Hybrids of Magnetic Nanoparticles with Double‐Hydrophilic Core/Shell Cylindrical Polymer Brushes and Their Alignment in a Magnetic Field

The synthesis of double‐hydrophilic core/shell cylindrical polymer brushes (CPBs), their hybrids with magnetite nanoparticles, and the directed alignment of these magnetic hybrid cylinders by a magnetic field are demonstrated. Consecutive grafting from a polyinitiator poly(2‐(2‐bromoisobutyryloxy)ethyl methacrylate) (PBIEM) of tert‐butyl methacrylate (tBMA) and oligo(ethylene glycol) methacrylate (OEGMA) using atom‐transfer radical polymerization (ATRP) and further de‐protection yields core/shell CPBs with poly(methacrylic acid) (PMAA) as the core and POEGMA as the shell, which is evidenced by ¹H NMR, gel permeation chromatography (GPC), and dynamic and static light scattering (DLS and SLS). The resulting core/shell brush is well soluble in water and shows a pH responsiveness because of its weak polyelectrolyte core. Pearl‐necklace structures are observed by cryogenic transmission electron microscopy (cryo‐TEM) at pH 4, while at pH 7, these structures disappear owing to the ionization of the core. A similar morphology is also found for the polychelate of the core/shell CPBs with Fe³⁺ ions. Superparamagnetic magnetite nanoparticles have also been prepared and introduced into the core of the brushes. The hybrid material retains the superparamagnetic property of the magnetite nanoparticles, which is verified by superconducting quantum interference device (SQUID) magnetization measurements. Large‐scale alignment of the hybrid cylinders in relatively low magnetic fields (40–300 mT) can easily be performed when deposited on a surface. which is clearly revealed by the atomic force microscopy (AFM) and TEM measurements.     

Multifunctional Nanoparticles Composed of A Poly( dl‐lactide‐coglycolide) Core and A Paramagnetic Liposome Shell for Simultaneous Magnetic Resonance Imaging and Targeted Therapeutics

A multifunctional nanoscale platform that is self‐assembled from a hydrophobic poly( dl ‐lactide‐coglycolide)(PLGA) core and a hydrophilic paramagnetic‐folate‐coated PEGylated lipid shell (PFPL; PEG=polyethylene glycol) is designed for simultaneous magnetic resonance imaging (MRI) and targeted therapeutics. The nanocomplex has a well‐defined core‐shell structure which is studied using confocal laser scanning microscopy (CLSM). The paramagnetic diethylenetriaminepentaacetic acid‐gadolinium (DTPA‐Gd) chelated to the shell layer exhibits significantly higher spin–lattice relaxivity (r₁) than the clinically used small‐molecular‐weight MRI contrast agent Magnevist^®. The PLGA core serves as a nanocontainer to load and release the hydrophobic drugs. From a drug‐release study, it is found that the modification of the PLGA core with a polymeric liposome shell can be a useful tool for reducing the drug‐release rate. Cellular uptake of folate nanocomplex is found to be higher than that of non‐folate‐nanocomplex due to the folate‐binding effect on the cell membrane. This work indicates that the multifunctional platform with combined characteristics applicable to MRI and drug delivery may have great potential in cancer chemotherapy and diagnosis.     

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.     

Hollow Two‐Layered Chiral Nanoparticles Consisting of Optically Active Helical Polymer/Silica: Preparation and Application for Enantioselective Crystallization

This article reports for the first time a novel category of hollow organic@inorganic hybrid two‐layered nanoparticles (NPs), in which the inner layer is formed by optically active helical polyacetylene, and the outer layer by silica. Such NPs show remarkable optical activity and are successfully used for enantioselective crystallization. To prepare such NPs, n‐butyl acrylate undergoes radical polymerization to first form poly(n‐butyl acrylate) (PBA) cores two shells by catalytic polymerization of substituted acetylene and sol–gel approach of TEOS (tetraethyl orthosilicate), respectively. Removal of the PBA cores provides the expected hollow core/shell NPs. The intense dircular dichroism (CD) effects demonstrate that the hollow chiral NPs possess considerable optical activity, arising from the helical substituted polyacetylenes forming the inner layer. The hollow NPs are further used as chiral templates to induce enantioselective crystallization of racemic alanines, demonstrating the significant potential applications of the hollow chiral NPs in chiral technologies. Also of particular significance is the detailed process of the induced crystallization observed by TEM. The strategy for preparing the hollow hybrid chiral NPs should be highlighted since it combines free radical polymerization and catalytic polymerization with sol–gel process in a single system, by which numerous advanced materials will be accessible.     

Core–Shell Nanoparticles: Characterizing Multifunctional Materials beyond Imaging—Distinguishing and Quantifying Perfect and Broken Shells

Core–shell nanoparticles (NPs) are amongst the most promising candidates in the development of new functional materials. Their fabrication and characterization are challenging, in particular when thin and intact shells are needed. To date no technique has been available that differentiates between intact and broken or cracked shells. Here a method is presented to distinguish and quantify these types of shells in a single cyclic voltammetry experiment by using the different electrochemical reactivities of the core and the shell material. A simple comparison of the charge measured during the stripping of the core material before and after the removal of the shell makes it possible to determine the quality of the shells and to estimate their thickness. As a proof‐of‐concept two multifunctional examples of core–shell NPs, Fe₃O₄@Au and Au@SnO₂, are used. This general and original method can be applied whenever core and shell materials show different redox properties. Because billions of NPs are probed simultaneously and at a low cost, this method is a convenient new screening tool for the development of new multifunctional core–shell materials and is hence a powerful complementary technique or even an alternative to the state‐of‐the‐art characterization of core–shell NPs by TEM.     

Harvesting Lost Photons: Plasmon and Upconversion Enhanced Broadband Photocatalytic Activity in Core@Shell Microspheres Based on Lanthanide‐Doped NaYF4, TiO2, and Au

Efficiently harvesting solar energy for photocatalysis remains very challenging. Rational design of architectures by combining nanocomponents of radically different properties, for example, plasmonic, upconversion, and photocatalytic properties, offers a promising route to improve solar energy utilization. Herein, the synthesis of novel, plasmonic Au nanoparticle decorated NaYF₄:Yb³⁺, Er³⁺, Tm³⁺‐core@porous‐TiO₂‐shell microspheres is reported. They exhibit high surface area, good stability, broadband absorption from ultraviolet to near infrared, and excellent photocatalytic activity, significantly better than the benchmark P25 TiO₂. The enhanced activity is attributed to synergistic effects from nanocomponents arranged into the nanostructured architecture in such a way that favors the efficient charge/energy transfer among nanocomponents and largely reduced charge recombination. Optical and energy‐transfer properties are modeled theoretically to support our interpretations of catalytic mechanisms. In addition to yielding novel materials and interesting properties, the current work provides physical insights that can contribute to the future development of plasmon‐enhanced broadband catalysts.     

Understanding the Host–Guest Interaction Between Responsive Core‐Crosslinked Hybrid Nanoparticles of Hyperbranched Poly(ether amine) and Dyes: The Selective Adsorption and Smart Separation of Dyes in Water

The host–guest interaction between polymer nanoparticles and guest molecules plays a key role in fields such as controlled drug delivery, separation, and nanosensors. To understand this host–guest interaction, a series of hybrid polymer nanoparticles (SiO_1.5‐hPEA NPs) are designed and prepared based on hyperbranched poly(ether amine) (hPEA) with the different hydrophobicity and functional groups. Their adsorption behavior to twelve hydrophilic dyes in aqueous solution is studied. The core‐crosslinked hybrid nanoparticles (SiO_1.5‐hPEA NPs) are prepared by direct dispersion of hPEA containing trimethoxysilyl moieties (TMS‐hPEA) in aqueous solution, which exhibit sharp multiresponse to temperature, pH, and ionic strength in aqueous solution. The effect of molecular structure of TMS‐hPEA on the host–guest interaction between SiO_1.5‐hPEA NPs and hydrophilic dyes is investigated in detail. The obtained SiO_1.5‐hPEA NPs interact selectively with different hydrophilic dyes in aqueous solution. The distribution coefficient (K) for partitioning of dyes between SiO_1.5‐hPEA NPs and water is proposed to define the strength of the host‐guest interaction between the nanoparticles and dyes. K increases with the increasing hydrophobicity of the hPEA backbone regardless of their charge states of SiO_1.5‐hPEA NPs and dyes. A methodology is demonstrated for the smart separation of a mixture of dyes in water using SiO_1.5‐hPEA NPs.     

Cover Picture: Controlled Encapsulation of Hydrophobic Liquids in Hydrophilic Polymer Nanofibers by Co‐electrospinning (Adv. Funct. Mater. 16/2006)

The cover shows an optical image of co‐electrospun nanofibers of poly(vinyl pyrrolidone) (outside) and hydrophobic oil (inside), irradiated by UV light. The resulting non‐woven mats present monosized beads regularly distributed along the nanofibers in work reported by Loscarteles and co‐workers on p. 2110. Only the beads fluoresce, due to special markers added to the oil, indicating that the oil is indeed wholly encapsulated inside the beads. There are many technical situations, such as various biological or medical applications, in which a hydrophobic fluid must be encapsulated inside a hydrophilic polymer shell in the form of tiny microscopic pieces. A novel approach is presented, based on the co‐electrospinning of the hydrophilic polymer melt (outside) and the hydrophobic fluid (inside), which results in beaded micro‐ and nanofibers, such that the hydrophobic fluid is efficiently encapsulated inside the beads. For the selected fluid couple, the low liquid–liquid surface tension and the high viscosity of the melt prevent the varicose break‐up of inner fluid in the coaxial electrified jet until the very end of the co‐electrospinning process. The resulting fibers present beads filled with the hydrophobic fluid, separated by a rather uniform distance whose length depends partially on the melt flow rate. The bead diameter grows with the inner flow rate, going from a monosized to a bisized distribution. In the case under study, the maximum relative (inner‐to‐outer) flow rate is one. The diameter of the solid fibers between beads scales well with existing theories for simple electrospinning.