Fabrication of Nanostructured Composite Microspheres Based on the Self‐Assembly of Polymers and Functional Nanomaterials

This Review examines recent developments in the morphological control of polymer microspheres fabricated via the phase separation of polymers as well as the alignment of functional nanoparticles inside microspheres prepared by so‐called bottom‐up synthesis techniques. Several methods for adjusting the internal and surface morphologies of polymer microspheres based on the phase separation of polymer blends and block copolymers are discussed, and the effects of microsphere size on phase separated structures and theoretical simulations of morphologies are also reviewed. The alignment of functional nanoparticles in phase separated polymer microspheres and applications of nanostructured and hybrid polymer microspheres are summarized.     

Local piezoelectric response of ZnO nanoparticles embedded in a photosensitive polymer

Local piezoelectric properties of ZnO nanoparticles (NPs) embedded in a photo‐epoxy polymer are investigated by piezoresponse force microscopy (PFM). Integrating ZnO NPs into a photosensitive SU‐8 polymer matrix not only retains the highly desired piezoelectric properties of the ZnO, but also preserves photosensitivity and optical transparency of the SU‐8 polymer. These results have strong implications for simple photolithography based low‐cost fabrication of piezoelectric microelectromechanicalsystems (MEMS) and nanoelectromechanicalsystems (NEMS) in both sensing and energy harvesting applications. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spontaneous formation of polymer nanoparticles by good-solvent evaporation as a nonequilibrium process

In recent years, polymer nanoparticles have been investigated with great interest due to their potential applications in the fields of electronics, photonics, and biotechnology. Here, we report the spontaneous formation of polymer nanoparticles from a clear solution containing a nonvolatile poor solvent by slow evaporation of a volatile good solvent. During evaporation of the good solvent, the solution gradually turns turbid. After evaporation, polymer nanoparticles of homogeneous shape and size are dispersed in the poor solvent. Homogeneous nucleation and successive growth of polymer particles takes place during the dynamic nonequilibrium process of solvent evaporation. The size of the particles, ranging from tens of nanometers to micrometer scale, depends on both polymer concentration and the solvent mixing ratio. Because of the physical generality of the particle formation mechanism, this procedure is applicable to a wide variety of polymers with suitable combinations of solvents. Here, we also show unique features, surface structures and surface properties of polymer nanoparticles prepared by this method.     

基于等离激元多重杂化效应的光吸收结构

近年来,以聚合物为代表的高分子材料由于具有比其他光吸收材料(如半导体材料、碳基材料以及贵金属纳米材料)更好的柔性和粘弹性而受到广泛关注.本文基于等离子体再聚合技术和磁控溅射工艺在聚合物材料层上制备了具有等离激元多重杂化效应的光吸收结构,该结构具有宽谱高吸收特性.该结构的制备工艺简单易行,对不同聚合物材料具有通用性,在光学器件领域具有广泛的应用前景.     

Thin films of metal-organic compounds and metal nanoparticle-embedded polymers for nonlinear optical applications

Thin films based on two very different metal-organic systems are developed and some nonlinear optical applications are explored. A family of zinc complexes which form perfectly polar assemblies in their crystalline state are found to organize as uniaxially oriented crystallites in vapor deposited thin films on glass substrate. Optical second harmonic generation from these films is investigated. A simple protocol is developed for thein-situ fabrication of highly monodisperse silver nanoparticles in a polymer film matrix. The methodology can be used to produce free-standing films. Optical limiting capability of the nanoparticle-embedded polymer film is demonstrated     

Near-Infrared-Absorbing Diketopyrrolopyrrole-Based Semiconducting Polymer Nanoparticles for Photothermal Therapy

Photothermal therapy, an excellent therapeutic approach, has received much attention in recent years. Herein, a novel diketopyrrolopyrrole polymer (DPP-BDP) is prepared, which shows intense near-infrared (NIR) optical absorption and admirable photothermal conversion efficacy. Impressively, after assembly into nanoparticles (DB-FA), the as-prepared conjugated polymer demonstrates a uniformly distributed size around 200 nm with remarkable NIR absorption at 808 nm. Additionally, it displays high biocompatibility and photostability. More interestingly, the obtained DB-FA NPs are uptaken by cancer cells and present excellent anticancer in vitro and in vivo under 0.8 W cm⁻² or 1 W cm⁻² NIR laser irradiation, respectively. Hence, this work is expected to pave the way for using conjugated-polymer nanoparticles as a powerful photothermal agents for anticancer applications.     

Preparation of a biocompatible magnetic film from an aqueous ferrofluid

Very promising nanoparticles for biomedical applications or in medical drug targeting are superparamagnetic nanoparticles based on a core consisting of iron oxides (SPION) that can be targeted through external magnets. Polyvinyl alcohol (PVA) is a unique synthetic biocompatible polymer that can be chemically cross-linked to form a gel. Biotechnology applications of magnetic gels include biosensors, targeted drug delivery, artificial muscles and magnetic buckles. These gels are produced by incorporating magnetic materials in the polymer composites. In this paper we report the synthesis of an aqueous ferrofluid and the preparation of a biocompatible magnetic gel with polyvinyl alcohol and glutharaldehyde (GTA). HClO₄ was used to induce the peptization since this kind of ferrofluid does not have surfactant. The magnetic gel was dried to generate a biocompatible film.     

Functionalization of γ-alumina cores by polyvinylpirrolidone: properties of the resulting biocompatible nanoparticles in aqueous suspension

A biocompatible polymer has been used to functionalize 45–50 nm diameter γ-alumina nanoparticles. Because the target was to use these systems in real applications, polyvinylpirrolidone (PVP) was chosen due to the characteristics of non-toxicity, biocompatibility, and feasibility of this polymer to form complexes with many cations and chemical species. This approach allows the use of these materials in medicine and food, textile, or pharmaceutical industry. The functionalization process required a previous attachment of an active group on the surface of the nanoparticles. Subsequently, a polymer chain was generated in situ, using vinyltrimethoxysilane (VTMS) and 1-vinyl-2-pyrrolidone (VP) as reactives. The morphology and topology of the nanocompound has been characterized in aqueous suspensions, attending to possible applications in this medium. The results obtained from the different techniques show that the polymer chain was successfully grafted to the nanoparticle surface, and allow an estimation of the size of the modified particle. Their electrical and conformational behavior have also been studied in different aqueous chemical environments.     

Thin films of Cu(II)-o,o′-dihydroxy azobenzene nanoparticle-embedded polyacrylic acid (PAA) for nonlinear optical applications developed by matrix assisted pulsed laser evaporation (MAPLE)

Thin films based on two different metal-organic systems are developed by MAPLE and their nonlinear optical applications are explored. A complex of o,o′-dihydroxy azobenzene with Cu²⁺ cation is found to organize as a non-central symmetric crystallite. A simple protocol is developed for the in situ fabrication of highly monodisperse copper-complex nanoparticles in a polymer film matrix of polyacrylic acid. The thin films were deposited on quartz substrates by MAPLE (matrix assisted pulsed laser evaporation) using a Nd:YAG laser working at 355 nm. Atomic force microscopy (AFM), Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), and optical second harmonic generation (SHG) were performed on the samples. The optical limiting capability of the nanoparticle-embedded polymer film is investigated.     

Integrated experimental and computational approach for nanoparticle flow analysis

We report a new method combining computational fluid dynamics and flow experiments with customized channels to understand the transport of nanoparticles. Iron oxide nanoparticles, being highly attractive for biomedical research are chosen as model nanoparticles for the transport studies. Four different polyvinyl pyrrolidone and polyethyleneimine coated iron oxide nanoparticles of hydrodynamic sizes ranging from 45–178 nm were synthesized. These nanoparticles were adjusted to different target mass concentrations and ran through a bent tube to determine flow velocity and mass loss, specific to the nanoparticles. Computational predictions were made for velocity and mass loss of fully developed flow of nanoparticles through bent channel, which compared well with experimental measurements. A diffusion dominated nanoparticle flow is predicted, based on our results. This work will provide a breakthrough for further experimental and computational research to help understand the nanoparticle targeted delivery and the design of nanoparticles for optimal delivery in biomedical applications.     

Role of silica nanoparticles in conductivity enhancement of nanocomposite solid polymer electrolytes: (PEGx NaBr): ySiO2

Nanocomposite solid polymer electrolytes (NCSPEs) with conducting species other than Li ions are being investigated for solid-state battery applications. Pristine solid polymer electrolytes (SPEs) do not show ionic conductivity suitable for batteries. Addition of inert fillers to SPEs is known to enhance the ionic conductivity. In this paper, we present the role of silica nanoparticles in enhancing the ionic conductivity in NCSPEs with sodium as conducting species. Sodium bromide is complexed with the host polyethylene glycol polymer by solution cast method and silica nanoparticles (SiO₂, average particle size 7 nm) are incorporated into the complex in small amounts. The composites are characterized by powder XRD and IR spectroscopy. Conductivity measurements are undertaken as a function of concentration of salt and also as a function of temperature using impedance spectroscopy. Addition of silica nanoparticles shows an enhancement in conductivity by 1–2 orders of magnitude. The results are discussed in terms of interaction of nanoparticles with the nonconducting anions.     

Mechanism for hierarchical self-assembly of nanoparticles on scaffolds derived from block copolymers

Lithographically patterned substrates can direct the self-assembly of block copolymer films into aligned structures that, in turn, template the self-organization of colloidal nanoparticles. Deposition on pristine diblock copolymer films does not lead to reproducible selective decoration, but films modified to have nanoscale corrugation act as scaffolds for highly selective nanoparticle adsorption. The mechanism for this selectivity relies on the lateral forces inherent to spin casting to remove all of the nanoparticle suspension not confined within the nanoscopic trenches. This technique does not rely on interactions between the surfactant capping molecules and the polymer and is therefore general to a wide class of nanoparticle materials. Prospects to obtain long-range ordering and associated potential applications are discussed.     

Polymer-supported metals and metal oxide nanoparticles: synthesis,characterization, and applications

Metal and metal oxide nanoparticles exhibit unique properties in regard to sorption behaviors, magnetic activity, chemical reduction, ligand sequestration among others. To this end, attempts are being continuously made to take advantage of them in multitude of applications including separation, catalysis, environmental remediation, sensing, biomedical applications and others. However, metal and metal oxide nanoparticles lack chemical stability and mechanical strength. They exhibit extremely high pressure drop or head loss in fixed-bed column operation and are not suitable for any flow-through systems. Also, nanoparticles tend to aggregate; this phenomenon reduces their high surface area to volume ratio and subsequently reduces effectiveness. By appropriately dispersing metal and metal oxide nanoparticles into synthetic and naturally occurring polymers, many of the shortcomings can be overcome without compromising the parent properties of the nanoparticles. Furthermore, the appropriate choice of the polymer host with specific functional groups may even lead to the enhancement of the properties of nanoparticles. The synthesis of hybrid materials involves two broad pathways: dispersing the nanoparticles (i) within pre-formed or commercially available polymers; and (ii) during the polymerization process. This review presents a broad coverage of nanoparticles and polymeric/biopolymeric host materials and the resulting properties of the hybrid composites. In addition, the review discusses the role of the Donnan membrane effect exerted by the host functionalized polymer in harnessing the desirable properties of metal and metal oxide nanoparticles for intended applications.     

PMA capped silver nanoparticles produced by UV-enhanced chemical process

An UV-enhanced single-step chemical bath process has been defined to produce precisely tailored colloidal solutions of silver nanoparticles capped with poly(methacrylic acid) (PMA) for bio-technological and packaging applications. The influence of the main process parameters on the nanoparticles chemical and structural characteristics, as well as on the reactions involved in the nanoparticle growth and polymer cross-linking, has been examined in details. A clear distinction between nanoparticle nucleation and growth, mediated by the available polymer functional groups and steric properties, has allowed to set up an effective controllable process and to obtain the desired colloids. The proper choice of the process parameters has led to a silver nanoparticles size smaller than 20 nm with a distribution peaked at less than 10 nm and stable over a period of one month.     

Polydopamine Nanoparticle as a Multifunctional Nanocarrier for Combined Radiophotodynamic Therapy of Cancer

Combination of different therapeutic strategies to treat cancer has attracted tremendous attention in recent years. Herein, the authors develop polydopamine (PDA) nanoparticles with polyethylene glycol (PEG) modification as a multifunctional nanocarrier for coloading photosensitizer chlorine6 (Ce6) and curcumin (Cur) for combined photodynamic therapy (PDT) and radiotherapy (RT) of cancer. PEGylated PDA nanoparticles (PDA‐PEG) exhibit well water soluble and biocompatible in different physiological solutions and cause no obvious toxicity to cancer cells. In this nanoparticle, the loaded Ce6 can trigger the generation of single oxygen under near‐infrared laser irradiation for PDT, while the loaded Cur can act as an excellent radiosensitizer under X‐ray irradiation for enhanced external RT. As demonstrated by in vitro and in vivo therapeutic efficiency, combined PDT and RT based on PDA‐PEG/Cur/Ce6 nanoparticles exhibits significant inhibition the growth of cancer cells, revealing perfect performance in cancer treatment. Therefore, the study not only presents a polymer‐based theranostic platform for cancer treatment but also demonstrates the potential applications of combined RT and PDT for the future clinic cancer therapy.     

Synthesis and assembly of magnetic nanoparticles for information and energy storage applications

This mini-review summarizes the recent advances in chemical synthesis and assembly of monodisperse magnetic nanoparticles for magnetic applications. After a brief introduction to nanomagnetism, the review focuses on recent developments in solution phase syntheses and assemblies of monodisperse Fe, CoFe, FePt and SmCo₅ nanoparticles. The review further outlines the structural and magnetic properties of these nanoparticles for magnetic information and energy storage applications.     

Discrepancy between different estimates of the hydrodynamic diameter of polymer-coated iron oxide nanoparticles in solution

We have synthesized iron oxide nanoparticles coated with a monolayer of dextran, with molecular weights of the polymer between 5 and 670 kDa. Transmission electron microscopy images confirm that the hard core has a crystalline diameter of approximately 12 nm. The hydrodynamic diameters of these coated nanoparticles in solution measured using dynamical light scattering and estimated from magnetic susceptibility studies vary from near 90 nm for the lightest polymer to 140 nm for the heaviest polymer. Conversely, fluorescence correlation spectroscopy measurements yield a diameter of approximately 55 nm for the 15?C20 kDa dextran coated nanoparticles, which is consistent with the expected value estimated from the sum of the hard-core diameter and monolayer dextran coating. We discuss the implications of this discrepancy for applications involving polymer-coated magnetic nanoparticles.     

Scalable Formation of Concentrated Monodisperse Lignin Nanoparticles by Recirculation-Enhanced Flash Nanoprecipitation

A highly controllable and scalable process for fabrication of large amounts of concentrated lignin nanoparticles (LNPs) is reported. These lignin core nanoparticles are formed through flash nanoprecipitation, however, scaling up of the fabrication process requires fundamental understanding of their operational formation mechanism and surface properties. It is shown how a semicontinuous synthesis system with a recirculation loop makes it possible to produce flash precipitated lignin nanoparticles in large amounts for practical applications. The roles of the process parameters, including flow rates and lignin concentration, are investigated and analyzed. The results indicate that the LNPs are formed by a process of continuous burst nucleation at the point of mixing without diffusive growth, which yields nanoparticles of highly uniform size following a modified LaMer nucleation and growth mechanism. This mechanism makes possible facile process control and scale-up. Effective control of the resulting nanoparticle size is achieved through the initial concentration of lignin in the injected solution. The impressive capability to produce suspensions of any predesigned multimodal distribution is demonstrated. The resulting nanofabrication technique can produce large volumes of concentrated LNP suspensions of high stability and tightly controlled size distributions for biological or agricultural applications.     

Enhanced Fluorescence Emission and Magnetic Alignment Control of Biphasic Functionalized Composite Janus Particles

Janus particles, particles that have two distinct aspects on their surface or interiors, have attracted much attention due to their potential for application. For the application of Janus particles to high‐resolution displays, and as light sources for optical circuits and fluorescent probes, the Janus particles should be nanosize to ensure high‐resolution display and analysis, responsive to external stimuli, and highly fluorescent. However, it is still a challenging issue to develop such highly fluorescent nanoscale Janus particles and control their alignment. Magnetoresponsive Janus particles, of which the orientation can be controlled by an external magnetic field, are prepared by the simple introduction of polymer‐coated magnetic nanoparticles (NPs) into the hemispheres of Janus particles. If these magnetoresponsive Janus particles can be combined with a strong fluorescence system, then they could be ideal candidates as components of the previously mentioned applications. In the present study, Janus particles are prepared with a fluorescent dye and gold nanoparticles (Au NPs) on one side. The optical properties of the resulting particles are assessed and discussed. Furthermore, the response of composite Janus particles containing dyes, Au NPs, and iron oxide NPs to an external magnetic field is discussed.     

Effect of titanium dioxide nanoparticles on polymer network formation

This work presents a study of the effect of nanoparticles on polymer composites to develop a powerful polymer dispersed liquid crystal materials. Tri propylene glycol diarcrylate/titanium dioxide nanocomposites were produced at various titanium dioxide fractions ranging between 0 and 1?wt%, through ultraviolet curing technique during 30?min. Different technics such as polarized optical microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermal gravimetric analysis were used to characterize the samples. A dynamic swelling of polymer network was also investigated. The evolution of the acrylic double-bond conversion shows a decrease in the absorption intensity at 1637?cm^?1. It is noted that the conversion rate decreases from 0.1 to 1?wt% of titanium dioxide nanoparticles. An increase in glass transition temperature is observed by differential scanning calorimetry. The thermogravimetric analysis results reveal a highly improved thermal stability upon the addition of the reinforcing phase. The follow of kinetics swelling of polymer network shows a decrease of the swell ratio with the inclusion of titanium dioxide nanoparticles.