Self-Flipping Solar Seesaw Evaporators Leverage Scaling to De-Scale.

Salt scaling poses a significant obstacle to the practical implementation of solar-driven evaporation for desalination. Attempts to mitigate scaling by enhancing mass transfer often lead to a compromise in evaporation efficiency due to associated heat loss. In the present work, a novel seesaw evaporator with a Janus structure to harness scaling for periodic self-descaling is reported. The seesaw evaporators are facilely fabricated by delignifying balsa wood and subsequently single-sided spray-coating it with soot and polydimethylsiloxane (PDMS). This unique Janus structure enables the evaporator to float on the brine while ensuring an ample supply of solution for evaporation. During evaporation, salt ions are transported directionally toward the cocked end of the evaporator to form scaling, triggering the seesaw evaporator to flip once a threshold is reached. The accumulated salts re-dissolve back into the solution. By adjusting the tilt angle, the evaporator can achieve an impressive evaporation rate of up to 2.65 kg m-2 h-1 when evaporating an 8 wt.% NaCl solution. Remarkably, these evaporators maintain a stable evaporation rate during prolonged 120 h operation and produce ≈3.93-6.35 L m⁻2·day⁻¹ of freshwater from simulated brines when assembled into an evaporation device.

Poly(N,N-diethylacrylamide)-endowed spontaneous emulsification during the breath figure process and the formation of membranes with hierarchical pores.

The spontaneous emulsification for the formation of water-in-oil (W/O) or oil-in-water (O/W) emulsions needs the help of at least one kind of the third component (surfactant or cosolvent) to stabilize the oil-water interface. Herein, with the water/CS2-soluble polymer poly(N,N-diethylacrylamide) (PDEAM) as a surfactant, the spontaneous formation of water-in-PDEAM/CS2 emulsions is reported for the first time. The strong affinity between PDEAM and water or the increase of PDEAM concentration will accelerate the emulsification process with high dispersed phase content. It is demonstrated that the spontaneous emulsification of condensed water droplets into the PDEAM/CS2 solution occurs during the breath figure process, resulting in porous films with two levels of pore sizes (i.e., micron and submicron). The emulsification degree and the amounts of submicron-sized pores increase with PDEAM concentration and solidifying time of the solution. This work brings about incremental interest in spontaneous emulsification that may happen during the breath figure process. The combination of these two simultaneous processes provides us with an option to build hierarchically porous structures with condensed and emulsified water droplets as templates. Such porous membranes may have great potential in fields such as separation, cell culture, and biosensing.

Polystyrenes with both hydrophilic and hydrophobic moieties: synthesis and self-assembly behaviors.

Fluorinated polymers are emerging as important alternatives for isoporous film fabrication by the breath figure technique, originating from the special characteristics endowed by fluorine elements such as low surface energy and good chemical stability. In this work, we design and synthesize polystyrenes (∼3600 Da) with perfluoroalkyl groups (-C3F7 or -C7F15) at both chain ends and hydrophilic oligo(ethylene glycol) units ((C2H4O)n, n = 1/2/3) in the chain middle by taking advantage of the bifunctional atom transfer radical polymerization (ATRP) initiators and post-substitution of the terminal bromine. We investigate the influence of the two disparate groups on the physical characteristics of the polymers and self-assembly behaviors during the dynamic breath figure process. It shows that the elongation of hydrophilic segments can greatly decrease the interfacial tension between the polymer solution and water (from 41.8 to 37.4 mN m-1), and the functionalization with perfluoroalkyl end groups diminishes the ability of the polymers to precipitate at the interface, as demonstrated by the cloud point results. Studies of the morphology of the porous films suggest that both low interfacial tension and strong capability of interfacial precipitation are beneficial to droplet stabilization and honeycomb pattern formation at low solution concentrations.

Rapid Immobilization of Silver Nanoparticles via Amino-quinone Coatings Enables Surface-Enhanced Raman Scattering Detection.

Immobilization of metal nanoparticles (NPs) on flexible substrates for surface-enhanced Raman scattering (SERS) has received great attention. Anchoring NPs on substrates generally involves the process of surface modification, thanks to its simple, universal, and nondestructive features. 2-Hydroxy-1,4-naphthoquinone (HNQ), a plant-derived compound used to dye hairs and nails, may interact with polyamine or metal ions to form a surface coating. Here, we report the formation of amino-quinone coatings via the co-deposition of HNQ and polyethyleneimine, which provides a functionalized platform to rapidly immobilize Ag NPs on substrates such as a poly(dimethylsiloxane) (PDMS) film to fabricate Ag-PDMS substrates for SERS detection. The detection concentrations are down to 10-8 M for rhodamine 6G. This work expands the system of surface co-deposition and further provides a facile route to prepare a highly efficient SERS substrate.

Surface Coatings via the Assembly of Metal-Monophenolic Networks.

Mussel-inspired surface modification has received significant interest in recent years because of its simplicity and versatility. The deposition systems are still mainly limited to molecules with catechol chemical structures. In this paper, we report a novel deposition system based on a monophenol, vanillic acid (4-hydroxy-3-methoxybenzoic acid), to fabricate metal-phenolic network coatings on various substrates. The results of the water contact angle and zeta potential reveal that the modified polypropylene microfiltration membrane is underwater superhydrophobic and positively charged, showing applications in oil/water separation and dye removal. Furthermore, the single-face modified Janus membrane is promising in switchable oil/water separation. The results demonstrate a novel example of the metal-monophenolic deposition system, which expands the toolbox of surface coatings and facilitates the understanding of the deposition of phenols.

Engineered Coatings via the Assembly of Amino-Quinone Networks.

Engineering coatings with precise physicochemical properties allows for control over the interface of a material and its interactions with the surrounding environment. However, assembling coatings with well-defined properties on different material classes remains a challenge. Herein, we report a co-assembly strategy to precisely control the structure and properties (e.g., thickness, adhesion, wettability, and zeta potential) of coatings on various materials (27 substrates examined) using quinone and polyamine building blocks. By increasing the length of the amine building blocks from small molecule diamines to branched amine polymers, we tune the properties of the films, including the thickness (from ca. 5 to ca. 50 nm), interfacial adhesion (0.05 to 5.54 nN), water contact angle (130 to 40°), and zeta potential (-42 to 28 mV). The films can be post-functionalized through the in situ formation of diverse nanostructures, including nanoparticles, nanorods, and nanocrystals. Our approach provides a platform for the rational design of engineered, substrate-independent coatings for various applications.

Surface Metallization of Porous Polymer Materials for Multifunctional Applications.

Porous materials have attracted great interest in recent years, and a variety of surface modification methods have been developed to endow porous materials with multifunctional applications. Herein, multifunctional porous materials are fabricated based on surface metallization. Metallized sponges with Ag and Cu are highly hydrophobic and are still hydrophobic under oil. The metallized sponges selectively adsorb oils from oil/water mixtures and can completely remove oils from water. We further demonstrate continuous oil-water separation by the metallized sponges with the aid of a peristaltic pump. The Ag-metallized materials show high catalytic performance for both chemical reduction and dye degradation. The catalytic reduction efficiency of 4-nitrophenol reaches 97.7% within 60 min and remains as high as 96% after 15 cycles. Moreover, the metallized materials show 99.99% bactericidal efficiency for both Staphylococcus aureus and Escherichia coli. Particularly, the Cu-metallized materials exhibit stable conductivity under deformation; and metal patterns are realized via the metallization method combined with a patterned mask, which may provide a feasible approach for flexible electronics. This work provides a versatile method to introduce metal coatings to porous materials, broadening the applications of porous materials.

Surface Deposition of Juglone/FeIII on Microporous Membranes for Oil/Water Separation and Dye Adsorption.

Deposition of dopamine and tannic acid has received great attention in the fields of surface and interface science and technology. The deposition behaviors of various metal-phenolic systems have been investigated, and it is generally accepted that at least one catechol group is essential to the formation of the coatings. Herein, we report a novel and effective surface-coating system based on the coordination complexes of FeIII ions with a natural product juglone that contains only one phenolic hydroxyl. We investigated the deposition behaviors of this novel system on various substrates. Microporous polypropylene membrane modified with juglone/FeIII coatings is superhydrophilic and underwater superoleophobic, showing high separation efficiency and good reusability for various oil/water emulsions. In addition, the modified membrane can adsorb anionic dyes and selectively remove them from dye mixtures with high efficiency. We further demonstrated that the coating is a result of the synergetic effect of juglone/FeIII coordination and FeIII hydrolysis. This work not only provides new insights into surface deposition systems but also expands the polyphenol family for surface coatings of multifunctional materials.

CuSO4/H2O2-Induced Rapid Deposition of Polydopamine Coatings with High Uniformity and Enhanced Stability.

Mussel-inspired polydopamine (PDA) deposition offers a promising route to fabricate multifunctional coatings for various materials. However, PDA deposition is generally a time-consuming process, and PDA coatings are unstable in acidic and alkaline media, as well as in polar organic solvents. We report a strategy to realize the rapid deposition of PDA by using CuSO4/H2O2 as a trigger. Compared to the conventional processes, our strategy shows the fastest deposition rate reported to date, and the PDA coatings exhibit high uniformity and enhanced stability. Furthermore, the PDA-coated porous membranes have excellent hydrophilicity, anti-oxidant properties, and antibacterial performance. This work demonstrates a useful method for the environmentally friendly, cost-effective, and time-saving fabrication of PDA coatings.

Highly Stable, Protein-Resistant Surfaces via the Layer-by-Layer Assembly of Poly(sulfobetaine methacrylate) and Tannic Acid.

Zwitterionic materials have received great attention because of the non-fouling property. As a result of the electric neutrality of zwitterionic polymers, their layer-by-layer (LBL) assembly is generally conducted under specific conditions, such as very low pH values or ionic strength. The formed multilayers are unstable at high pH or in a high ionic strength environment. Therefore, the formation of highly stable multilayers of zwitterionic polymers via the LBL assembly process is still challenging. Here, we report the LBL assembly of poly(sulfobetaine methacrylate) (PSBMA) with a polyphenol, tannic acid (TA), for protein-resistant surfaces. The assembly process was monitored by a quartz crystal microbalance (QCM) and variable-angle spectroscopic ellipsometry (VASE), which confirms the formation of thin multilayer films. We found that the (TA/PSBMA)n multilayers are stable over a wide pH range of 4-10 and in saline, such as 1 M NaCl or urea solution. The surface morphology and chemical composition were characterized by specular reflectance Fourier transform infrared spectroscopy (FTIR/SR), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Furthermore, (TA/PSBMA)n multilayers show high hydrophilicity, with a water contact angle lower than 15°. A QCM was used to record the dynamic protein adsorption process. Adsorption amounts of bovine serum albumin (BSA), lysozyme (Lys), and hemoglobin (Hgb) on (TA/PSBMA)20 multilayers decreased to 0.42, 52.9, and 37.9 ng/cm(2) from 328, 357, and 509 ng/cm(2) on a bare gold chip surface, respectively. In addition, the protein-resistance property depends upon the outmost layer. This work provides new insights into the LBL assembly of zwitterionic polymers.

Ordered microporous membranes templated by breath figures for size-selective separation.

Membranes with highly uniform pore size are important in various fields. Here we report the preparation and performance of ordered membranes, the pore diameter of which is on the micrometer scale. The ordered membranes fabricated at two-phase interfaces enable a high-resolution and energy-saving separation process. Moreover, a possible mechanism for the formation of through-pores has been proposed and experimentally verified.

Glycopolymer brushes for the affinity adsorption of RCA120: effects of thickness, grafting density, and epitope density.

The interactions between glycopolymer brushes and lectin are very important for the development of affinity membrane chromatography in protein separation. Here, we report the combination of surface-initiated atom transfer radical polymerization (SI-ATRP) and surface plasmon resonance (SPR) to investigate the relationship between the structure of glycopolymer brushes and the affinity adsorption of lectin. The glycopolymer brushes were fabricated from self-assembly of 11-mercapto-1-undecanol (MUD)/1-undecanethiol (UDT) mixture, immobilization of ATRP initiators, and then SI-ATRP of 2-lactobionamidoethyl methacrylate (LAMA). Brush thickness and grafting density were adjusted by controlling polymerization time and thiol ratio in MUD/UDT mixture, respectively. Sugar epitope density was also controlled through copolymerization of 2-hydroxylethyl methacrylate (HEMA) with LAMA. Ricinus communis agglutinin (RCA(120)), one kind of lectin that can bind galactose specifically, was chosen to study the effects of brush architectures on lectin adsorption. SPR results indicate not only the thickness but also the grafting density and the epitope density of glycopolymer brushes can achieve the best performance of sugar cluster effect in affinity adsorption of lectin. In addition, the mass transport effect is crucial in the adsorption process. We propose that it is important to keep the balance between the sugar cluster effect and the mass transport effect in the preparation of high-performance affinity membrane chromatography.

Honeycomb-patterned film segregated with phenylboronic acid for glucose sensing.

Phenylboronic acid (PBA)-functionalized materials have attracted considerable attention because of their potential applications in many fields. In this paper, we report a PBA-segregated honeycomb-patterned porous film (HPPF) for glucose sensing. Polystyrene-block-poly(acrylic acid-co-acrylamidophenylboronic acid) with different contents of PBA pendants was synthesized via atom transfer radical polymerization (ATRP) followed by a coupling reaction. PBA-functionalized HPPFs were then fabricated by the breath figure method. Results indicate that the composition of the copolymers and the relative humidity play key roles in pore size and regularity of the films. Using Alizarin Red S (ARS) that does not emit fluorescence itself as a fluorescent probe, it is confirmed that PBA pendants are mainly distributed at the pore wall, instead of at the outer surface of HPPFs. This distribution is caused by the segregation of hydrophilic PBA-blocks toward the condensed water droplets, which act as templates for the pore formation. Quartz crystal microbalance results demonstrate that the PBA-functionalized HPPFs show high sensitivity in glucose sensing, which is owing to the segregation of PBA pendants at the pore wall as well as the large specific surface area of the porous films.

Selective layer-by-layer self-assembly on patterned porous films modulated by Cassie-Wenzel transition.

We describe a robust and facile approach to the selective modification of patterned porous films via layer-by-layer (LBL) self-assembly. Positively charged honeycomb-patterned films were prepared from polystyrene-block-poly(N,N-dimethyl-aminoethyl methacrylate) (PS-b-PDMAEMA) and a PS/PDMAEMA blend by the breath figure method followed by surface quaternization. Alginate and chitosan were alternately deposited on the films via LBL self-assembly. The assembly on the PS-b-PDMAEMA film exhibits two stages with different growth rates, as elucidated by water contact angles, fluorescence microscopy, and quartz crystal microbalance results. The assembly can be controlled on the top surface or across all surfaces of the film by changing the number of deposition cycles. We confirm that there exists a Cassie-Wenzel transition with an increase in deposition cycles, which is responsible for the tunable assembly. For the PS/PDMAEMA film, the pores can be completely wetted and the polyelectrolytes selectively assemble inside the pores, instead of on the top surface. The controllable selective assembly forms unique hierarchical structures and opens a new route for surface modification of patterned porous films.

Less-Ordered Hydration Shell around Poly(N,N-diethylacrylamide) Is Insensitive to the Clouding Transition.

Raman multivariate curve resolution (Raman-MCR) is applied to examine how the hydration shell around poly(N,N-diethylacrylamide) (PDEAM) changes upon heating, in comparison with poly(N-isopropylacrylamide) (PNIPAM), both of which undergo a clouding transition near room temperature. We report that PDEAM possesses a less-ordered and smaller hydration shell than PNIPAM. Furthermore, the PDEAM hydration-shell structure is insensitive to the occurrence of clouding, indicating the coil-globule transition and aggregation of multiple chains can be achieved without the hydration-shell structural transformation.

Controllable construction of carbohydrate microarrays by site-directed grafting on self-organized porous films.

Carbohydrate-protein interactions are critical in many biological processes. However, the interactions between individual carbohydrates and proteins are often of low affinity and difficult to study. Recent development of carbohydrate microarrays provides an effective tool to explore the interaction. In this work, carbohydrate microarrays were controllably constructed by grafting of a carbohydrate-containing monomer on self-organized honeycomb-patterned films. The films were prepared from an amphiphilic block copolymer, poly(styrene-block-(2-hydroxyethyl methacrylate)), by a breath figure method. Three-dimensional fluorescence results demonstrate that the hydroxyl groups aggregate mainly inside the pores, which afford a chance of site-directed surface modification. 2-(2,3,4,6-Tetra-O-acetyl-beta-D-glucosyloxy)ethyl methacrylate was selectively grafted in the pores by a surface-initiated atom transfer radical polymerization. Characterization by attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, and contact angle measurements confirms the site-directed growth of the glycopolymer chains. Further specific recognition of the carbohydrate microarrays to lectin (concanavalin A) leads to an organized microarray of protein, and hence this approach also opens a new route to fabricating other functional microarrays such as protein-patterned surfaces.

Tunable assembly of nanoparticles on patterned porous film.

This paper describes an approach to fully selective assembly of nanoparticles on patterned porous surface. Copolymers of polystyrene-block-poly(N,N-dimethylaminoethyl methacrylate) synthesized by atom transfer radical polymerization were used to prepare honeycomb-patterned porous films by the breath figure method. The regularity and pore size of the films can be modulated by changing the polymer composition and casting conditions such as concentration and airflow speed. Positively charged films were fabricated directly from the quaternized copolymers or by surface quaternization. X-ray photoelectron spectroscopy and adsorption of negatively charged fluorescein sodium salt confirmed the quaternization. Then assembly of negatively charged silica nanoparticles from its aqueous dispersion was performed. Results indicate that they assemble on the external surface of patterned porous films that without prewetting. For prewetted films, the nanoparticles assemble both on the external surface and in the pores. Poly(acrylic acid) deposited from its aqueous solution can serve as an effective blocking layer, which directs the selective assembly of nanoparticles into the pores, instead of the external surface of the film. It is concluded that the Cassie-Wenzel transition is the key to the selective assembly on the highly porous films. The well-defined selective assembly forms unique hierarchical structures of nanoparticles and greatly enlarges the diversity of structures of nanoparticle aggregates. This general approach also opens a straightforward route to the selective modification of patterned porous films.

Recognition mechanism of theophylline-imprinted polymers: two-dimensional infrared analysis and density functional theory study.

Molecular imprinting polymers (MIPs) are synthetic materials having specific cavities tailored for a target molecule. Thoroughly understanding the molecular recognition mechanism is favorable for the rational design, preparation, and application of MIPs. In this work, theophylline (THO)-imprinted poly(acrylonitrile-co-acrylic acid) (PANCAA) films with acrylic acid (AA) as the functional monomer were fabricated and a set of concentration-dependent Fourier transform infrared (FT-IR) spectra were collected. Two-dimensional (2D) correlation analysis of the spectra and density functional theory (DFT) calculation were conducted to evaluate the molecular recognition mechanism. DFT at the B3LYP/6-31+G(d,p) level is efficacious to calculate the binding energies (DeltaE) and the theoretical vibration frequencies for the possible configurations of THO_AA complexes. An optimized cyclic hydrogen-bonded configuration (complex THO_AA1) has the highest binding energy (-16.63 kcal mol(-1)) that is more stable than others. In addition, the experimental vibrations of the carbonyl groups in the FT-IR spectra were assigned on the basis of the DFT results. Moreover, methylacrylic acid (MAA) and caffeine (CAF) as compared analogues were also investigated. The DFT-based theoretical predictions are coincident with the reported results.

Diffusion and structure of water in polymers containing N-vinyl-2-pyrrolidone.

Poly(N-vinyl-2-pyrrolidone) (PVP), a water-soluble polymer, is known for its excellent biocompatibility. It is generally recognized that the properties of polymers may be profoundly affected by the structure of water absorbed in them. In this study, Fourier transform infrared (FT-IR) in attenuated total reflection (ATR) and transmission mode was performed to examine the diffusion and structure of water in PVP and its copolymers. The obtained spectra were analyzed using two-dimensional (2D) IR with the aid of density functional theory (DFT) calculations. The 2D IR of time-resolved FT-IR/ATR spectra shows that type II water between 3300 and 3500 cm(-1) occurs earlier during the water absorption process, which is also demonstrated by transmission FT-IR at the initial stage of water absorption. Conversely, type II water changes last when desorption takes place. Results from DFT calculations indicate that type II water might be monomeric or dimeric water molecules interacting with a carbonyl group in the pyrrolidone moiety. Furthermore, it is found that vibrations less than 3300 cm(-1) (type I water) arise from water molecules involved in a carbonyl group interacting with more than two water molecules. It is reasonable that the transmission FT-IR spectra of film with an extra low water amount hardly show vibration bands below 3300 cm(-1); however, this region is distinct in the FT-IR/ATR spectra of fully swollen film. In addition, vibration bands between 3800 and 3500 cm(-1) (type III water) are assigned to free water or water with relatively weak hydrogen bonding, as supported by the transmission FT-IR spectra of polyacrylonitrile (PAN) and the calculation results. Therefore, the diffusion process and the structures of water in PVP and its copolymers can be successfully accessed on the basis of the 2D IR analysis and DFT calculations.

Cytocompatibility of poly(acrylonitrile-co-N-vinyl-2-pyrrolidone) membranes with human endothelial cells and macrophages.

Polyacrylonitrile modified with N-vinyl-2-pyrrolidone (NVP) shows good hemocompatibility. This work, which aims to evaluate the cytocompatibility of membranes fabricated from poly(acrylonitrile-co-N-vinyl-2-pyrrolidone) (PANCNVP), studied the adhesion of macrophages and endothelial cell (EC) cultures. It was found that PANCNVP membranes with higher NVP content decreased the adhesion of both macrophages and ECs. Compared with polyacrylonitrile and tissue culture polystyrene control, however, these PANCNVP membranes promoted the proliferation of ECs. Furthermore, the viability of ECs cultured on the PANCNVP membrane surfaces was also relatively competitive. Both static and dynamic water contact angle measurements were conducted to explain the nature of cell adhesion to the PANCNVP membranes. On the basis of these results and the phenomena of water swelling and water states reported previously, it was presumed that the coexistence of large amounts of bound water and free water induced by NVP moieties are responsible for the lower adhesion and better function of cells adhering to the PANCNVP membranes.