Synthesis of Gadolinium‐Labeled Shell‐Crosslinked Nanoparticles for Magnetic Resonance Imaging Applications

Shell‐crosslinked knedel‐like nanoparticles (SCKs; “knedel” is a Polish term for dumplings) were derivatized with gadolinium chelates and studied as robust magnetic‐resonance‐imaging‐active structures with hydrodynamic diameters of 40 ± 3 nm. SCKs possessing an amphiphilic core–shell morphology were produced from the aqueous assembly of diblock copolymers of poly‐(acrylic acid) (PAA) and poly(methyl acrylate) (PMA), PAA₅₂–b–PMA₁₂₈, and subsequent covalent crosslinking by amidation upon reaction with 2,2′‐(ethylenedioxy)bis(ethylamine) throughout the shell layer. The properties of these materials, including non‐toxicity towards mammalian cells, non‐immunogenicity within mice, and capability for polyvalent targeting, make them ideal candidates for utilization within biological systems. The synthesis of SCKs derivatized with Gd^III and designed for potential use as a unique nanometer‐scale contrast agent for MRI applications is described herein. Utilization of an amino‐functionalized diethylenetriaminepentaacetic acid–Gd analogue allowed for direct covalent conjugation throughout the hydrophilic shell layer of the SCKs and served to increase the rotational correlation lifetime of the Gd. In addition, the highly hydrated nature of the shell layer in which the Gd was located allowed for rapid water exchange; thus, the resulting material demonstrated large ionic relaxivities (39 s^–1 mM^–1) in an applied magnetic field of 0.47 T at 40 °C and, as a result of the large loading capacity of the material, also demonstrated high molecular relaxivities (20 000 s^–1 mM^–1).     

Facile Synthesis of Nanostructured Carbon through Self‐Assembly between Block Copolymers and Carbohydrates

A simple and direct wet chemistry method is reported to simultaneously synthesize nanostructured carbon films and particles through self‐assembly of poly(styrene)‐poly(4‐vinylpyridine) (PS‐P4VP) and carbohydrate precursors (turanose, raffinose, glucose, etc.) in two fabrication processes—spin‐coating and aerosol processing. Starting with a homogeneous solution containing PS‐P4VP and carbohydrates, evaporation of solvent during either spin‐coating or an aerosol process leads to the formation of ordered mesostructured films and particles. High temperature treatment in argon atmosphere removes PS fragments, carbonizes carbohydrates and partial PVP fragments, and results in ordered nanoporous carbon films and particles. SEM, TEM, and GISAXS characterization indicates that these nanostructured carbon materials exhibit large nanopores (> 20 nm), controlled 1–3 dimensional structures, and controlled surface chemistry. Nitrogen sorption isotherms and electrochemistry characterization indicates the accessibility of the carbon nanopores to both gas phase and aqueous phase. Results suggest that the nanostructured carbon films and particles can be tuned through solvent annealing, precursor concentration, and choice of block copolymers used. These carbon materials present varied practical applications for sorption and separation, sensors, electrode materials, etc.     

Micropattern Formation by Molecular Migration via UV‐induced Dehydration of Block Copolymers

A novel UV lithographic technique for the patterning of the block copolymer (Pluronic) thin films is developed. The present method is based on UV‐induced water affinity changes in block copolymer films. By water vapor post‐treatment of the film, a difference in water content is established between UV illuminated and unilluminated sections, which can induce an osmotic pressure at the interface. This osmotic pressure drives the migration of Pluronic molecules, resulting in formation of patterns on the block copolymer films. Remarkably, this patterning method requires neither initiators nor polymerizable moieties which are essential for a conventional photolithographic approach. Additionally, the etching process is bypassed, eliminating the use of destructive acids or organic solvents and making this an environmentally friendly patterning protocol. It is reported that Pluronic is photo‐responsive to UV exposure, which causes the dehydration of the PEO‐PPO‐PEO backbone.     

Cover Picture: Synthesis of Gadolinium‐Labeled Shell‐Crosslinked Nanoparticles for Magnetic Resonance Imaging Applications (Adv. Funct. Mater. 8/2005)

Robust, amphiphilic core–shell nanoparticles that are selectively labeled with gadolinium in the hydrophilic and water‐swollen shell layer are depicted in the cover picture. These well‐defined nanostructured materials exhibit high relaxivity, a large loading capacity, and are based upon a biocompatible platform for ultimate function in magnetic resonance imaging (MRI) applications, as reported by Wooley and co‐workers on p. 1248. Shell‐crosslinked knedel‐like nanoparticles (SCKs; “knedel” is a Polish term for dumplings) were derivatized with gadolinium chelates and studied as robust magnetic‐resonance‐imaging‐active structures with hydrodynamic diameters of 40 ± 3 nm. SCKs possessing an amphiphilic core–shell morphology were produced from the aqueous assembly of diblock copolymers of poly‐(acrylic acid) (PAA) and poly(methyl acrylate) (PMA), PAA₅₂–b–PMA₁₂₈, and subsequent covalent crosslinking by amidation upon reaction with 2,2′‐(ethylenedioxy)bis(ethylamine) throughout the shell layer. The properties of these materials, including non‐toxicity towards mammalian cells, non‐immunogenicity within mice, and capability for polyvalent targeting, make them ideal candidates for utilization within biological systems. The synthesis of SCKs derivatized with Gd^III and designed for potential use as a unique nanometer‐scale contrast agent for MRI applications is described herein. Utilization of an amino‐functionalized diethylenetriaminepentaacetic acid–Gd analogue allowed for direct covalent conjugation throughout the hydrophilic shell layer of the SCKs and served to increase the rotational correlation lifetime of the Gd. In addition, the highly hydrated nature of the shell layer in which the Gd was located allowed for rapid water exchange; thus, the resulting material demonstrated large ionic relaxivities (39 s^–1 mM^–1) in an applied magnetic field of 0.47 T at 40 °C and, as a result of the large loading capacity of the material, also demonstrated high molecular relaxivities (20 000 s^–1 mM^–1).     

Smart Nanostructured Materials based on Self‐Assembly of Block Copolymers

Nanoscale fabrication of smart materials relying on the molecular self‐assembly of block copolymers (BCPs) has been recognized as a valuable platform for various next‐generation functional structures. In this Progress Report, the recent advances in the BCP self‐assembly process, which has paved the way for viable applications of emerging nanotechnologies, are highlighted. Effective light‐induced self‐assembly based on photothermal annealing of high‐χ BCPs and conformal 3D surface nanopatterning exploiting chemically modified graphene flexible substrates are reviewed as the typical instances of advanced BCP‐based nanofabrication methodologies. Additionally, relevant potential application fields are suggested, namely, graphene nanoribbon field effect transistors, highly tunable refractive index metasurfaces for visible light, high‐sensitivity surface‐enhanced Raman spectroscopy, 2D transition metal dichalcogenide nanopatterning, sequential infiltration synthesis, and organic photovoltaics. Finally, the future research direction as well as innovative applications of these smart nanostructured materials is proposed.     

NIR‐Activated Supersensitive Drug Release Using Nanoparticles with a Flow Core

Near infrared (NIR) light‐activated supersensitive drug release via photothermal conversion is of particular interest due to its advantages in spatial and temporal control. However, such supersensitive drug release is rarely reported for polymeric nanoparticles. In this study, polymeric nanoparticles observed with flowable core can achieve NIR‐activated supersensitive drug release under the assistance of photothermal agent. It is demonstrated that only 5 s NIR irradiation (808 nm, 0.3 W cm^?2) leads to 17.8% of doxorubicin (DOX) release, while its release is almost completely stopped when the NIR laser is switched off. In contrast, the control, poly(d ,l ‐lactide) nanoparticles with rigid cores, do not exhibit such supersensitive effect. It is demonstrated that intraparticle temperature is notably increased during photothermal conversion by detecting fluorescein lifetime using a time‐correlated single photon counting (TCSPC) technique, which is the main driving force for such supersensitive drug release from hydrophobic flow core. In contrast, rigid chain of nanoparticular core hinders drug diffusion. Furthermore, such NIR light‐activated supersensitive drug release is demonstrated, which significantly enhances its anticancer efficacy, resulting in overcoming of the resistance of cancer cells against DOX treatment in vitro and in vivo. This simple and highly universal strategy provides a new approach to fabricate NIR light‐activated supersensitive drug delivery systems.     

Solid‐State NMR Investigations of the Unusual Effects Resulting from the Nanoconfinement of Water within Amphiphilic Crosslinked Polymer Networks

Two types of solid‐state ¹⁹F NMR spectroscopy experiments are used to characterize phase‐separated hyperbranched fluoropolymer–poly(ethylene glycol) (HBFP–PEG) crosslinked networks. Mobile (soft) domains are detected in the HBFP phase by a rotor‐synchronized Hahn echo under magic‐angle spinning conditions, and rigid (hard) domains by a solid echo with no magic‐angle spinning. The mobility of chains is detected in the PEG phase by ¹H → ¹³C cross‐polarization transfers with ¹H spin‐lock filters with and without magic‐angle spinning. The interface between HBFP and PEG phases is detected by a third experiment, which utilized a ¹⁹F → ¹H–(spin diffusion)–¹H → ¹³C double transfer with ¹³C solid‐echo detection. The results of these experiments show that composition‐dependent PEG inclusions in the HBFP glass rigidify on hydration, consistent with an increase in macroscopic tensile strength.     

Efficient Self‐Assembly Synthesis of Uniform CdS Spherical Nanoparticles‐Au Nanoparticles Hybrids with Enhanced Photoactivity

The treatment of environmental pollution has become one of the most critical issues in the world. Despite the progress made in the study of semiconductor photocatalysis, it is still a challenge to obtain photocatalysts with high activity through relatively simple fabrication processes. In this work, monodisperse CdS spherical nanoparticles (SNPs) of various sizes and good crystallinity are obtained by only adjusting the starting ratio of reactants and the reaction temperature, exhibiting high photocatalytic performances. The photocatalytic rate constant of the ≈ 100 nm CdS SNPs, especially, is more than double that of P25. Furthermore, 3‐mercaptopropyltrimethoxysilane is used to assist the interaction between ≈ 200 nm CdS SNPs and citrate‐stabilized Au nanoparticles (NPs). The significant increase of photocatalytic activity is confirmed by the degradation of Rodamine B (RhB) under Xe light irradiation. At the optimal Au concentration (0.5 wt%), the prepared nanohybrids show the highest photocatalytic activity, exceeding that of pure CdS two times. The superior photocatalytic performances of the CdS SNPs‐Au nanohybrids can be attributed to the intimate interfacial contact between CdS SNPs and Au NPs, which is a contributing factor to the improvement of transfer and the fate of photogenerated charge carriers from CdS SNPs to Au NPs.     

Selective Immobilization of Nanoparticles on Surfaces by Molecular Recognition using Simple Multiple H‐bonding Functionalities

Using a complementary pair of simple alkylthiolates with hydrogen‐bonding moieties, functionalized Au₅₅ clusters could be selectively deposited onto self‐assembled monolayers on gold that carry the opposite functionality. The deposition can be readily controlled by the medium in which the clusters are dissolved and by the density of the functionalities in the self‐assembled monolayers, and yields single clusters as well as two‐dimensional cluster assemblies on the surface. The clusters are sufficiently strongly bound to give structures that are stable at ambient temperature, and that allow scanning tunneling spectroscopy on single clusters on the surface.     

Surface‐Shielding Nanostructures Derived from Self‐Assembled Block Copolymers Enable Reliable Plasma Doping for Few‐Layer Transition Metal Dichalcogenides

Precise modulation of electrical and optical properties of 2D transition metal dichalcogenides (TMDs) is required for their application to high‐performance devices. Although conventional plasma‐based doping methods have provided excellent controllability and reproducibility for bulk or relatively thick TMDs, the application of plasma doping for ultrathin few‐layer TMDs has been hindered by serious degradation of their properties. Herein, a reliable and universal doping route is reported for few‐layer TMDs by employing surface‐shielding nanostructures during a plasma‐doping process. It is shown that the surface‐protection oxidized polydimethylsiloxane nanostructures obtained from the sub‐20 nm self‐assembly of Si‐containing block copolymers can preserve the integrity of 2D TMDs and maintain high mobility while affording extensive control over the doping level. For example, the self‐assembled nanostructures form periodically arranged plasma‐blocking and plasma‐accepting nanoscale regions for realizing modulated plasma doping on few‐layer MoS₂, controlling the n‐doping level of few‐layer MoS₂ from 1.9 × 10¹¹ cm^?2 to 8.1 × 10¹¹ cm^?2 via the local generation of extra sulfur vacancies without compromising the carrier mobility.     

Impact of Reactive Amphiphilic Copolymers on Mechanical Properties and Cell Responses of Fibrin‐Based Hydrogels

Mechanical properties of hydrogels can be modified by the variation of structure and concentration of reactive building blocks. One promising biological source for the synthesis of biocompatible hydrogels is fibrinogen. Fibrinogen is a glycoprotein in blood, which can be transformed enzymatically to fibrin playing an important role in wound healing and clot formation. In the present work, it is demonstrated that hybrid hydrogels with their improved mechanical properties, tunable internal structure, and enhanced resistance to degradation can be synthesized by a combination of fibrinogen and reactive amphiphilic copolymers. Water‐soluble amphiphilic copolymers with tunable molecular weight and controlled amounts of reactive epoxy side groups are used as reactive crosslinkers to reinforce fibrin hydrogels. In the present work, copolymers that can influence the mechanical properties of fibrin‐based hydrogels are used. The reactive copolymers increase the storage modulus of the hydrogels from 600 Pa to 30 kPa. The thickness of fibrin fibers is regulated by the copolymer concentration. It could be demonstrated that the fibrin‐based hydrogels are biocompatible and support cell proliferation. Their degradation rate is considerably slower than that of native fibrin gels. In conclusion, fibrin‐based hydrogels with tunable elasticity and fiber thickness useful to direct cell responses like proliferation and differentiation are produced.     

Conception of Stretchable Resistive Memory Devices Based on Nanostructure‐Controlled Carbohydrate‐block‐Polyisoprene Block Copolymers

It is discovered that the memory‐type behaviors of novel carbohydrate‐block ‐polyisoprene (MH‐b ‐PI) block copolymers‐based devices, including write‐once‐read‐many‐times, Flash, and dynamic‐random‐access‐memory, can be easily controlled by the self‐assembly nanostructures (vertical cylinder, horizontal cylinder, and order‐packed sphere), in which the MH and PI blocks, respectively, provide the charge‐trapping and stretchable function. With increasing the flexible PI block length, the stretchability of the designed copolymers can be significantly improved up to 100% without forming cracks. Thus, intrinsically stretchable resistive memory devices (polydimethylsiloxane(PDMS)/carbon nanotubes(CNTs)/MH‐b ‐PI thin film/Al) using the MH‐b ‐PI thin film as an active layer is successfully fabricated and that using the MH‐b ‐PI_12.6k under 100% strain exhibits an excellent ON/OFF current ratio of over 10⁶ (reading at ?1 V) with stable V _set around ?2 V. Furthermore, the endurance characteristics can be maintained over 500 cycles upon 40% strain. This work establishes and represents a novel avenue for the design of green carbohydrate‐derived and stretchable memory materials.     

Ultrafast Assembly of PS‐PDMS Block Copolymers on 300 mm Wafers by Blending with Plasticizers

Next‐generation lithography techniques based on the self‐assembly of block copolymers (BCPs) are promising methods for high‐resolution pattering. BCPs with a high incompatibility (high‐χ), such as polystyrene‐polydimethylsiloxane (PS‐PDMS), show encouraging results in terms of resolution. In the strong segregation regime, the high diffusive energy barrier of PS‐PDMS excessively reduces the self‐assembly kinetics; this is why solvent–vapor annealing is typically adopted to shorten the self‐assembly time. Plasticizers are generally used to reduce the glass transition temperature (T_g) of polymers. In this study, commercial plasticizers such as dioctylsebacate and diisooctyl adipate are blended with PS‐PDMS polymers, and their influence on the self‐assembly process is investigated. The intrinsic PS selectivity of the plasticizers brings the BCP to form PS‐PDMS micelles, which results in highly ordered self‐assembled body‐centered cubic spherical PS‐PDMS after spin‐coating without any annealing. The negligible vapor pressure of plasticizers and the decrease of T_g allow the high mobility of PS‐PDMS micelles in thin films. A transition into a stable horizontal cylindrical morphology is then possible by ultrafast thermal annealing (30 s). The complete process, from the BCP deposition to the final pattern transfer into Si, is presented on 300 mm standard wafers, which makes this method promising for microelectronic industrial integration.     

Solar Cells with Enhanced Photocurrent Efficiencies Using Oligoaniline‐Crosslinked Au/CdS Nanoparticles Arrays on Electrodes

Different configurations of CdS nanoparticles (NPs) are linked to Au electrodes by electropolymerization of thioaniline‐functionalized CdS NPs onto thioaniline‐functionalized Au‐electrodes. In one configuration, thioaniline‐functionalized CdS NPs are electropolymerized in the presence of thioanline‐modified Au NPs to yield an oligoaniline‐crosslinked CdS/Au NPs array. The NP‐functionalized electrode generates a photocurrent with a quantum yield that corresponds to ca. 9%. The photocurrent intensities are controlled by the potential applied on the electrode, and the redox‐state of the oligoaniline bridge. In the oxidized quinoide state of the oligoaniline units, the bridges act as electron acceptors that trap the conduction‐band electrons that are transported to the electrode and lead to high quantum yield photocurrents. The reduced π‐donor oligoaniline bridges act as π‐donor sites that associate N,N′‐dimethyl‐4,4′‐bipyridinium, MV²⁺, by donor/acceptor interactions, K_a = 5270 M^?1. The associated MV²⁺ acts as an effective trap of the conduction‐band electrons, and in the presence of triethanolamine (TEOA) as an electron donor, high photocurrent values are measured (ca. 12% quantum yield). The electropolymerization of thioaniline‐functionalized Au NPs and thioaniline‐modified CdS NPs in the presence of MV²⁺ yields a MV²⁺‐imprinted NP array. The imprinted array exhibits enhanced affinities toward the association of MV²⁺ to the oligoaniline π‐donor sites, K_a = 2.29 × 10⁴ M^?1. This results in the effective trapping of the conduction‐band electrons and an enhanced quantum yield of the photocurrent, ca. 34%. The sacrificial electron donor, TEOA, was substituted with the reversible donor I₃^?. A solar cell consisting of the imprinted CdS/Au NPs array, with MV²⁺ and I₃^?, was constructed. The cell generated a photocurrent with a quantum yield of 4.7%.     

Synthesis of Amphiphilic Copolymers of Poly(ethylene oxide) and Poly(ϵ‐caprolactone) with Different Architectures,and Their Role in the Preparation of Stealthy Nanoparticles

Well‐defined copolymers of biocompatible poly(?‐caprolactone) (PCL) and poly(ethylene oxide) (PEO) are synthesized by two methods. Graft copolymers with a gradient structure are prepared by ring‐opening copolymerization of ?‐caprolactone (?CL) with a PEO macromonomer of the ?CL‐type. The ?CL polymerization is initiated by a PEO macroinitiator to prepare diblock copolymers. These amphiphilic copolymers are used as stabilizers for biodegradable poly(D,L ‐lactide) (PLA) nanoparticles prepared by a nanoprecipitation technique. The effect of the copolymer characteristic features (architecture, composition, and amount) on the nanoparticle formation and structure is investigated. The average size, size distribution, and stability of aqueous suspensions of the nanoparticles is measured by dynamic light scattering. For comparison, an amphiphilic random copolymer, poly(methyl methacrylate‐co‐methacrylic acid) (P(MMA‐co‐MA)), is synthesized. The stealthiness of the nanoparticles is analyzed in relation to the copolymer used as stabilizer. For this purpose, the activation of the complement system by nanoparticles is investigated in vitro using human serum. This activation is much less important whenever the nanoparticles are stabilized by a PEO‐containing copolymer rather than by the P(MMA‐co‐MA) amphiphile. The graft copolymers with a gradient structure and the diblock copolymers with similar macromolecular characteristics (molecular weight and hydrophilicity) are compared on the basis of their capacity to coat PLA nanoparticles and to make them stealthy.     

Antibacterial Surface Coatings from Zinc Oxide Nanoparticles Embedded in Poly(N‐isopropylacrylamide) Hydrogel Surface Layers

Despite multiple research approaches to prevent bacterial colonization on surfaces, device‐associated infections are currently responsible for about 50% of nosocomial infections in Europe and significantly increase health care costs, which demands development of advanced antibacterial surface coatings. Here, novel antimicrobial composite materials incorporating zinc oxide nanoparticles (ZnO NP) into biocompatible poly(N‐isopropylacrylamide) (PNIPAAm) hydrogel layers are prepared by mixing the PNIPAAm prepolymer with ZnO NP, followed by spin‐coating and photocrosslinking. Scanning electron microscopy (SEM) characterization of the composite film morphology reveals a homogeneous distribution of the ZnO NP throughout the film for every applied NP/polymer ratio. The optical properties of the embedded NP are not affected by the matrix as confirmed by UV‐vis spectroscopy. The nanocomposite films exhibit bactericidal behavior towards Escherichia coli (E. coli) for a ZnO concentration as low as ≈0.74 μg cm^?2 (1.33 mmol cm^?3), which is determined by inductively coupled plasma optical emission spectrometry. In contrast, the coatings are found to be non‐cytotoxic towards a mammalian cell line (NIH/3T3) at bactericidal loadings of ZnO over an extended period of seven days. The differential toxicity of the ZnO/hydrogel nanocomposite thin films between bacterial and cellular species qualifies them as promising candidates for novel biomedical device coatings.     

Orientational Switching of Mesogens and Microdomains in Hydrogen‐Bonded Side‐Chain Liquid‐Crystalline Block Copolymers Using AC Electric Fields

In this report, we show that the microstructures of hydrogen‐bonded side‐chain liquid‐crystalline block copolymers can be rapidly aligned in an alternating current (AC) electric field at temperatures below the order–disorder transition but above the glass transition. The structures and their orientation were measured in real time with synchrotron X‐ray scattering. Incorporation of mesogenic groups with marked dipolar properties is a key element in this process. A mechanism related to the dissociation of hydrogen bonds is proposed to account for the fast orientation switching of the hydrogen‐bonded blends.     

Beyond State of the Art Honeycomb Membranes: High Performance Ordered Arrays from Multiprogrammable Linear‐Dendritic Block Copolymers

A new generation of honeycomb membranes is herein described from a novel library of multipurpose linear‐dendritic block copolymers. These are accomplished by combining atom transfer radical polymerization together with dendrimer chemistry and click reactions. The resulted amorphous block copolymers, with T_g between 30 and 40 °C, display three important functions, i.e., pore generating aromatic groups, crosslinking azides, and multiple dendritic functional groups. All block copolymers enable the successful fabrication of honeycomb membranes through the facile breath figure method. The peripheral dendritic functionality is found to influence the porous morphologies from closed pored structure with pore size of 1.12 μm² to open pore structure with pore size 10.26 μm². Facile UV crosslinking of the azides yields membranes with highly durable structural integrity. Upon crosslinking, the pH and thermal stability are extended beyond the noncrosslinked membranes in which the porous integrity is maintained up to 400 °C and pH 1–14. Taking into account the straightforward and cost‐efficient strategy to generate ordered, functional, and structurally stable honeycomb membranes on various solid substrates, it is apparent that these multipurpose block copolymers may unlock future applications including use as molds for soft lithography.     

Facile Fabrication and Superparamagnetism of Silica‐Shielded Magnetite Nanoparticles on Carbon Nitride Nanotubes

Using conventional methods to synthesize magnetic nanoparticles (NPs) with uniform size is a challenging task. Moreover, the degradation of magnetic NPs is an obstacle to practical applications. The fabrication of silica‐shielded magnetite NPs on carbon nitride nanotubes (CNNTs) provides a possible route to overcome these problems. While the nitrogen atoms of CNNTs provide selective nucleation sites for NPs of a particular size, the silica layer protects the NPs from oxidation. The morphology and crystal structure of NP–CNNT hybrid material is investigated by transmission electron microscopy (TEM) and X‐ray diffraction. In addition, the atomic nature of the N atoms in the NP–CNNT system is studied by near‐edge X‐ray absorption fine structure spectroscopy (nitrogen K‐edge) and calculations of the partial density of states based on first principles. The structure of the silica‐shielded NP–CNNT system is analyzed by TEM and energy dispersive X‐ray spectroscopy mapping, and their magnetism is measured by vibrating sample and superconducting quantum interference device magnetometers. The silica shielding helps maintain the superparamagnetism of the NPs; without the silica layer, the magnetic properties of NP–CNNT materials significantly degrade over time.