Poly(N‐isopropylacrylamide)‐Clay Nanocomposite Hydrogels with Responsive Bending Property as Temperature‐Controlled Manipulators

Novel poly(N‐isopropylacrylamide)‐clay (PNIPAM‐clay) nanocomposite (NC) hydrogels with both excellent responsive bending and elastic properties are developed as temperature‐controlled manipulators. The PNIPAM‐clay NC structure provides the hydrogel with excellent mechanical property, and the thermoresponsive bending property of the PNIPAM‐clay NC hydrogel is achieved by designing an asymmetrical distribution of nanoclays across the hydrogel thickness. The hydrogel is simply fabricated by a two‐step photo polymerization. The thermoresponsive bending property of the PNIPAM‐clay NC hydrogel is resulted from the unequal forces generated by the thermoinduced asynchronous shrinkage of hydrogel layers with different clay contents. The thermoresponsive bending direction and degree of the PNIPAM‐clay NC hydrogel can be adjusted by controlling the thickness ratio of the hydrogel layers with different clay contents. The prepared PNIPAM‐clay NC hydrogels exhibit rapid, reversible, and repeatable thermoresponsive bending/unbending characteristics upon heating and cooling. The proposed PNIPAM‐clay NC hydrogels with excellent responsive bending property are demonstrated as temperature‐controlled manipulators for various applications including encapsulation, capture, and transportation of targeted objects. They are highly attractive material candidates for stimuli‐responsive “smart” soft robots in myriad fields such as manipulators, grippers, and cantilever sensors.     

Porous Structures: In situ Porous Structures: A Unique Polymer Erosion Mechanism in Biodegradable Dipeptide‐Based Polyphosphazene and Polyester Blends Producing Matrices for Regenerative Engineering (Adv. Funct. Mater. 17/2010)

Synthetic biodegradable polymers serve as temporary substrates that accommodate cell infiltration and tissue in‐growth in regenerative medicine. To allow tissue in‐growth and nutrient transport, traditional three‐dimensional (3D) scaffolds must be prefabricated with an interconnected porous structure. Here we demonstrated for the first time a unique polymer erosion process through which polymer matrices evolve from a solid coherent film to an assemblage of microspheres with an interconnected 3D porous structure. This polymer system was developed on the highly versatile platform of polyphosphazene‐polyester blends. Co‐substituting a polyphosphazene backbone with both hydrophilic glycylglycine dipeptide and hydrophobic 4‐phenylphenoxy group generated a polymer with strong hydrogen bonding capacity. Rapid hydrolysis of the polyester component permitted the formation of 3D void space filled with self‐assembled polyphosphazene spheres. Characterization of such self‐assembled porous structures revealed macropores (10–100 μm) between spheres as well as micro‐ and nanopores on the sphere surface. A similar degradation pattern was confirmed in vivo using a rat subcutaneous implantation model. 12 weeks of implantation resulted in an interconnected porous structure with 82–87% porosity. Cell infiltration and collagen tissue in‐growth between microspheres observed by histology confirmed the formation of an in situ 3D interconnected porous structure. It was determined that the in situ porous structure resulted from unique hydrogen bonding in the blend promoting a three‐stage degradation mechanism. The robust tissue in‐growth of this dynamic pore forming scaffold attests to the utility of this system as a new strategy in regenerative medicine for developing solid matrices that balance degradation with tissue formation.     

Supercritical‐Fluid‐Assisted One‐Pot Synthesis of Biocompatible Core(γ‐Fe2O3)/Shell(SiO2) Nanoparticles as High Relaxivity T2‐Contrast Agents for Magnetic Resonance Imaging

Monodisperse iron oxide/microporous silica core/shell composite nanoparticles, core(γ‐Fe₂O₃)/shell(SiO₂), with a diameter of approximately 100 nm and a high magnetization are synthesized by combining sol–gel chemistry and supercritical fluid technology. This one‐step processing method, which is easily scalable, allows quick fabrication of materials with controlled properties and in high yield. The particles have a specific magnetic moment (per kg of iron) comparable to that of the bulk maghemite and show superparamagnetic behavior at room temperature. The nanocomposites are proven to be useful as T₂ MRI imaging agent. They also have potential to be used in NMR proximity sensing, theranostic drug delivery, and bioseparation.     

Generic Strategy of Preparing Fluorescent Conjugated‐Polymer‐Loaded Poly(DL‐lactide‐co‐Glycolide) Nanoparticles for Targeted Cell Imaging

A general strategy for the preparation of highly fluorescent poly(DL‐lactide‐co‐glycolide) (PLGA) nanoparticles (NPs) loaded with conjugated polymers (CPs) is reported. The process involves encapsulation of organic‐soluble CPs with PLGA using a modified solvent extraction/evaporation technique. The obtained NPs are stable in aqueous media with biocompatible and functionalizable surfaces. In addition, fluorescent properties of the CP‐loaded PLGA NPs (CPL NPs) could be fine‐tuned by loading different types of CPs into the PLGA matrix. Four types of CPL NPs are prepared with a volume‐average hydrodynamic diameter ranging from 243 to 272 nm. The application of CPL NPs for bio‐imaging is demonstrated through incubation with MCF‐7 breast cancer cells. Confocal laser scanning microscopy studies reveal that the CPL NPs are internalized in cytoplasm around the nuclei with intense fluorescence. After conjugation with folic acid, cellular uptake of the surface‐functionalized CPL NPs is greatly enhanced via receptor‐mediated endocytosis by MCF‐7 breast cancer cells, as compared to that for NIH/3T3 fibroblast cells, which indicates a selective targeting effect of the folate‐functionalized CPL NPs in cellular imaging. The merits of CPL NPs, such as low cytotoxicity, high fluorescence, good photostability, and feasible surface functionalization, will inspire extensive study of CPL NPs as a new generation of probes for specific biological imaging and detection.     

Superparamagnetic Nanostructures for Off‐Resonance Magnetic Resonance Spectroscopic Imaging

This study proposes a new method to generate positive contrast in magnetic resonance imaging (MRI) using superparamagnetic contrast agents. Superparamagnetic nanostructures consisting of octahedron manganese ferrite nanoparticles embedded in spherical nanogels are fabricated using a bottom‐up approach. The composite nanoparticles are strongly magnetized in an external magnetic field and produce a unique NMR frequency shift in water protons, which can be demonstrated in MR spectroscopy and imaging to be different from the bulk pool. Moreover, the particles exhibit excellent colloidal stability in aqueous media and good cell biocompatibility. Hence, these particles are potentially useful as biomarkers by taking advantage of the positive contrast effects produced in MRI.     

Enhanced Antibacterial Activity of Nanocrystalline ZnO Due to Increased ROS‐Mediated Cell Injury

An innovative study aimed at understanding the influence of the particle size of ZnO (from the microscale down to the nanoscale) on its antibacterial effect is reported herein. The antibacterial activity of ZnO has been found to be due to a reaction of the ZnO surface with water. Electron‐spin resonance measurements reveal that aqueous suspensions of small nanoparticles of ZnO produce increased levels of reactive oxygen species, namely hydroxyl radicals. Interestingly, a remarkable enhancement of the oxidative stress, beyond the level yielded by the ZnO itself, is detected following the antibacterial treatment. Likewise, an exposure of bacteria to the small ZnO nanoparticles results in an increased cellular internalization of the nanoparticles and bacterial cell damage. An examination of the antibacterial effect is performed on two bacterial species: Escherichia coli (Gram negative) and Staphylococcus aureus (Gram positive). The nanocrystalline particles of ZnO are synthesized using ultrasonic irradiation, and the particle sizes are controlled using different solvents during the sonication process. Taken as a whole, it is apparent that the unique properties (i.e., small size and corresponding large specific surface area) of small nanometer‐scale ZnO particles impose several effects that govern its antibacterial action. These effects are size dependent and do not exist in the range of microscale particles.     

Swelling Behavior of Multiresponsive Poly(methacrylic acid)‐block‐‐poly(N‐isopropylacrylamide) Brushes Synthesized Using Surface‐Initiated Photoiniferter‐Mediated Photopolymerization

Surface‐initiated photoiniferter‐mediated photopolymerization (SI‐PMP) in presence of tetraethylthiuram disulfide is used to directly synthesize surface‐grafted poly(methacrylic acid)‐block‐poly(N‐isopropylacrylamide) (PMAA‐b‐PNIPAM) layers. The response of these PMAA‐b‐PNIPAM bi‐level brushes to changes in pH, temperature and ionic strength is investigated by using in‐situ multi‐angle ellipsometry to measure changes in solvated layer thickness. As expected for a block copolymer architecture, PMAA blocks swell as pH is increased, with the maximum change in the thickness occurring near pH = 5, and PNIPAM blocks exhibit lower critical solution temperature (LCST) behavior, marked by a broad transition between swollen and collapsed states. The response of the bi‐level brushes to changes in added salt at constant pH is complex, as the swelling behaviors of both the weak polyelectrolyte, PMAA, and thermoresponsive PNIPAM are affected by changes in ionic strength. This work demonstrates not only the robustness of SI‐PMP for making novel, bi‐level stimuli‐responsive brushes, but also the complex links between synthesis, structure, and response of these materials.     

Triple‐Shape Polymeric Composites (TSPCs)

In this paper, the fabrication and characterization of triple‐shape polymeric composites (TSPCs) that, unlike traditional shape memory polymers (SMPs), are capable of fixing two temporary shapes and recovering sequentially from the first temporary shape (shape 1) to the second temporary shape (shape 2), and eventually to the permanent shape (shape 3) upon heating, are reported. This is technically achieved by incorporating non‐woven thermoplastic fibers (average diameter ～760 nm) of a low‐T_m semicrystalline polymer into a T_g‐based SMP matrix. The resulting composites display two well‐separated transitions, one from the glass transition of the matrix and the other from the melting of the fibers, which are subsequently used for the fixing/recovery of two temporary shapes. Three thermomechanical programming processes with different shape fixing protocols are proposed and explored. The intrinsic versatility of this composite approach enables an unprecedented large degree of design flexibility for functional triple‐shape polymers and systems.     

Enhanced Electrical Switching and Electrochromic Properties of Poly(p‐phenylenebenzobisthiazole) Thin Films Embedded with Nano‐WO3

The electrical switching and electrochromic phenomena of a novel nanocomposite comprising poly(p‐phenylenebenzobisthiazole) (PBZT) and tungsten oxide (WO₃) nanoparticles are investigated as a function of the nanoparticle loading. Both dissolving PBZT and doping PBZT backbone structure with acid are achieved by one simple step. Chlorosulfonic acid (CSA) is used as a solvent and spontaneously transformed to sulfuric acid upon exposure to moisture. The formed sulfuric acid serves as doping agent to improve the electrical conductivity of PBZT. The most significant enhancement of electrical switching is observed in the nanocomposites with low weight fraction (5%). The electrical conductivity of 5% WO₃/PBZT nanocomposite thin film is increased by about 200 times and 2 times, respectively, as compared to those of the as‐received PBZT and PBZT/CSA thin films. As the nanoparticle loading increases to 20% and 30%, the nanocomposites follow an ohmic conduction mechanism. Stable electrical conductivity switching is observed before and after applying a bias on the pristine PBZT and WO₃/PBZT nanocomposite thin films. Electrochromic phenomena of both PBZT and WO₃/PBZT nanocomposite thin films with high contrast ratio are observed after applying a bias (3 V). The mechanisms of the nanoparticles in enhancing the electrical switching and electrochromic properties are proposed.     

Random Copolymer Films with Molecular‐Scale Compositional Heterogeneities that Interfere with Protein Adsorption

Smooth surfaces with compositional heterogeneities at a molecular‐length scale are presented with the goal of disrupting surface–protein interactions. These surfaces are synthesized by utilizing photoinitiated chemical vapor deposition (piCVD) to deposit thin films of random copolymers consisting of highly hydrophilic and highly hydrophobic comonomers. Swellability, wettability, and surface roughness could be systematically controlled by tuning the copolymer composition. The surface composition was dynamic, and the surface reconstructed based on the hydration state of the film. Proteins adsorbed to the copolymer films less readily than to either of the respective homopolymers, indicating a synergistic effect resulting from the random copolymer presenting molecular‐scale compositional heterogeneity. These results provide direct evidence that protein adsorption can be disrupted by such surfaces and a simple analytical model suggests that the heterogeneities occur over areas encompassing 4–5 repeat units of the polymer. The synthetic method used to create these films can be used to coat arbitrary geometries, enabling practical utility in a number of applications.     

Silver/Reduced Graphene Oxide Hydrogel as Novel Bactericidal Filter for Point‐of‐Use Water Disinfection

Nanomaterials open an alternative way for water disinfection. However, limitations such as aggregation, toxicity, and complex post‐treatment block their practical application. In this study, an antibacterial silver/reduced graphene oxide (Ag/rGO) hydrogel consisting of controlled porous rGO network and well‐dispersed Ag nanoparticle is synthesized by a facile hydrothermal reaction. Scanning electron microscopy, transmission electron microscope, X‐ray diffraction, mercury porosimetry, and Fourier transform IR spectroscopy are employed to characterize the Ag/rGO hydrogel. The 3D structure of the rGO network serves as an excellent support for Ag nanoparticles. Disinfection experiments show that the Ag/rGO hydrogel exhibits good efficacy against Escherichia coli when used as a bactericidal filter driven by gravity. The mechanistic study indicates that bacteria cells are inactivated due to cell membrane damage induced by silver nanoparticles and rGO nanosheets when they flow through Ag/rGO hydrogel. Moreover, due to the retaining of Ag by rGO, the leaching level of silver from Ag/rGO hydrogel is considerably lower than the drinking water standard. This study sheds new light on designing antibacterial materials for point‐of‐use water disinfection application.     

Size Effect on Properties of Varistors Made From Zinc Oxide Nanoparticles Through Low Temperature Spark Plasma Sintering

Conditions for the elaboration of nanostructured varistors by spark plasma sintering (SPS) are investigated, using 8‐nm zinc oxide nanoparticles synthesized following an organometallic approach. A binary system constituted of zinc oxide and bismuth oxide nanoparticles is used for this purpose. It is synthesized at room temperature in an organic solution through the hydrolysis of dicyclohexylzinc and bismuth acetate precursors. Sintering of this material is performed by SPS at various temperatures and dwell times. The determination of the microstructure and the chemical composition of the as‐prepared ceramics are based on scanning electron microscopy and X‐ray diffraction analysis. The nonlinear electrical characteristics are evidenced by current–voltage measurements. The breakdown voltage of these nanostructured varistors strongly depends on grain sizes. The results show that nanostructured varistors are obtained by SPS at sintering temperatures ranging from 550 to 600 °C.     

Ultrasmall Graphene Oxide Supported Gold Nanoparticles as Adjuvants Improve Humoral and Cellular Immunity in Mice

Adjuvants play an important role in vaccines. Alum and MF59 are two dominant kinds of adjuvants used in humans. Both of them, however, have limited capacity to generate the cellular immune response required for vaccines against cancers and viral diseases. It is desirable to develop new and efficient adjuvants with the aim of improving the cellular immune response against the antigen. Here, the feasibility and efficiency of ultrasmall graphene oxide supported gold nanoparticles (usGO‐Au) as a new immune adjuvant to improve immune responses are explored. usGO‐Au is obtained from reduction of chloroauric acid using usGO and then decorated with ovalbumin (OVA, a model antigen) through physical adsorption to construct usGO‐Au@OVA. As the results show, the as‐synthesized usGO‐Au@OVA can efficiently stimulate RAW264.7 cells to secrete tumor necrosis factor‐α (TNF‐α), a mediator for cellular immune response. In vivo studies demonstrate that usGO‐Au@OVA can also promote robust OVA specific antibody response, CD8⁺ T cells proliferation, and different cytokines secretion. The results indicate that using usGO‐Au as an adjuvant can stimulate potent humoral and cellular immune responses against antigens, which may promote better understanding of cellular immune response and facilitate potential applications for cancer and viral vaccines.     

Strongly‐Coupled Freestanding Hybrid Films of Graphene and Layered Titanate Nanosheets: An Effective Way to Tailor the Physicochemical and Antibacterial Properties of Graphene Film

An effective way to tailor the physicochemical properties of graphene film is developed by combining colloidal suspensions of reduced graphene oxide (rG‐O) nanosheets and exfoliated layered titanate nanosheets for the fabrication of freestanding hybrid films comprised of stacked and overlapped nanosheets. A flow‐directed filtration of such mixed colloidal suspensions yields freestanding hybrid films comprised of strongly‐coupled rG‐O and titanate nanosheets with tunable chemical composition. This is the first example of highly flexible hybrid films composed of graphene and metal oxide nanosheets. The intimate incorporation of layered titanate nanosheets into the graphene film gives rise not only to an increase of mechanical strength but also to increased surface roughness, chemical stability, and hydrophilicity; thus, the physicochemical properties of the graphene film can be tuned by hybridization with inorganic nanosheets. These freestanding hybrid films of rG‐O‐layered titanate show unprecedentedly high antibacterial property, resulting in the complete sterilization of Escherichia coli O157:H7 (≈100%) in the very short time of 15 min. The antibacterial activity of the hybrid film is far superior to that of the pure graphene film, underscoring the beneficial effect of the layered metal oxide nanosheets in improving the functionality of the graphene film.     

Silica‐Coated Manganese Oxide Nanoparticles as a Platform for Targeted Magnetic Resonance and Fluorescence Imaging of Cancer Cells

Monodisperse silica‐coated manganese oxide nanoparticles (NPs) with a diameter of ～35 nm are synthesized and are aminated through silanization. The amine‐functionalized core–shell NPs enable the covalent conjugation of a fluorescent dye, Rhodamine B isothiocyanate (RBITC), and folate (FA) onto their surface. The formed Mn₃O₄@SiO₂(RBITC)–FA core–shell nanocomposites are water‐dispersible, stable, and biocompatible when the Mn concentration is below 50 µg mL^?1 as confirmed by a cytotoxicity assay. Relaxivity measurements show that the core–shell NPs have a T₁ relaxivity (r₁) of 0.50 mM ^?1 s^?1 on the 0.5 T scanner and 0.47 mM ^?1 s^?1 on the 3.0 T scanner, suggesting the possibility of using the particles as a T₁ contrast agent. Combined flow cytometry, confocal microscopy, and magnetic resonance imaging studies show that the Mn₃O₄@SiO₂(RBITC)–FA nanocomposites can specifically target cancer cells overexpressing FA receptors (FARs). Findings from this study suggest that the silica‐coated Mn₃O₄ core–shell NPs could be used as a platform for bimodal imaging (both magnetic resonance and fluorescence) in various biological systems.     

In Situ Porous Structures: A Unique Polymer Erosion Mechanism in Biodegradable Dipeptide-based Polyphosphazene and Polyester Blends Producing Matrices for Regenerative Engineering

Synthetic biodegradable polymers serve as temporary substrates that accommodate cell infiltration and tissue in-growth in regenerative medicine. To allow tissue in-growth and nutrient transport, traditional three-dimensional (3D) scaffolds must be prefabricated with an interconnected porous structure. Here we demonstrated for the first time a unique polymer erosion process through which polymer matrices evolve from a solid coherent film to an assemblage of microspheres with an interconnected 3D porous structure. This polymer system was developed on the highly versatile platform of polyphosphazene-polyester blends. Co-substituting a polyphosphazene backbone with both hydrophilic glycylglycine dipeptide and hydrophobic 4-phenylphenoxy group generated a polymer with strong hydrogen bonding capacity. Rapid hydrolysis of the polyester component permitted the formation of 3D void space filled with self-assembled polyphosphazene spheres. Characterization of such self-assembled porous structures revealed macropores (10-100 μm) between spheres as well as micro- and nanopores on the sphere surface. A similar degradation pattern was confirmed in vivo using a rat subcutaneous implantation model. 12 weeks of implantation resulted in an interconnected porous structure with 82-87% porosity. Cell infiltration and collagen tissue in-growth between microspheres observed by histology confirmed the formation of an in situ 3D interconnected porous structure. It was determined that the in situ porous structure resulted from unique hydrogen bonding in the blend promoting a three-stage degradation mechanism. The robust tissue in-growth of this dynamic pore forming scaffold attests to the utility of this system as a new strategy in regenerative medicine for developing solid matrices that balance degradation with tissue formation.