have shown great potential for reversible adhesion in dry environments. Preliminary work has also been conducted to enhance the adhesion of these materials in wet conditions by coating them with polymers that include dopamine methacrylamide (DMA), a synthetic sticky polymer inspired by the material found naturally in the holdfasts of mussels. These coated materials demonstrated wet adhesion enhancement at the nano-scale, but not at the macro-scale and not when compared to unpatterned materials. In this work, we take previously-developed gecko-inspired patterned arrays of fibers with mushroom-shaped tips which have demonstrated enhanced adhesion with respect to unpatterned materials in dry conditions and coat them with these same synthetic mussel-inspired polymers to enhance adhesion in fully-submerged wet environments. DMA-containing polymers were synthesized through a multistep process and applied to an array of micro-scale polyurethane fibers by stamping. Material samples were tested in a custom-built adhesion measurement system in contact with a 6 mm glass hemisphere in both dry and wet conditions. Flat DMA-stamped samples demonstrated as much as 7 times enhancement over uncoated samples, while patterned, coated samples demonstrated as much as 23 times adhesion enhancement. The sample also maintained 65% of its adhesive ability over 100 test cycles. These materials are the first to demonstrate reversible fibrillar adhesion in wet conditions at the macro-scale with respect to both unpatterned and uncoated materials on non-flat surfaces using intermolecular forces instead of suction forces. Versatile reversible materials capable of adhering to non-flat surfaces in wet conditions should continue to be studied for their value for a wide array of medical device applications.

In this work, we take previously developed gecko-foot-hair-inspired elastomer microfiber arrays with film-terminated and mushroom-shaped tips that have demonstrated enhanced adhesion with respect to unpatterned materials under dry conditions and coat them with synthetic DOPA-containing mussel-inspired polymers to enhance adhesion repeatedly in fully submerged wet environments. A new protocol for the development of this hybrid patterned, coated adhesive, which is suitable for use in contact with both wet and dry nonflat surfaces, is described. The experimental evaluation of repeatable adhesion under both wet and dry conditions for these materials is described and compared with unpatterned and/or uncoated materials. Macroscale reversible fibrillar adhesion enhancement on a nonflat, smooth glass surface when compared with unpatterned materials under fully submerged conditions is demonstrated with no suction effect.