Tailoring the Weight of Surface and Intralayer Edge States to Control LUMO Energies.

The energies of the frontier molecular orbitals determine the optoelectronic properties in organic films, which are crucial for their application, and strongly depend on the morphology and supramolecular structure. The impact of the latter two properties on the electronic energy levels relies primarily on nearest-neighbor interactions, which are difficult to study due to their nanoscale nature and heterogeneity. Here, an automated method is presented for fabricating thin films with a tailored ratio of surface to bulk sites and a controlled extension of domain edges, both of which are used to control nearest-neighbor interactions. This method uses a Langmuir-Schaefer-type rolling transfer of Langmuir layers (rtLL) to minimize flow during the deposition of rigid Langmuir layers composed of π-conjugated molecules. Using UV-vis absorption spectroscopy, atomic force microscopy, and transmission electron microscopy, it is shown that the rtLL method advances the deposition of multi-Langmuir layers and enables the production of films with defined morphology. The variation in nearest-neighbor interactions is thus achieved and the resulting systematically tuned lowest unoccupied molecular orbital (LUMO) energies (determined via square-wave voltammetry) enable the establishment of a model that functionally relates the LUMO energies to a morphological descriptor, allowing for the prediction of the range of accessible LUMO energies.

In Situ SERS Sensing by a Laser-Induced Aggregation of Silver Nanoparticles Templated on a Thermoresponsive Polymer.

A stimuli-responsive (pH- and thermoresponsive) micelle-forming diblock copolymer, poly(1,2-butadiene)290-block-poly(N,N-dimethylaminoethyl methacrylate)240 (PB-b-PDMAEMA), was used as a polymer template for the in situ synthesis of silver nanoparticles (AgNPs) through Ag+ complexation with PDMAEMA blocks, followed by the reduction of the bound Ag+ with sodium borohydride. A successful synthesis of the AgNPs on a PB-b-PDMAEMA micellar template was confirmed by means of UV-Vis spectroscopy and transmission electron microscopy, wherein the shape and size of the AgNPs were determined. A phase transition of the polymer matrix in the AgNPs/PB-b-PDMAEMA metallopolymer hybrids, which results from a collapse and aggregation of PDMAEMA blocks, was manifested by changes in the transmittance of their aqueous solutions as a function of temperature. A SERS reporting probe, 4-mercaptophenylboronic acid (4-MPBA), was used to demonstrate a laser-induced enhancement of the SERS signal observed under constant laser irradiation. The local heating of the AgNPs/PB-b-PDMAEMA sample in the laser spot is thought to be responsible for the triggered SERS effect, which is caused by the approaching of AgNPs and the generation of "hot spots" under a thermo-induced collapse and the aggregation of the PDMAEMA blocks of the polymer matrix. The triggered SERS effect depends on the time of a laser exposure and on the concentration of 4-MPBA. Possible mechanisms of the laser-induced heating for the AgNPs/PB-b-PDMAEMA metallopolymer hybrids are discussed.

Polyether-Based Diblock Terpolymer Micelles with Pendant Anthracene Units-Light-Induced Crosslinking and Limitations Regarding Reversibility.

The synthesis of 9-methylanthracenyl glycidyl ether (AnthGE) as a crosslinkable monomer that can be applied in anionic ring opening polymerization is reported. Diblock terpolymers of the composition methoxy-poly(ethylene oxide)-block-poly(2-ethylhexyl glycidyl ether-co-9-methylanthracenyl glycidyl ether) (mPEO-b-P(EHGE-co-AnthGE) with 10 to 24 wt% of AnthGE are synthesized and characterized. Their micellization behavior, as well as their light-induced core-crosslinking via irradiation with UV light (λ = 365 nm) is studied. The results are compared with studies on the dimerization, and the dimer cleavage via irradiation with UV-C light (λ = 254 nm), of the same diblock terpolymer in organic solution, and the small-molecule model compound 9-methoxymethylanthracene. Differences in 1 H NMR spectra of the crosslinked or dimerized compounds and reaction kinetics of the dimerization reactions under different conditions suggest possible side reactions for the case of the core-crosslinking of micelles in aqueous solution. These side reactions limit the reversibility of the anthracene dimerization reaction in aqueous solutions, even if the anthracene molecule is encapsulated within the hydrophobic core of a polymeric micelle.

Polymer Micelles Composed of Molecular-Bottlebrush-Based Surfactants: Precisely Controlling Aggregation Number Corresponding to Polyhedral Structures.

Over the past few decades, there has been remarkable progress in the construction of self-assemblies in the field of supramolecular chemistry, such as micelles with precisely controlled and refined structures. One promising approach represents the previously proposed concept of Platonic micelles, in which the aggregation number (Nagg ) is discretized in accordance with vertexes of regular polyhedra (i.e., Platonic solids), i.e., 4, 6, 8, 12, and 20 units. Herein, attempt is made to construct Platonic polymer micelles using rigid and persistent architecture of molecular-bottlebrush-based surfactant (MBS). The structure of MBS micelles is carefully elucidated using small-angle X-ray and light scattering and analytical centrifugation measurements. This study shows that the Nagg of MBS micelles is consistent with one of the Platonic numbers when Nagg is intentionally set in the range of 4-20. In addition, some of the MBS micelles demonstrate a discontinuous change in Nagg , when the salt concentration is changed, which is an important factor in controlling micellar Nagg . This is one of the characteristic aggregation behaviors of Platonic micelles in surfactant systems, which strongly indicates the formation of Platonic micelles from macromolecular surfactants.

Core-Cross-linked Fluorescent Worm-Like Micelles for Glucose-Mediated Drug Delivery.

We herein report the fabrication of core-crosslinked, fluorescent, and surface-functionalized worm-like block copolymer micelles as drug delivery vehicles. The polyether-based diblock terpolymer [allyl-poly(ethylene oxide)-block-poly(2-ethylhexyl glycidyl ether-co-furfuryl glycidyl ether)] was synthesized via anionic ring opening polymerization, and self-assembly in water as a selective solvent led to the formation of long filomicelles. Subsequent cross-linking was realized using hydrophobic bismaleimides as well as a designed fluorescent cross-linker for thermally induced Diels-Alder reactions with the furfuryl units incorporated in the hydrophobic block of the diblock terpolymer. As a fluorescent cross-linker, we synthesized and incorporated a cyanine 5-based bismaleimide in the cross-linking process, which can be used for fluorescence tracking of the particles. Furthermore, we covalently attached glucose to the allyl end groups present on the surface of the micelles to investigate active glucose-mediated transport into suitable cell lines. First studies in 2D as well as 3D cell culture models suggest a glucose-dependent uptake of the particles into cells despite their unusually large size compared to other nanoparticle systems used in drug delivery.

Triple-Responsive Polyampholytic Graft Copolymers as Smart Sensors with Varying Output.

Three triggers result in two measurable outputs from polymeric sensors: multiresponsive polyampholytic graft copolymers respond to pH-value and temperature, as well as the type and concentration of metal cations and therefore, allow the transformation of external triggers into simply measurable outputs (cloud point temperature (TCP ) and surface plasmon resonance (SPR) of encapsulated silver nanoparticles). The synthesis relies on poly(dehydroalanine) (PDha) as the reactive backbone and gives straightforward access to materials with tunable composition and output. In particular, a rather high sensitivity toward the presence of Cu2+ , Co2+ , and Pb2+ metal cations is found.