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Temporal activation of biological processes by visible light and subsequent return to an inactive state in the absence of light is an essential characteristic of photoreceptor cells. Inspired by these phenomena, light-responsive materials are very attractive due to the high spatiotemporal control of light irradiation, with light being able to precisely orchestrate processes repeatedly over many cycles. Herein, it is reported that light-driven proton transfer triggered by a merocyanine-based photoacid can be used to modulate the permeability of pH-responsive polymersomes through cyclic, temporally controlled protonation and deprotonation of the polymersome membrane. The membranes can undergo repeated light-driven swelling-contraction cycles without losing functional effectiveness. When applied to enzyme loaded-nanoreactors, this membrane responsiveness is used for the reversible control of enzymatic reactions. This combination of the merocyanine-based photoacid and pH-switchable nanoreactors results in rapidly responding and versatile supramolecular systems successfully used to switch enzymatic reactions ON and OFF on demand., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

A 'grafting-from' approach to synthesize microparticle-supported conjugated polyelectrolyte brushes is presented. Poly(3-bromohexylthiophene) is selectively grown from monodisperse organosilica microparticles by surface-initiated Kumada catalyst-transfer polycondensation (SI-KCTP) and then ionizable amino groups are introduced by a two-step polymer analogous transformation. Optical properties of the resulting microparticle-supported conjugated polyelectrolyte brushes were found to be dependent on the surrounding chemical environment and thus the particles are promising materials for sensor applications., (Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Surface-initiated Kumada catalyst-transfer polycondensation of poly(9,9-dioctylfluorene) (PFO) was performed from organosilica microparticles that resulted in PFO brushes with densely grafted PFO chains with a significantly enhanced propensity to adopt planar and ordered conformations (beta-phase).

Herein, we present a new paradigm in the engineering of nanostructured hybrids between conjugated polymer and inorganic materials via a chain-growth surface-initiated Kumada catalyst-transfer polycondensation (SI-KCTP) from particles. Poly(3-hexylthiophene), P3HT, a benchmark material for organic electronics, was selectively grown by SI-KCTP from (nano)particles bearing surface-immobilized Ni catalysts supported by bidentate phosphorus ligands, that resulted in hairy (nano)particles with end-tethered P3HT chains. Densely grafted P3HT chains exhibit strongly altered optical properties compared to the untethered counterparts (red shift and vibronic fine structure in absorption and fluorescence spectra), as a result of efficient planarization and chain-aggregation. These effects are observed in solvents that are normally recognized as good solvents for P3HT (e.g., tetrahydrofurane). We attribute this to strong interchain interactions within densely grafted P3HT chains, which can be tuned by changing the surface curvature (or size) of the supporting particle. The hairy P3HT nanoparticles were successfully applied in bulk heterojunction solar cells.

Graft work: The first surface-initiated and site-specific palladium-catalyzed Suzuki polycondensation that allows selective grafting and patterning of semiconducting and emissive poly[9,9-bis(2-ethylhexyl)fluorene] (1) at room temperature is developed (see scheme). The patterning is demonstrated by AFM (see image).

We describe a new method to grow conductive polymer (CP) brushes of regioregular head-to-tail poly(3-alkylthiophenes) (P3AT) via surface-initiated polycondensation of 2-bromo-5-chloromagnesio-3-alkylthiophene. A simple procedure for the preparation of the Ni(II) macroinitiator by the reaction of Ni(PPh3)4 with photocross-linked poly-4-bromostyrene films was developed. Exposure of the initiator layers to the monomer solution leads to selective chain growth polycondensation of the monomer from the surface, resulting in P3AT brushes in a very economical way. In contrast to the P3AT films prepared by traditional solvent casting methods, our approach leads to mechanically robust CP films, stable against delamination. We believe that our approach will be helpful in the fabrication of all-plastic devices.

The multiple application of reductive amination on primary amino groups of first and second generation poly(propyleneimine) dendrimers is used as a one-pot approach to introduce twice the amount of the oligosaccharide units as surface groups, compared to initially present amino groups in the first and second generation dendrimers. This was proven by (1)H NMR, MALDI-TOF-MS, and LILBID-MS analysis. The size of these dendrimers was determined by the hydrodynamic radius using pulsed field gradient NMR and dynamic light scattering. Molecular modeling confirmed the presence of dense-shell dendrimers. These dendrimers exhibit a generation dependent Cu(II)/dendrimer ratio in an aqueous environment, highlighting these materials as possible metal-carrier systems with a well-defined oligosaccharide protection shell for application in a biological environment.

The surface properties of films made of p-methoxyphenacyl derivative terpolymers, associated with photocleavage by UV irradiation, and their optical patterning are investigated. The deprotection reaction has been monitored by UV and FTIR spectroscopy, contact angle measurements, and X-ray photoelectron spectroscopy, revealing the photoremoval of the protecting p-methoxyphenacyl group in high yields under mild conditions. Parallel and serial patterning of the films has been performed by selective irradiation through optical masks and by laser irradiation via fiber tips of a scanning near-field optical microscope, respectively. By irradiation of photolabile protected functional groups, free carboxylic groups become exposed to the surface with which fluorescent dyes and proteins can be associated specifically.

Deposition of multiwalled carbon nanotubes modified by poly(2-vinylpyridine) (CNT-g-P2VP) from aqueous dispersions at low pH is an effective method to prepare homogeneous ultrathin films with a tunable CNTs density. A percolation threshold of 0.25 mug/cm2 and a critical exponent alpha = 1.24 have been found from dc conductivity measurements. The sheet resistance value agrees with the percolation theory for 2D films. According to AFM and electrical measurements, even when only 5% of the surface is covered by CNT-g-P2VPs, the sheet resistance is of the order of 1 MOmega/sq, which indicates that conductivity is imparted by a network of an ultralow density. When the film transmittance decreases down to approximately 70% at 550 nm, the occupied surface area is approximately 15% and sheet resistance falls down to approximately 90 kOmega/sq. These data show that undesired in-plane clustering does not occur upon the dispersion casting of the films and that high-quality networks of CNT-g-P2VPs are built up. The electrosteric stabilization of the CNT-g-P2VP dispersions in water at low pH is at the origin of this desired behavior. Although the multiwalled CNT films prepared in this work are less conductive and less transparent than the SWNTs films, they could find applications, e.g., in touch screens, reflective displays, EMI shielding, and static charge dissipation.

Brain processes underlying spoken language comprehension comprise auditory encoding, prosodic analysis and linguistic evaluation. Auditory encoding usually activates both hemispheres while language-specific stages are lateralized: analysis of prosodic cues are right-lateralized while linguistic evaluation is left-lateralized. Here, we investigated to what extent the absence of prosodic information influences lateralization. MEG brain-responses indicated that syntactic violations lead to early bi-lateral brain responses for syntax violations. When the pitch of sentences was flattened to diminish prosodic cues, the brain's syntax response was lateralized to the right hemisphere, indicating that the missing pitch was generated automatically by the brain when it was absent. This represents a Gestalt phenomenon, since we perceive more than is actually presented.

Neuromagnetic fields were recorded from the left cerebral hemisphere of six healthy right-handed subjects under three different conditions: (1) externally triggered rapid voluntary extension and flexion of the right hand, (2) passive extension and flexion of the right hand, and (3) stimulation of the skin of the right index finger by means of air pressure. Location analysis using the current density analysis did not reveal any differences between motor evoked field I (MEF I) in active and passive movements, and met the maximum of cerebral activation in the contralateral precentral region. In contrast, the sensory evoked field was located clearly in the contralateral postcentral region. Additionally, a significantly shorter latency of MEF I (with respect to movement onset) was observed in flexion compared with extension in both passive and active movements. These results support the assumption that MEF I is generated by cortical activation resulting from proprioceptive, probably muscle spindle, input. The current density analysis has proved to be an appropriate method for investigating movement-related fields. Furthermore, the described method seems to be appropriate for evaluating the processes of cortical reorganization and the influence of neurorehabilitation within longitudinal studies in patients with lesions in motor centers of the brain.

Previous electrophysiological studies had found an early anterior negativity often with a maximum over the left hemisphere to correlate with the early detection of an error in the syntactic structure of a sentence. In this paper, the cortical structures involved in such early syntactic parsing processes were localized using MEG. Subjects were presented with acoustic sentences and asked to judge their syntactic correctness. The subjects' brain responses to syntactic violations were recorded with a 148-channel whole-head magnetometer. Dipole source localization was performed using a realistically shaped standard volume conductor model with fMRI constraints. The results show that the early syntactic parsing processes are supported by temporal regions, possibly the planum polare, as well as by fronto-lateral regions. As indicated by the resultant dipole strengths, these regions are activated bilaterally with a dominance in the left hemisphere for four out of the five subjects. The contribution of the left temporal regions to the early syntactic processes seems to be larger than that of the left fronto-lateral regions.

Studies based on whole-head MEG recordings are providing more and more impressive results. In such recordings, the MEG sensors are several centimeters away from the scalp and the positions of the MEG sensors with respect to the head differ from subject to subject, and from session to session for the same subject. In this paper, a method is presented and tested to estimate the scalp MEG distributions from whole-head MEG measurements. The goal is to remove the discrepancy of MEG measurements caused by the various sensor positions with respect to the head, as well as to reduce the smearing effect caused by the distance of the MEG sensors from the scalp. The MEG measurement was first projected to a hypothetical dipole layer within the head volume conductor model using the inverse solution. The scalp MEG estimation was then obtained from the resultant dipole layer by the forward solution. The results from simulation studies, phantom experiments, and the auditory evoked field analysis demonstrated that, with reasonable signal to noise ratios, this method is a feasible way to achieve our goals.

We investigated the influence of noise on brain responses to spoken sentences in MEG. Sixteen subjects had to listen to acoustically presented sentences and judge their syntactic correctness. Sentences were either presented on a silent background or with noise. Noise had differential effects on early auditory and syntactic processes. While noise affected early auditory processes only in the right hemisphere, noise had a general effect on syntactical processes. The evoked responses to syntactic violations compared with correct sentences, namely an early left anterior negativity, were significantly suppressed when noise was present The noise suppression effect, however, was not lateralized.