2D Plasmonic Molecules via Hydrogen Bond Interaction between Polymer-Grafted Nanoparticles.

The use of macromolecular design features to regulate non-covalent bonding on the nanoscale is a young and emerging fabrication strategy for advanced nanostructures. For the first time, we describe a self-assembly method to create a series of 2D plasmonic molecules (PMs) using hydrogen-bond interaction between a pair of polymer-capped gold nanoparticles (hydrogen-bond donor and acceptor). Due to the nature of hydrogen-bond interaction, we found that polymer interaction and solvation compete with each other during the self-assembly process, which turns out to be the most important condition for controlling the coordination number of PMs. We have conducted an extensive study on the solvent effect, which has helped us to design and fabricate a series of precise PMs with high symmetry.

Free-Radical Propagation Rate Coefficients of Diethyl Itaconate and Di-n-Propyl Itaconate Obtained via PLP-SEC.

The propagation step is one of the key reactions in radical polymerization and knowledge about its kinetics is often vital for understanding and designing polymerization processes leading to new materials or optimizing technical processes. Arrhenius expressions for the propagation step in free-radical polymerization of diethyl itaconate (DEI) as well as di-n-propyl itaconate (DnPI) in bulk, for which propagation kinetics was yet unexplored, were thus determined via pulsed-laser polymerization in conjunction with size-exclusion chromatography (PLP-SEC) experiments in the temperature range of 20 to 70 °C. For DEI, the experimental data was complemented by quantum chemical calculation. The obtained Arrhenius parameters are A = 1.1 L·mol-1·s-1 and Ea = 17.5 kJ·mol-1 for DEI and A = 1.0 L·mol-1·s-1 and Ea = 17.5 kJ·mol-1 for DnPI.

Gold nanoparticle ring arrays from core-satellite nanostructures made to order by hydrogen bond interactions.

Polyethylene glycol-grafted gold nanoparticles are attached to silica nanoparticle cores via hydrogen bonding in a controlled fashion, forming well-defined core-satellite structures in colloidal solution. For separating these complex structures effectively from the parental nanoparticles, a straightforward and easy protocol using glass beads has been developed. The attached gold nanoparticles show unique surface mobility on the silica core surface, which allows for nanoparticle rearrangement into a 2D ring pattern surrounding the silica nanoparticle template when the core-satellite structures are cast to a planar surface. When etching away the silica core under conditions in which the polymer shell fixes the satellites to the substrate, highly ordered ring-shaped patterns of gold nanoparticles are formed. By variation of the size of the parental particles - 13 to 28 nm for gold nanoparticles and 39 to 62 nm for silica nanoparticles - a great library of different ring-structures regarding size and particle number is accessible with relative ease. The proposed protocol is low-cost and can easily be scaled up. It moreover demonstrates the power of hydrogen bonds in polymers as a dynamic anchoring tool for creating nanoclusters with rearrangement ability. We believe that this concept constitutes a powerful strategy for the development of new and innovative nanostructures.

Efficacy of occlusive wraps used for delivery room care.

BACKGROUND: Guidelines advise for more than 20 years to use occlusive plastic wraps for temperature management during delivery room care but data on efficacy of different types of wrap are still scarce. METHODS: A random sample of seven different types of plastic wrap was tested using prewarmed aluminium blocks. RESULTS: The most effective wrap increased the time to cool by 2°C by one-third for the core and by 100% for the surface whereas the least effective wrap led to even faster heat loss compared with no wrap at all. The least effective wrap concerning all capacities tested was made from polyurethane that contains potentially toxic and narcotic monomers. Heat and water retention did not correlate to wrap thickness. DISCUSSION: Large differences in heat and water retention capacity warrant a careful choice of the type of wrap as some might be counterproductive. Wraps containing polyurethane should not be used.

Increasing the Gas Barrier Properties of Polyethylene Foils by Coating with Poly(methyl acrylate)-Grafted Montmorillonite Nanosheets.

Low-density polyethylene (LDPE) foils were coated with a thin film of polymer-grafted Montmorillonite (MMT) nanosheets, which form a barrier against gas diffusion due to their unique brick-and-mortar arrangement. The MMT nanosheets were grafted with poly(methyl acrylate) (PMA), a soft and flexible polymer. Already very thin films of this nanocomposite could reduce gas permeability significantly. The impact of the topology of the surface-grafted polymer on gas permeability was also studied. It was found that grafting MMT nanosheets with a mixture of star-shaped and linear PMA and with PMA that is cross-linked via hydrogen bonds further decrease gas permeability. The presented strategy is quick and simple and allows for the easy formation of effective gas barrier coatings for LDPE foils, as used in food packaging.

Self-Compounded Nanocomposites: toward Multifunctional Membranes with Superior Mechanical, Gas/Oil Barrier, UV-Shielding, and Photothermal Conversion Properties.

Nanocomposites combine multiple favorable properties to achieve intriguing functionalities, but the formation of nanocomposites with only one constituent with the inclusion of multiple superior properties is still not known. Herein, novel self-compounded nanocomposite membranes from one single polymer-cellulose cinnamate (CCi)-with multiple outstanding properties are reported. The self-compounded membranes contain two distinct morphologies as CCi nanoparticles (CCi-NPs) and a CCi polymer matrix, while CCi-NPs are either firmly embedded in the CCi matrix or fused with adjacent CCi-NPs. The unique self-compounded nanostructure endows the membranes with a tensile strength of 94 MPa and Young's modulus of 3.1 GPa. The water vapor permeability, oxygen permeability, and oil permeability reach as low as (0.94 ± 0.03) × 10-11 g m-1 s-1 Pa-1, (8.48 ± 2.39) ×10-13 cm3·cm/cm2·s·cmHg, and 0.008 ± 0.003 g mm m-2 day-1, respectively. Moreover, self-compounded CCi nanocomposite membranes also demonstrate UV-shielding and photothermal conversion properties. UVB and UVC light are entirely blocked, while UVA light is partly blocked. The temperature increases from room temperature to 120 °C within 1 min under UV irradiation. In addition, CCi membranes also show remarkable thermal and humidity resistance. Based on these outstanding properties, CCi membranes are applied as food packaging materials. This work offers a new avenue to construct nanocomposites with multiple superior properties from one constituent, which is promising for diverse applications.

Near-Infrared-Triggered Photothermal Aggregation of Polymer-Grafted Gold Nanorods in a Simulated Blood Fluid.

Gold nanorods were decorated with thermoresponsive copolymers of tailored architecture and constructed from N-isopropyl acrylamide and acrylamide. The copolymers were prepared via reversible addition-fragmentation chain transfer polymerization (RAFT) and immobilized on the gold nanorod surface taking advantage of the aurophilicity of its inherently formed trithiocarbonate groups. The topology as well as the average molecular weight of the copolymers was altered using either a monofunctional or 3-arm star RAFT agent. Two-dimensional arrays of the self-assembled core-shell nanostructures were fabricated by drop-casting showing tunable interparticle spacings. In a simulated blood fluid, the lower critical solution temperature of the nanohybrids could be modified over a significant temperature range around body temperature by adjusting the copolymer composition, the architecture, and/or the size of the polymer. The intrinsic photothermal properties of the gold nanorods were utilized to trigger particle aggregation by irradiation at 808 nm in the optical window of human tissues. In effect, a new nanohybrid system with remotely controllable aggregation via an external NIR-light stimulus for nanomedical applications was developed.

Macroscalar Helices Co-Assembled from Chirality-Transferring Temperature-Responsive Carbohydrate-Based Bolaamphiphiles and 1,4-Benzenediboronic Acid.

We present the first example of macroscalar helices co-assembled from temperature-responsive carbohydrate-based bolaamphiphiles (CHO-Bolas) and 1,4-benzenediboronic acid (BDBA). The CHO-Bolas contained hydrophilic glucose or mannose moieties and a hydrophobic coumarin dimer. They showed temperature-responsive reversible micelle-to-vesicle transition (MVT) in aqueous solutions. After the binding of carbohydrate moieties with boronic acids of BDBA in their alkaline solutions, right-handed helices were formed via the temperature-driven chirality transfer of d-glucose or d-mannose from the molecular to supramolecular level. These helices were co-assembled by unreacted BDBA, boronate esters (B-O-C bonds) between CHO-Bolas and BDBA, as well as boroxine anhydrides (B-O-B bonds) of self-condensed BDBA. After heating at 300 °C under nitrogen, the helices displayed excellent morphological stability. Moreover, they emitted bright blue luminescence caused by strong self-condensation of BDBA and decomposition of coumarin dimers.

Prediction of Kinetically Stable Nanotheranostic Superstructures: Integral of First-Passage Times from Constrained Simulations.

The kinetics of forming multifunctional nanostructures, such as nanotheranostic superstructures, is often highly protracted, involving macroscopic time scales and resulting in nanostructures that correspond to kinetically stable states rather than thermodynamic equilibrium. Predicting such kinetically stable nanostructures becomes a great challenge due to the widely different, relevant time scales that are implicated in the formation kinetics of nano-objects. We develop a methodology, integral of first-passage times from constrained simulations (IFS), to predict kinetically stable, planet-satellite nanotheranostic superstructures. The simulation results are consistent with our experimental observations. The developed methodology enables the exploration of time scales from molecular vibrations of 10-3 ns toward macroscopic scales, 1010 ns, which permits the rational design and prediction of kinetically stable nanotheranostic superstructures for applications in nanomedicine.

Supramolecular Self-Assembly of ß3 -Peptides Mediated by Janus-Type Recognition Units.

To gain mechanistic insights, natural systems with biochemical relevance are inspiring for the creation of new biomimetics with unique properties and functions. Despite progress in rational design and protein engineering, folding and intramolecular organization of individual components into supramolecular structures remains challenging and requires controlled methods. Foldamers, such as ß-peptides, are structurally well defined with rigid conformations and suitable for the specific arrangement of recognition units. Herein, we show the molecular arrangement and aggregation of ß3 -peptides into a hexameric helix bundle. For this purpose, ß-amino acid side chains were modified with cyanuric acid and triamino-s-triazine as complementary recognition units. The pre-organization of the ß3 -peptides leads these Janus molecule pairs into a hexameric arrangement and a defined rosette nanotube by stacking. The helical conformation of the subunits was indicated by circular dichroism spectroscopy, while the supramolecular arrangement was detected by dynamic light scattering and confirmed by high-resolution electrospray ionization mass spectrometry (ESI-HRMS).

Controlled Arrangement of Gold Nanoparticles on Planar Surfaces via Constrained Dewetting of Surface-Grafted RAFT Polymer.

Linear and four-arm star polystyrene samples prepared by RAFT polymerization were grafted to gold surfaces directly via their thiocarbonylthio-end groups. Nanoscale polymer patterns were subsequently formed via constrained dewetting. The patterned polymer films then served as a template for the precise arrangement of gold nanoparticles in a monolayer with a well-defined and regular structure. Using star polymers as a linker between the planar gold surface and the particles, the structural stability of the arranged particles can be further enhanced. The surface-bound nanocomposite films made of polymer and nanoparticles can also reversibly switch their nanostructures by simple wetting or dewetting treatment.

Mesoporous-silica-coated palladium-nanocubes as recyclable nanocatalyst in C-C-coupling reaction - a green approach.

We report the straightforward design of a recyclable palladium-core-silica-shell nanocatalyst showing an excellent balance between sufficient stability and permeability. The overall process - design, catalysis and purification - is characterized by its sustainability and simplicity accompanied by a great recycling potential and ultra high yields in C-C-coupling reactions.

Micellar Catalysis for Ruthenium(II)-Catalyzed C-H Arylation: Weak-Coordination-Enabled C-H Activation in H2 O.

Chemoselective C-H arylations were accomplished through micellar catalysis by a versatile single-component ruthenium catalyst. The strategy provided expedient access to C-H-arylated ferrocenes with wide functional-group tolerance and ample scope through weak chelation assistance. The sustainability of the C-H arylation was demonstrated by outstanding atom-economy and recycling studies. Detailed computational studies provided support for a facile C-H activation through thioketone assistance.

Silica-Coated Magnetite Nanoparticles Carrying a High-Density Polymer Brush Shell of Hydrophilic Polymer.

Integrating the properties of magnetite nanoparticles (MNPs) and high-density polymer brushes in one structure requires sophisticated synthetic designs and effective chemical approaches. A simple and versatile strategy for the fabrication of hydrophilic-polymer-capped magnetite-core-silica-shell nanohybrids with well-defined structure employing reverse microemulsion technique and reversible addition-fragmentation chain transfer (RAFT) polymerization is presented. The high-density polymer brush allows precise patterning of the magnetic nanohybrids with a tunable interparticle distance ranging from 20 nm to 80 nm by controlling the polymer size. The high structural precision provides a near stand-alone state of the MNPs in the nanohybrids with effectively inhibited magnetic interaction, as shown by superconducting quantum interference device (SQUID) measurements.

Palladium-Catalyzed 4-Fold Domino Reaction for the Synthesis of a Polymeric Double Switch.

A palladium-catalyzed 4-fold domino reaction consisting of two carbopalladation reactions and two C-H activation reactions, followed by the introduction of an acrylate moiety, led to the tetra-substituted helical alkene A2, using the dialkyne A3 as a substrate. The alkene was copolymerized with butyl acrylate by using the reversible addition-fragmentation chain transfer polymerization (RAFT) to give the desired polymeric switch A1.

Surface Modification of Wood Flour via ARGET ATRP and Its Application as Filler in Thermoplastics.

Wood flour is particularly suitable as a filler in thermoplastics because it is environmentally friendly, readily available, and offers a high strength-to-density ratio. To overcome the insufficient interfacial adhesion between hydrophilic wood and a hydrophobic matrix, a thermoplastic polymer was grafted from wood flour via surface-initiated activators regenerated by electron transfer-atom transfer radical polymerization (SI-ARGET ATRP). Wood particles were modified with an ATRP initiator and subsequently grafted with methyl acrylate for different polymerization times in the absence of a sacrificial initiator. The successful grafting of poly(methyl acrylate) (PMA) was demonstrated using attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and water contact angle (WCA) measurements. To confirm the control over the polymerization, a cleavable ATRP initiator was immobilized on the particles, allowing the detachment of the grafted polymer under mild conditions. The grafted particles were incorporated into a PMA matrix using solvent casting and their influence on the mechanical properties (Young's modulus, yield strength, and toughness) of the composite was investigated. Tensile testing showed that the mechanical properties improved with increasing polymerization time and increasing ratio of incorporated grafted particles.

Polyethylene-Grafted Gold and Silver Nanoparticles Using Catalyzed Chain Growth (CCG).

We report an efficient synthesis route for the formation of gold/silver-core⁻PE-shell nanohybrids in a simple self-assembly approach using PE with strong aurophilicity and argentophilicity, via thiol- and trithiocarbonate terminated moieties. This united the unique properties of polyethylene (PE) with gold and silver nanoparticles, using the well-defined end-group design of PE. These nanocomposites showed a similar solubility as PE, as confirmed by dynamic light scattering, and could be fully incorporated into a polyethylene matrix with different particle contents, as visualized by transmission electron microscopy. Using UV/vis-spectroscopy, we observed reversible, thermoresponsive aggregation/deaggregation properties in the nanohybrids, validating the strong and effective anchoring of PE on gold/silver surfaces.

Thermoreversible Self-Assembly of Perfluorinated Core-Coronas Cellulose-Nanoparticles in Dry State.

Self-assembly of nanoparticles (NPs) forming unique structures has been investigated extensively over the past few years. However, many self-assembled structures by NPs are irreversible, because they are generally constructed using their suspensions. It is still challenging for NPs to reversibly self-assemble in dry state, let alone of polymeric NPs with general sizes of hundreds of nm. Herein, this study reports a new reversible self-assembly phenomenon of NPs in dry state, forming thermoreversible strip-like supermolecular structures. These novel NPs of around 150 nm are perfluorinated surface-undecenoated cellulose nanoparticles (FSU-CNPs) with a core-coronas structure. The thermoreversible self-assembled structure is formed after drying in the air at the interface between FSU-CNP films and Teflon substrates. Remarkably, the formation and dissociation of this assembled structure are accompanied by a reversible conversion of the surface hydrophobicity, film transparency, and anisotropic properties. These findings show novel feasibility of reversible self-assembly of NPs in dry state, and thereby expand our knowledge of self-assembly phenomenon.

Thermosensitive Cation-Selective Mesochannels: PNIPAM-Capped Mesoporous Thin Films as Bioinspired Interfacial Architectures with Concerted Functions.

Rational design and elaborate modular construction of interfacial architectures in which molecular transport is mediated by responsive/adaptive nanostructures has become a growing and fertile field of research in supramolecular materials chemistry. This work presents, for the first time, the use of PNIPAM-capped mesoporous silica thin films as thermosensitive cation-selective mesochannels. Thus far, this feature has only been observed in thermosensitive biological channels. The interfacial architecture created here accomplishes its specific functions through the concerted or simultaneous action of spatially addressed subunits with temperature response and ion exclusion capabilities. The thermo-perm-selectivity effect stems from the synergistic interplay between the pH-dependent electrostatic characteristics of the silica scaffold and the thermo-controlled steric effects introduced by the capping brush layer. It is hoped that the "nanoarchitectonic" approach presented here will provide new routes toward the generation of heterosupramolecular nanosystems displaying addressable transport properties similar to those encountered in biological ion channels.

Uniform Distance Scaling Behavior of Planet-Satellite Nanostructures Made by Star Polymers.

Planet-satellite nanostructures from RAFT star polymers and larger (planet) as well as smaller (satellite) gold nanoparticles are analyzed in experiments and computer simulations regarding the influence of arm number of star polymers. A uniform scaling behavior of planet-satellite distances as a function of arm length was found both in the dried state (via transmission electron microscopy) after casting the nanostructures on surfaces and in the colloidally dispersed state (via simulations and small-angle X-ray scattering) when 2-, 3-, and 6-arm star polymers were employed. This indicates that the planet-satellite distances are mainly determined by the arm length of star polymers. The observed discrepancy between TEM and simulated distances can be attributed to the difference of polymer configurations in dried and dispersed state. Our results also show that these distances are controlled by the density of star polymers end groups, and the number of grabbed satellite particles is determined by the magnitude of the corresponding density. These findings demonstrate the feasibility to precisely control the planet-satellite structures at the nanoscale.