Copolymerization Kinetics of Dopamine Methacrylamide during PNIPAM Microgel Synthesis for Increased Adhesive Properties.

Combining stimuli-responsive properties of gels with adhesive properties of mussels is highly interesting for a large field of applications as, e.g., in life science. Therefore, the present paper focuses on the copolymerization of poly(N-isopropylacrylamide) (PNIPAM) microgels with dopamine methacrylamide (DMA). A detailed understanding of reaction kinetics is crucial to figure out an optimized synthesis strategy for tailoring microgels with adhesive properties. The present study addresses the influence of relevant synthesis parameters as the injection time of DMA during the microgel synthesis and the overall reaction time of the microgel. Reaction kinetics were studied by mass spectrometry of time samples taken during the microgel synthesis. This allowed us to determine the monomer consumption of NIPAM, the cross-linker N,N'-methylenebisacrylamide (BIS), and DMA. A second-order reaction kinetics was found for DMA incorporation. The amount of DMA incorporated in the resulting microgel was successfully determined by a combination of UV-vis and NMR spectroscopy to level off limitations of both methods. The dependence of the hydrodynamic radius on temperature was determined by DLS measurements for the microgels. While an early injection of DMA stops the PNIPAM polymerization due to scavenging, it greatly enhances the reaction speed of DMA. The faster reaction of DMA and the incomplete NIPAM and BIS conversion also compensate for shorter reaction times with respect to the incorporated amount of DMA. On the contrary, a later injection of DMA leads to a full NIPAM monomer and BIS cross-linker consumption. An overall reaction time of 60 min ensures the DMA incorporation. Longer reaction times lead to clumping. First adhesion tests show an increased adhesion of P(NIPAM-co-DMA) microgels compared to pure PNIPAM microgels, when mechanical stress is applied.

Immobilization of Gold Nanoparticles in Spherical Polymer Brushes Observed by Small-Angle X-ray Scattering.

Nanosized gold nanoparticles (AuNPs) are of great interest in areas such as catalysts or imaging but are easy to aggregate due to high surface activity. To stabilize AuNPs, two approaches were employed to immobilize AuNPs in spherical polymer brushes (SPBs), namely, the in situ preparation of AuNPs within the brush layer of SPBs and external addition of preprepared citrate-capped AuNPs. The distribution and stability of AuNPs in SPBs were studied by small-angle X-ray scattering (SAXS). SAXS results demonstrated that the in situ-prepared AuNPs were mainly located on the inner layer and their amount decreased from inside to outside. In the case of external addition of preprepared AuNPs, the cationic SPB showed obvious immobilization, while almost no AuNPs were immobilized in the anionic SPB. The stable immobilization of the AuNPs in SPBs was the result of multiple interactions including complexation and electrostatic interaction. SAXS was validated to be a distinctive and powerful characterization method to provide theoretical guidance for the stable immobilization of AuNPs.

Dendrimer-Based Polyion Complex Vesicles: Loops Make Loose.

Associations of amphiphiles assume their various morphologies according to the so-called packing parameter under thermodynamic control. However, one may raise the question of whether polymers can always relax fast enough to obey thermodynamic control, and how this may be checked. Here, a case of polyion complex (PIC) assemblies where the morphology appears to be subject to kinetic control is discussed. Poly (ethylene oxide)-b-(styrene sulfonate) block copolymers are combined with cationic PAMAM dendrimers of various generations (2-7). The PEO-PSS diblocks, and the corresponding PSS-PEO-PSS triblocks should have nearly identical packing parameters, but surprisingly creat different assemblies, namely core-shell micelles and vesicles, respectively. Moreover, the micelles are very stable against added salt, whereas the vesicles are not only much more sensitive to added salt, but also appear to exchange matter on relevant time scales. The small and largely quenched early-stage precursor complexes are responsible for the morphological and dynamic differences, implying that kinetic control may also be a way to obtain particles with well-defined and useful properties. The exciting new finding that triblocks produce more "active" vesicles will hopefully trigger the exploration of more pathways, and so learn how to tune PICsomes toward specific applications.

Regulated Polyelectrolyte Nanogels for Enzyme Encapsulation and Activation.

Polyelectrolyte (PE) nanogels consisting of cross-linked PE networks integrate the advanced features of both nanogels and PEs. The soft environment and abundant intrinsic charges are of special interest for enzyme immobilization. However, the crucial factors that regulate enzyme encapsulation and activation remain obscure to date. Herein, we synthesized cationic poly (dimethyl aminoethyl methacrylate), PDMAEMA, nanogels with well-defined size and cross-link degrees and fully investigated the effects of different control factors on lipase immobilization. We demonstrate that the cationic PDMAEMA nanogels indeed enable efficient and safe loading of anionic lipase without disturbing their structures. Strong charge interaction achieved by tuning pH and larger particle size are favorable for lipase loading, while the enhanced enzymatic activity demands nanogels with smaller size and a moderate cross-link degree. As such, PDMAEMA nanogels with a hydrodynamic radius of 35 nm and 30% cross-linker fraction display the optimal catalytic efficiency, which is fourfold of that of free lipase. Moreover, the immobilization endows enhanced enzymatic activity in a broad scope of pH, ionic strength, and temperature, demonstrating effective protection and activation of lipase by the designed nanogels. Our study validates the crucial controls of the size and structure of PE nanogels on enzyme encapsulation and activation, and the revealed findings shall be helpful for designing functional PE nanogels and boosting their applications for enzyme immobilization.

Dual-Functionalized Crescent Microgels for Selectively Capturing and Killing Cancer Cells.

In cancer therapy, the selective targeting of cancer cells while avoiding side effects to normal cells is still full of challenges. Here, we developed dual-functionalized crescent microgels, which selectively captured and killed lung cancer cells in situ without killing other cells. Crescent microgels with the inner surface of the cavity functionalized with antibody and containing glucose oxidase (GOX) in the gel matrix have been produced in a microfluidic device. These microgels presented high affinity and good selectivity to lung cancer cells and retained them inside the cavities for extended periods of time. Exposing the crescent hydrogels to physiological concentrations of glucose leads to the production of a locally high concentration of H2 O2 inside the microgels' cavities, due to the catalytic action by GOX inside the gel matrix, which selectively killed 90 % cancer cells entrapped in the microgel cavities without killing the cells outside. Our strategy to create synergy between different functions by incorporating them in a single microgel presents a novel approach to therapeutic systems, with potentially broad applications in smart materials, bioengineering and biomedical fields.

Controlled Fabrication of Micropatterned Supramolecular Gels by Directed Self-Assembly of Small Molecular Gelators.

Herein, the micropatterning of supramolecular gels with oriented growth direction and controllable spatial dimensions by directing the self-assembly of small molecular gelators is reported. This process is associated with an acid-catalyzed formation of gelators from two soluble precursor molecules. To control the localized formation and self-assembly of gelators, micropatterned poly(acrylic acid) (PAA) brushes are employed to create a local and controllable acidic environment. The results show that the gel formation can be well confined in the catalytic surface plane with dimensions ranging from micro- to centimeter. Furthermore, the gels show a preferential growth along the normal direction of the catalytic surface, and the thickness of the resultant gel patterns can be easily controlled by tuning the grafting density of PAA brushes. This work shows an effective "bottom-up" strategy toward control over the spatial organization of materials and is expected to find promising applications in, e.g., microelectronics, tissue engineering, and biomedicine.

Mineralized Supramolecular Hydrogels Bearing Tunable Thermo-Responsiveness.

Although a variety of biomimetic mineralized materials have been created in the lab, the vast majority of these manmade examples lack response to external stimuli. Here, mineralized supramolecular hydrogels with on-demand thermo-responsiveness that are formed by a simple, physical crosslinking between amorphous CaCO3 (ACC) nanoparticles and poly(acrylic acid) (PAA) are reported. Upon the addition of Na2 CO3 solution into a mixture composed of PAA and CaCl2 , amorphous ACC nanoparticles are formed in situ and simultaneously crosslinked by PAA chains, giving rise to the mineralized hydrogels. Interestingly, upon tuning the content of the formed ACC, hydrogels with different types of thermo-responsiveness can be easily obtained, and the transparencies of the resulting hydrogels are dramatically changed during the temperature-driven phase transitions. As an application, these thermo-responsive mineralized hydrogels are used to control the exposure of UV light, which is successfully applied to switch fluorescent signals in response to temperature.

Kinetic, isotherm, and thermodynamic studies of the adsorption of dyes from aqueous solution by cellulose-based adsorbents.

In this study, a highly efficient and eco-friendly porous cellulose-based aerogel was synthesized by grafting polyethyleneimine onto quaternized cellulose (PQC) to remove the anionic dye Congo Red (CR). The prepared aerogel had a good flexibility and formability. The adsorbents were characterized by scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy and elemental analysis. The results showed that there were many amino groups on CE/PQC aerogel and the structure was porous, which increased the adsorption capacity. The effects of initial concentration, adsorbent dose, contact time, temperature, and pH on the dye sorption were all investigated. The adsorption mechanism was also explored, including adsorption kinetics, adsorption isotherms and thermodynamic studies of adsorption. The results showed that the adsorption kinetics and isotherms fitted the pseudo-second-order kinetic model and Langmuir isotherm, respectively. The Langmuir isotherm revealed that the maximum theoretical adsorption capacity of the aerogels for CR was 518.403 mg g-1. The thermodynamic parameters including Gibbs free energy change (ΔG0), enthalpy change (ΔH0) and entropy change (ΔS0), showed the adsorption process was exothermic and spontaneous. These results imply that this new absorbent can be universally and effectively used for the removal of dyes from industrial textile wastewater.

A Supramolecular Crosslinker To Give Salt-Resistant Polyion Complex Micelles and Improved MRI Contrast Agents.

Three-component mixtures (diblock copolymer/metal ion/oligoligand) can assemble into micellar particles owing to a combination of supramolecular polymerization and electrostatic complex formation. Such particles cover a large range of compositions, but the electrostatic forces keeping them together make them rather susceptible to disintegration by added salt. Now it is shown how the salt stability can be tuned continuously by employing both a bis-ligand and a tris-ligand, and varying the ratio of these in the mixture. For magnetic ions such as MnII and FeIII , the choice of the multiligand also affects the ion/water interaction and, hence, the magnetic relaxivity. As an example, MnII -based nanoparticles with a very high longitudinal relaxivity (10.8 mm-1 s-1 ) were investigated that are not only biocompatible but also feature strong contrast enhancement in target organs (liver, kidney), as shown by T1 -weighted in vivo magnetic resonance imaging (MRI).

Ultrastretchable, Tough, and Notch-Insensitive Hydrogels Formed with Spherical Polymer Brush Crosslinker.

Spherical polymer brushes, poly(acrylic acid) (PAA)-grafted polystyrene nanoparticle (PAA@PS), are employed as the macro-crosslinker to prepare PAA hydrogels. Benefitting from the innumerable hydrogen bonds between highly entangled PAA chains both in bulk and on the polymer brush, the PAA/PAA@PS hydrogels combine desirable stretchability, toughness, and notch-insensitivity. The uniaxial tensile tests show a very high fracture elongation up to 9.1 × 103 % while the fracture toughness reaches 3.0 MJ m-3 and the maximum swelling ratio of the hydrogel can be 2.0 × 103 as well. After being loaded with silver nanoparticles, the PAA/PAA@PS hydrogels are employed as a recyclable catalyst successfully.

Construction of Compact Polyelectrolyte Multilayers Inspired by Marine Mussel: Effects of Salt Concentration and pH As Observed by QCM-D and AFM.

Biomimetic multilayers based on layer-by-layer (LbL) assembly were prepared as functional films with compact structure by incorporating the mussel-inspired catechol cross-linking. Dopamine-modified poly(acrylic acid) (PAADopa) was synthesized as a polyanion to offer electrostatic interaction with the prelayer polyethylenimine (PEI) and consecutively cross-linked by zinc to generate compact multilayers with tunable physicochemical properties. In situ layer-by-layer growth and cross-linking were monitored by a quartz crystal microbalance with dissipation (QCM-D) to reveal the kinetics of the process and the influence of Dopa chemistry. Addition of Dopa enhanced the mass adsorption and led to the formation of a more compact structure. An increase of ionic strength induced an increase in mass adsorption in the Dopa-cross-linked multilayers. This is a universal approach for coating of various surfaces such as Au, SiO2, Ti, and Al2O3. Roughness observed by AFM in both wet and dry conditions was compared to confirm the compact morphology of Dopa-cross-linked multilayers. Because of the pH sensitivity of Dopa moiety, metal-chelated Dopa groups can be turned into softer structure at higher pH as revealed by reduction of Young's modulus determined by MFP-3D AFM. A deeper insight into the growth and mechanical properties of Dopa-cross-linked polyelectrolyte multilayers was addressed in the present study. This allows a better control of these systems for bioapplications.

[Intraocular Pressure Sensor Based on a Contact Lens].

Intraocular pressure detection has a great significance for understanding the status of eye health, prevention and treatment of diseases such as glaucoma. Traditional intraocular pressure detection needs to be held in the hospital. It is not only time-consuming to doctors and patients, but also difficult to achieve 24 hour-continuous detection. Microminiaturization of the intraocular pressure sensor and wearing it as a contact lens, which is convenient, comfortable and noninvasive, can solve this problem because the soft contact lens with an embedded micro fabricated strain gauge allows the measurement of changes in corneal curvature to correlate to variations of intraocular pressure. We fabricated a strain gauge using micro-electron mechanical systems, and integrated with the contact lens made of polydimethylsiloxane (PDMS) using injection molding. The experimental results showed that the sensitivity was 100. 7 µV/µm. When attached to the corneal surface, the average sensitivity of sensor response of intraocular pressure can be 125.8 µV/mm Hg under the ideal condition.

Mussel-Inspired Photografting on Colloidal Spheres: A Generalized Self-Template Route to Stimuli-Responsive Hollow Spheres for Controlled Pesticide Release.

A thermo-controlled pesticide release system composed of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) thin film grafted polydopamine (PDA) (PDMAEMA-g-PDA) microcapsules is reported. SiO2 microparticles are used as a template to prepare PDA-coated SiO2 microparticles. The thermally-responsive PDMAEMA thin films are grafted on PDA surfaces using a metal-free surface-initiated photopolymerization approach without adding any photo-initiator or photosensitizer under UV light irradiation. The subsequent acid etching yields PDMAEMA-g-PDA hollow microcapsules. PDMAEMA-g-PDA microcapsules exhibit well-controlled release of avermectin (Av). The results show that the loading ability of PDMAEMA-g-PDA microcapsules of Av is up to 52.7% (w/w). The release kinetics of Av demonstrate that Av@PDMAEMA-g-PDA microcapsules exhibit temperature-controlled release performance. This work is significant for controlled release systems. This simple design is expected to be used in various applications, such as in controlled drug release and agriculture-related fields.

Rheology and adhesion of poly(acrylic acid)/laponite nanocomposite hydrogels as biocompatible adhesives.

Biocompatible nanocomposite hydrogels (NC gels) consisting of poly(acrylic acid) (PAA) and nanosized clay (Laponite) were successfully synthesized by in situ free-radical polymerization of acrylic acid (AA) in aqueous solutions of Laponite. The obtained NC gels were uniform and transparent. Their viscosity, storage modulus G', and loss modulus G″ increased significantly upon increasing the content of Laponite and the dose of AA, while exhibiting a maximum with increasing the neutralization degree of AA. They showed tunable adhesion by changing the dose of Laponite and monomer as well as the neutralization degree of AA, as determined by 180° peel strength measurement. The maximal adhesion was shown when reaching a balance between cohesion and fluidity. A homemade Johnson-Kendall-Roberts (JKR) instrument was employed to study the surface adhesion behavior of the NC gels. The combination of peel strength, rheology, and JKR measurements offers the opportunity of insight into the mechanism of adhesion of hydrogels. The NC gels with tunable adhesion should be ideal candidates for dental adhesive, wound dressing, and tissue engineering.

Enhancement of enzymatic activity by magnetic spherical polyelectrolyte brushes: a potential recycling strategy for enzymes.

Interactions between amyloglucosidase and magnetic spherical polyelectrolyte brushes (MSPB) were studied by turbidimetric titration, which reveals reversible and tunable behaviors of pH-dependent enzyme-SPB binding. Quantitative thermodyanmic parameters including binding affinity and stoichiometry between enzyme and SPBs were further measured by isothermal titration calorimetry (ITC). A large amount of enzyme can be loaded in MSPB without loss of MSPB stability. We demonstrated that the enzymatic activity of amyloglucosidase bound in MSPB could be greatly enhanced (catalytic reaction rate, k(bound) = 1.36k(free)) compared to free enzyme acitivity in solution. This is tremendous improvement from other carrier systems that usually lead to a significant decrease of enzymatic activity. Both the high enzyme loading capacity and the enhancement of the catalytic activity probably arise from the Coulombic interactions between the enzyme and MSPB. These findings provide a practical strategy for enhancement of enzyme activity and enzyme recycling by MSPB.

Binding between proteins and cationic spherical polyelectrolyte brushes: effect of pH, ionic strength, and stoichiometry.

Cationic spherical polyelectrolyte brushes (SPBs) were synthesized by photoemulsion polymerization, consisting of a polystyrene core with a diameter around 80 nm and a poly(2-aminoethylmethacrylate hydrochloride) (PAEMH) shell with a thickness from 10 to 50 nm densely grafted on the core surface. The binding of various proteins onto SPBs was observed by turbidimetric titration, dynamic light scattering (DLS), zeta potential, and isothermal titration calorimetry (ITC). The binding, aggregation, and releasing of proteins by SPB can be tuned by modulating pH. The pH regions of binding for bovine serum albumin (BSA), ß-lactoglobulin (BLG), and papain onto SPBs are markedly different and tunable by ionic strength and stoichiometry between protein and SPB. Binding energetics, affinity, and amount of various proteins onto cationic SPBs were determined by ITC. These findings lay the foundation for SPB applications in the protein purification and selective immobilization of different proteins, enzymes, and antibodies.

[Effects of chain length of polyacrylic acid (PAA) on proteins adsorption of polystyrene-polyacrylic acid (PS-PAA) spherical polyelectrolyte brushes].

We studied the interaction between proteins and polystyrene-polyacrylic acid (PS-PAA) spherical polyelectrolyte brushes with different polyacrylic acid (PAA) chain lengths, including the physical adsorption and chemical adsorption in PBS buffer. Results showed that the amount of bovine serum albumin (BSA) physically adsorbed on PS-PAA spherical polyelectrolyte brushes decreased to a minimum of 33 microg/mg whereas the amount of streptavidin (SA) chemically adsorbed increased with the increase of chain length and carboxyl quantity. The biotin binding capacity of streptavidin chemically adsorbed on PS-PAA spherical polyelectrolyte brushes was roughly evaluated via enzyme competitive inhibition.

Boronic acid-functionalized spherical polymer brushes for efficient and selective enrichment of glycoproteins.

Glycoproteins are related to many biological activities and diseases, and thereby their efficient capture and enrichment for diagnostics and proteomics have emerged to exhibit great significance. However, the lack of materials with high binding capacity and selectivity is still a big obstacle for further application. Herein, we reported a facile and eco-friendly approach to fabricate spherical polymer brushes with multiple boronic acid groups. Specifically, the whole process can be divided into three steps, the polystyrene (PS) core was obtained by traditional emulsion polymerization, followed by immobilization of a home-made photoinitiator. Subsequently, boronic acid-functionalized polymer chains (PBA) were chemically grafted via photo-emulsion polymerization, leading to spherical polymer brushes (PS-PBA) with boronate affinity. The particle size, morphology, and composition of as-prepared spherical polymer brushes were systematically characterized. The characteristics of glycoproteins binding to the spherical polymer brushes under different conditions, including pH values and ionic strength, were also investigated. PS-PBA brushes possess fast binding speed (30 min) and high binding capacity for glycoprotein ovalbumin (OVA) (377.0 mg g-1) under physiological pH conditions at 25 °C, because the low steric hindrance of flexible polymeric PBA chains facilitates the interaction between boronic acid groups and glycoproteins. Moreover, the binding capacity of PS-PBA brushes for glycoprotein OVA was ∼6.7 times higher than that for non-glycoprotein bovine serum albumin (BSA), indicating the excellent selective adsorption. This study provided a facile and efficient approach for the fabrication of boronic acid-functionalized materials that will be useful in the enrichment and separation of glycoproteins for the diagnosis of diseases.

PEG-α-CD/AM/liposome @amoxicillin double network hydrogel wound dressing-Multiple barriers for long-term drug release.

Wound infection and poor wound healing are the major challenges of wound treatment. Antibiotic drug treatment is the effective way to inhibit wound infection. It is necessary to achieve sustained release of antibiotics to get a longer treatment for wound infection. The double network hydrogels based on liposome, polyethylene glycol (PEG), α- cyclodextrin (α-CD) and acrylamide (AM) were developed, in which liposome acts as amoxicillin repository. Because the drug would release from the multiple barriers including two cavities of liposome and α-CD, as well as polyethylene glycol -α- cyclodextrin/acrylamide (PEG-CD/AM) double network, the PEG-α-CD/AM/liposome @amoxicillin double network hydrogels could achieve sustained drug release. The drug release assay showed that the dressing could release amoxicillin continuously until 12 days, than that of 8th day for single-network hydrogel releasing. The antibacterial ratio of the hydrogel could reach above 80%. What's more, the hydrogels present adjustable mechanical strength by changing the ratio of the components. The swelling ratio proved that the hydrogel had potential ability to absorb wound exudates. The cytotoxicity test of the hydrogels demonstrated excellent biocompatibility. These results indicated that this study can provide a new thought for antibacterial wound dressing and has a broad application prospect.

Difunctional Fluorescence Nanoparticles for Accurate Tracing of Nanopesticide Fate and Crop Protection Prepared by Flash Nanoprecipitation.

Facile fabrication of difunctional nanoparticles (NPs) for pesticide delivery and imaging is still a fascinating challenge. Here, water-dispersible difunctional NPs were developed using flash nanoprecipitation (FNP) where self-assembling amphiphilic block copolymers were used to encapsulate a highly hydrophobic model pesticide, Lambda-cyhalothrin, and the fluorescent dye Nile red. The particle size (ranging from 158 to 280 nm) and fluorescence property of NPs could be controlled by varying the flow rate or Nile red feed concentration. The aggregation state and rearrangement of the dye molecules in the NPs were also investigated. IVIS imaging and confocal laser scanning microscopy analysis demonstrated that the resulting difunctional nanopesticide particles could allow accurate in situ tracking of the pesticide on the leaf surface, while effectively avoiding interference from chlorophyll autofluorescence. The difunctional NP suspension maintained high insecticidal activity and stability. This work demonstrates the feasibility and great potential of the FNP method in universal fabrication of multifunctional NPs with in situ pesticide tracing and crop protection capabilities.