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.

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.

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.

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.

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.

Fibrous membranes electrospinning from acrylonitrile-based polymers: specific absorption behaviors and states of water.

Fibrous membranes with a fiber diameter ranging from 80 to 800 nm are prepared from polyacrylonitrile and poly[acrylonitrile-co-(N-vinyl-2-pyrrolidone)] by the electrospinning process. The parameters can be controlled to fabricate fibrous membranes with similar fiber diameters (between 600 and 800 nm) for further studies on the swelling behaviors and water states. Water swelling experiments indicate that the fibrous membrane has a great capacity for water sorption, which reaches a maximum in a few minutes because of its extremely high porosity. Furthermore, a remarkable overshoot occurs as a result of polymer chain relaxation and the non-compact structure of the fibrous membranes. Contrary to the dense membrane, the equilibrium water content in the fibrous membrane decreases with the content of hydrophilic NVP though the maximum is almost the same. Results from DSC experiments demonstrate that only non-freezable bound water and free water can be distinguished in the fibrous membrane. On the basis of the results of water swelling and DSC experiments, it is concluded that the specific behaviors of the fibrous membranes are induced by the non-compact and pore-fiber discontinuous structure, which is different from either dense membranes or hydrogels. [GRAPHS: SEE TEXT] DSC curves of fully swollen electrospun fibrous membranes and of fully swollen dense membranes with different NVP contents.

Tethering poly(ethylene glycol)s to improve the surface biocompatibility of poly(acrylonitrile-co-maleic acid) asymmetric membranes.

To improve the surface biocompatibility, asymmetric membranes fabricated from poly(acrylonitrile-co-maleic acid)s (PANCMAs) synthesized by water-phase precipitation copolymerization were tethered (or immobilized) with poly(ethylene glycol)s (PEGs) by esterification reaction. Chemical changes on the membrane surface were characterized by Fourier transform infrared spectroscopy and elemental analysis to confirm the immobilization of PEG onto the PANCMA membranes. The hydrophilicity and blood compatibility of the PEG-tethered PANCMA membrane were investigated by water contact angle, water absorption, protein adsorption, plasma platelets adhesion and cell adhesion measurements, and the results were compared with the corresponding PANCMA membranes. It was found that, after the tethering of PEG, the hydrophilicity of the membrane can be improved significantly, and the protein adsorption, platelets adhesion and macrophage attachment on the membrane surface are obviously suppressed. Furthermore, not only the content of maleic acid in PANCMA, which influences the tethering density of PEG, but also the molecular weight of PEG has great effect on the surface modification of PANCMA membranes for biocompatibility.

Novel acrylonitrile-based copolymers containing phospholipid moieties: synthesis and characterization.

Novel acrylonitrile-based copolymers containing phospholipid moieties were synthesized by a three-step process, which included the copolymerization of acrylonitrile and 2-hydroxyethyl methacrylate (HEMA) in water and the reaction of the resulting poly[acrylonitrile-co-(2-hydroxyethyl methacrylate)]s (PANCHEMA) with 2-chloro-2-oxo-1,3,2-dioxaphospholane (COP) followed by the ring-opening reaction of COP with trimethylamine. The chemical structure of PANCHEMA and the phospholipid-containing acrylonitrile-based copolymers (PLCANCP) was analyzed with FT-IR spectroscopy, (1)H and (31)P NMR, and XPS. Surface properties of the studied copolymers were evaluated by the pure water contact angle, protein adsorption and platelets adhesion measurements. The water contact angle measured by sessile drop method decreased for the polymers in the following sequence: PAN, PANCHEMA, and PLCANCP. The adsorption amount of bovine serum albumin and the adhesive number of platelet followed the same decline sequence. These results demonstrate that the biocompatibility of the acrylonitrile-based copolymer membranes could be improved efficiently by the introduction of phospholipid moieties.

Hemocompatibility of poly(acrylonitrile-co-N-vinyl-2-pyrrolidone)s: swelling behavior and water states.

Hemocompatibility is an essential aspect of blood contacting polymers. Knowledge of the relationship between polymer structure and hemocompatibility is important in designing such polymers. In this work, the effect of swelling behavior and states of water on the hemocompatibility of poly(acrylonitrile-co-N-vinyl-2-pyrrolidone) (PANCNVP) films was studied. Platelet adhesion and plasma recalcification time tests were used to evaluate the hemocompatibility of the films. Considering the importance of surface properties on the hemocompatibility of polymers, static water contact angles were measured by both sessile drop and captive bubble methods. It was found that, on the film surface of PANCNVP with a higher NVP content, adhered platelets were remarkably suppressed and the recalcification time was longer. The total water content adsorbed on the PANCNVP film was determined through swelling experiments performed at temperatures of interest. Differential scanning calorimetry and thermogravimetric analysis were used to probe the states of water in the films. Based on the results from these experiments, it was hypothesized that the better hemocompatibility of PANCNVP films with higher NVP contents was due to their higher free water content, because water molecule exchange at the polymer/liquid interface, facilitated by a high free water content, is unfavorable for the formation of surface bound water, which causes poor hemocompatibility. [diagram in text].

Fabrication of perforated isoporous membranes via a transfer-free strategy: enabling high-resolution separation of cells.

Thin perforated membranes with ordered pores are ideal barriers for high-resolution and high-efficiency selective transport and separation of biological species. However, for self-assembled thin membranes with a thickness less than several micrometers, an additional step of transferring the membranes onto porous supports is generally required. In this article, we present a facile transfer-free strategy for fabrication of robust perforated composite membranes via the breath figure process, and for the first time, demonstrate the application of the membranes in high-resolution cell separation of yeasts and lactobacilli without external pressure, achieving almost 100% rejection of yeasts and more than 70% recovery of lactobacilli with excellent viability. The avoidance of the transfer step simplifies the fabrication procedure of composite membranes and greatly improves the membrane homogeneity. Moreover, the introduction of an elastic triblock copolymer increases the interfacial strength between the membrane and the support, and allows the preservation of composite membranes in a dry state. Such perforated ordered membranes can also be applied in other size-based separation systems, enabling new opportunities in bioseparation and biosensors.

Polydopamine gradients by oxygen diffusion controlled autoxidation.

We report a simple and facile protocol to fabricate mussel-inspired polydopamine (PDA) gradients on different surfaces. An oxygen diffusion phenomenon was used for dopamine autoxidation to form thickness gradients of PDA on different substrates. These PDA gradients showed gradual changes in thickness, roughness, wettability and light transmittance.

Facilitated and site-specific assembly of functional polystyrene microspheres on patterned porous films.

Functional patterned materials have received considerable attention because of their potential applications in biochips, sensors, and optical or electronic materials. Here, we report a versatile approach to functional patterned films based on facilitated and site-specific assembly of microspheres. This method includes the hierarchical formation of honeycomb-patterned porous films from amphiphilic block copolymers and the assembly of functional polystyrene microspheres driven by the gravity and the electrostatic interaction. Polystyrene microspheres containing carboxyl groups with a narrow size distribution were synthesized by dispersion polymerization. Honeycomb-patterned porous films were prepared from polystyrene-block-poly(N,N-dimethylaminoethyl methacrylate) (PS-b-PDMAEMA) by the breath figure method and then quaternized. We found that direct deposition of the microspheres on the patterned films reaches high filling ratio only when using ethanol dispersions that can wet the film pores. Plasma treatment of the films improves the hydrophilicity and introduces charged species to the external surface as well as the pore surface, leading to nonspecific assembly of microspheres. Negatively charged microspheres dispersed in buffer solution show a facilitated and site-specific assembly on the quaternized film. The electrostatic interaction as well as the gravity facilitates the assembly and the suborder arrangement of the hydrophilic PDMAEMA block around the pores is responsible for the site-specific assembly. In addition, we demonstrate the applicability of this method in preparing photoluminescent patterns by the assembly of porphyrinated microspheres, which is useful in various fields such as intelligent sensing.

Polymer surfaces structured with random or aligned electrospun nanofibers to promote the adhesion of blood platelets.

Fibrous membranes (nonwoven meshes) prepared via electrospinning technique have great potential in tissue engineering. This work is the first study on the behaviors of blood platelets at the nanostructured surface generated by electrospinning. Poly[acrylonitrile-co-(N-vinyl-2-pyrrolidone)] (PANCNVP) that shows excellent antiplatelet adhesion ability was directly electrospun onto its dense membrane surface. Polyacrylonitrile (PAN) samples were used as controls. The depth as well as the density of the nanofibers can be easily controlled. The results showed that the PANCNVP dense membrane certainly suppressed the activation and adhesion of platelets. However, whether the nanofibers and underlying membranes were composed of PAN or PANCNVP, the nanostructured surfaces promoted the activation, adhesion, and orientation of platelets. It was also found that, if the space between fibers was too large or the depth of fibers was too small, the nanostructured surface did not change the property of antiplatelet adhesion of PANCNVP. The promotion of activation and adhesion of platelets was obviously due to the presence of nanofibers, which induced the changes of surface topography and charge.

Surface modification of polyacrylonitrile-based membranes by chemical reactions to generate phospholipid moieties.

A novel approach for the surface modification of poly(acrylonitrile-co-2-hydroxyethyl methacrylate) (PANCHEMA) membranes by introducing phospholipid moieties is presented, which involved the reaction of the hydroxyl groups on the membrane surface with 2-chloro-2-oxo-1,3,2-dioxaphospholane (COP) followed by the ring-opening reaction of COP with trimethylamine. The chemical changes of phospholipid-modified acrylonitrile-based copolymers (PMANCP) membranes were characterized by Fourier transfer infrared spectroscopy and X-ray photoelectron spectroscopy. The surface properties of PMANCP membranes were evaluated by pure water contact angle, protein adsorption, and platelet adhesion measurements. Pure water contact angles measured by the sessile drop method on PMANCP membranes were obviously lower than those measured on the PANCHEMA membranes and decreased with the increase of the content of phospholipid moieties on the membrane surface. It was found that the bovine serum albumin adsorption and platelet adhesion were suppressed significantly with the introduction of phospholipid moieties on the membranes surface. These results demonstrated that the described process was an efficient way to improve the surface biocompatibility for the acrylonitrile-based copolymer membrane.