Sequential In-Situ Growth of Layered Conjugated Polymers for Optoelectronics Under Electrochemical Control.

Layered optoelectronic devices are manufactured using multistep procedures that require high precision in the spatial positioning of individual materials. Current technology uses costly and tedious procedures and instrumentation. In this work instead, we propose an approach which exploits the fundamental properties of the substrate to direct the growth of the next layer, here controlled by an electrochemical potential. We have electrochemically synthesized and characterized a series of polymeric materials that are most commonly used in the field. The films produced show gradient monomer ratios embedded in the polymeric film as a function of the distance from the working electrode. Under the optimized conditions, reproducible construction of simple electronic elements, e. g., rectifying diodes, is achieved. We argue that the sequential in situ method leads to gradient composition of polymer chains and the film resulting in the rectification of electric current. We discuss how this system can open new avenues in advanced optoelectronic applications, such as organic light-emitting diodes (OLEDs) or field-effect transistors (OFETs).

Glycocalix[4]arenes and their affinity to a library of galectins: the linker matters.

Galectins are lectins that bind ß-galactosides. They are involved in important extra- and intracellular biological processes such as apoptosis, and regulation of the immune system or the cell cycle. High-affinity ligands of galectins may introduce new therapeutic approaches or become new tools for biomedical research. One way of increasing the low affinity of ß-galactoside ligands to galectins is their multivalent presentation, e.g., using calixarenes. We report on the synthesis of glycocalix[4]arenes in cone, partial cone, 1,2-alternate, and 1,3-alternate conformations carrying a lactosyl ligand on three different linkers. The affinity of the prepared compounds to a library of human galectins was determined using competitive ELISA assay and biolayer interferometry. Structure-affinity relationships regarding the influence of the linker and the core structure were formulated. Substantial differences were found between various linker lengths and the position of the triazole unit. The formation of supramolecular clusters was detected by atomic force microscopy. The present work gives a systematic insight into prospective galectin ligands based on the calix[4]arene core.

Reversible Lectin Binding to Glycan-Functionalized Graphene.

The monolayer character of two-dimensional materials predestines them for application as active layers of sensors. However, their inherent high sensitivity is always accompanied by a low selectivity. Chemical functionalization of two-dimensional materials has emerged as a promising way to overcome the selectivity issues. Here, we demonstrate efficient graphene functionalization with carbohydrate ligands-chitooligomers, which bind proteins of the lectin family with high selectivity. Successful grafting of a chitooligomer library was thoroughly characterized, and glycan binding to wheat germ agglutinin was studied by a series of methods. The results demonstrate that the protein quaternary structure remains intact after binding to the functionalized graphene, and that the lectin can be liberated from the surface by the addition of a binding competitor. The chemoenzymatic assay with a horseradish peroxidase conjugate also confirmed the intact catalytic properties of the enzyme. The present approach thus paves the way towards graphene-based sensors for carbohydrate-lectin binding.

Surface-Confined Macrocyclization via Dynamic Covalent Chemistry.

Surface-confined synthesis is a promising approach to build complex molecular nanostructures including macrocycles. However, despite the recent advances in on-surface macrocyclization under ultrahigh vacuum, selective synthesis of monodisperse and multicomponent macrocycles remains a challenge. Here, we report on an on-surface formation of [6 + 6] Schiff-base macrocycles via dynamic covalent chemistry. The macrocycles form two-dimensional crystalline domains on the micrometer scale, enabled by dynamic conversion of open-chain oligomers into well-defined ∼3.0 nm hexagonal macrocycles. We further show that by tailoring the length of the alkyl substituents, it is possible to control which of three possible products-oligomers, macrocycles, or polymers-will form at the surface. In situ scanning tunneling microscopy imaging combined with density functional theory calculations and molecular dynamics simulations unravel the synergistic effect of surface confinement and solvent in leading to preferential on-surface macrocyclization.

Thermoreversible magnetic nanochains.

The reversible organization of nanomagnets into highly anisotropic assemblies is of considerable interest for many applications, including theragnostic strategies in vivo. The current preparation strategies lead to structures that are not stable without the permanent presence of an applied magnetic field (MF); otherwise, irreversible assemblies are produced with moderate shape anisotropy at nanoscales. Here, we present a new approach based on the thermoreversible Diels-Alder reaction in the presence of an external MF that enables the assembly of single-domain nanomagnets into narrow chains with lengths of several micrometers. The MF-assisted click chemistry approach included (i) the synthesis of nanoparticles through a modified hydrothermal method, (ii) their functionalization via ligand exchange, (iii) the MF-assisted formation of chains, and (iv) the linkage of the nanomagnets in the presence of the magnetic field. Moreover, the chains can be again disassembled at elevated temperatures through a retro-Diels-Alder reaction. We thus demonstrated for the first time that MF-assisted click chemistry is a convenient method for large-scale preparation of highly anisotropic assemblies of nanosized magnets that can be reversibly decomposed by thermal treatment.

Spatially Resolved Covalent Functionalization Patterns on Graphene.

Spatially resolved functionalization of 2D materials is highly demanded but very challenging to achieve. The chemical patterning is typically tackled by preventing contact between the reagent and material, which brings various accompanying challenges. Photochemical transformation on the other hand inherently provides remote high spatiotemporal resolution using the cleanest reagent-a photon. Herein, we combine two competing reactions on a graphene substrate to create functionalization patterns on a micrometer scale via the Mitsunobu reaction. The mild reaction conditions allow introduction of covalently dynamic linkages, which can serve as reversible labels for surface- or graphene-enhanced Raman spectroscopy characterization of the patterns prepared. The proposed methodology thus provides a pathway for local introduction of arbitrary functional groups on graphene.

Proton-Gradient-Driven Oriented Motion of Nanodiamonds Grafted to Graphene by Dynamic Covalent Bonds.

Manipulating nanoscopic objects by external stimuli is the cornerstone of nanoscience. Here, we report the implementation of dynamic covalent chemistry in the reversible binding and directional motion of fluorescent nanodiamond particles at a functionalized graphene surface via imine linkages. The dynamic connections allow for controlling the formation and rupture of these linkages by external stimuli. By introduction of pH gradients, the nanoparticles are driven to move along the gradient due to the different rates of the imine condensation and hydrolysis in the two environments. The multivalent nature of the particle-to-surface connection ensures that particles remain attached to the surface, whereas its dynamic character allows for exchange reaction, thus leading to displacement yet bound behavior in two-dimensional space. These results open a pathway for thermodynamically controlled manipulation of objects on the nanoscale.

6,7-dimethoxy-coumarin as a probe of hydration dynamics in biologically relevant systems.

Coumarin derivatives are well known fluorescence reporters for investigating biological systems due to their strong micro-environment sensitivity. Despite having wide range of environment sensitive fluorescence probes, the potential of 6,7-dimethoxy-coumarin has not been studied extensively so far. With a perspective of its use in protein studies, namely using the unnatural amino acid technology or as a substrate for hydrolase enzymes, we study acetyloxymethyl-6,7-dimethoxycoumarin (Ac-DMC). We investigate the photophysics and hydration dynamics of this dye in aerosol-OT (AOT) reverse micelles at various water contents using the time dependent fluorescence shift (TDFS) method. The TDFS response in AOT reverse micelles from water/surfactant ratio of 0 to 20 confirms its sensitivity towards the hydration and mobility of its microenvironment. Moreover, we show that the fluorophore can be efficiently quenched by halide ions. Hence, we conclude that the 6,7-dimethoxy-methylcoumarin fluorophore is useful for studying hydration parameters in biologically relevant systems.

Selective self-assembly and light emission tuning of layered hybrid perovskites on patterned graphene.

The emission of light in two-dimensional (2-D) layered hybrid organic lead halide perovskites, namely (R-NH3)2PbX4, can be effectively tuned using specific building blocks for the perovskite formation. Herein this behaviour is combined with a non-covalent graphene functionalization allowing excellent selectivity and spatial resolution of the perovskite film growth, promoting the formation of hybrid 2-D perovskite : graphene heterostructures with uniform coverage of up to centimeter scale graphene sheets and arbitrary shapes down to 5 µm. Using cryo-Raman microspectroscopy, highly resolved spectra of the perovskite phases were obtained and the Raman mapping served as a convenient spatially resolved technique for monitoring the distribution of the perovskite and graphene constituents on the substrate. In addition, the stability of the perovskite phase with respect to the thermal variation was inspected in situ by X-ray diffraction. Finally, time-resolved photoluminescence characterization demonstrated that the optical properties of the perovskite films grown on graphene are not hampered. Our study thus opens the door to smart fabrication routes for (opto)-electronic devices based on 2-D perovskites in contact with graphene with complex architectures.

Functionalization of Hydrogenated Chemical Vapour Deposition-Grown Graphene by On-Surface Chemical Reactions.

The reactivity of hydrogenated graphene when treated with oxidising agents, KMnO4 and KIO4 , as well as alkylated with benzyl bromide (BnBr) was studied. The probed reactions are strictly limited to the partly hydrogenated form of graphene in which most of the hydrogen atoms are located in activated benzylic/allylic positions. This, in turn, clearly demonstrates the presence of hydrogen attached to the graphene lattice. Attachment of the benzyl group was also unequivocally demonstrated by characteristic vibrations recorded in the surface-enhanced Raman spectra, and all reactions were shown to proceed solely on hydrogenated graphene as evidenced by the comparison with pristine chemical vapour deposition-grown graphene.

Tuning the Reactivity of Graphene by Surface Phase Orientation.

Tuning the local reactivity of graphene is a subject of paramount importance. Among the available strategies, the activation/passivation of graphene by copper substrate is very promising because it enables the properties of graphene to be influenced without any transfer procedure, since graphene can be grown directly on copper. Herein, it is demonstrated that the reactivity of graphene towards fluorination is strongly influenced by the face of the surface of the copper substrate. Graphene on the copper foil was probed and grain orientations were identified. The results of the reactivity were evaluated by means of X-ray photo electron and Raman spectroscopy. Graphene on the grains with a surface orientation close to the (111) face is the most reactive, whereas graphene on the grains close to the (110) surface is least reactive. The long-term stability test showed that the decomposition of fluorinated graphene was slowest on the grains with a surface orientation close to the (111) face. The results are consistent with the variation of the mechanical strain of graphene on different faces of copper. In contrast, no clear correlation of the graphene reactivity with doping induced by different facets was found.

Control of Imine Exchange Kinetics with Photoswitches to Modulate Self-Healing in Polysiloxane Networks by Light Illumination.

Various aldehyde-containing photoswitches have been developed whose reactivity toward amines can be controlled externally. A thermally stable bifunctional diarylethene, which in its ring-closed form exhibits imine formation accelerated by one order of magnitude, was used as a photoswitchable crosslinker and mixed with a commercially available amino-functionalized polysiloxane to yield a rubbery material with viscoelastic and self-healing properties that can be reversibly tuned by irradiation.

Covalent Reactions on Chemical Vapor Deposition Grown Graphene Studied by Surface-Enhanced Raman Spectroscopy.

Graphene is a material of unmatched properties and eminent potential in disciplines ranging from physics, to chemistry, to biology. Its advancement to applications with a specific function requires rational design and fine tuning of its properties, and covalent introduction of various substituents answers this requirement. We challenged the obstacle of non-trivial and harsh procedures for covalent functionalization of pristine graphene and developed a protocol for mild nucleophilic introduction of organic groups in the gas phase. The painstaking analysis problem of monolayered materials was addressed by using surface-enhanced Raman spectroscopy, which allowed us to monitor and characterize in detail the surface composition. These deliverables provide a toolbox for reactivity of fluorinated graphene under mild reaction conditions, providing structural freedom of the species to-be-grafted to the single-layer graphene.

Acylhydrazones as Widely Tunable Photoswitches.

Molecular photoswitches have attracted much attention in biological and materials contexts. Despite the fact that existing classes of these highly interesting functional molecules have been heavily investigated and optimized, distinct obstacles and inherent limitations remain. Considerable synthetic efforts and complex structure-property relationships render the development and exploitation of new photoswitch families difficult. Here, we focus our attention on acylhydrazones: a novel, yet underexploited class of photochromic molecules based on the imine structural motif. We optimized the synthesis of these potent photoswitches and prepared a library of over 40 compounds, bearing different substituents in all four crucial positions of the backbone fragment, and conducted a systematic study of their photochromic properties as a function of structural variation. This modular family of organic photoswitches offers a unique combination of properties and the compounds are easily prepared on large scales within hours, through an atom-economic synthesis, from commercially available starting materials. During our thorough spectroscopic investigations, we identified photoswitches covering a wide range of thermal half-lives of their (Z)-isomers, from short-lived T-type to thermally stable P-type derivatives. By proper substitution, excellent band separation between the absorbance maxima of (E)- and (Z)-isomers in the UV or visible region could be achieved. Our library furthermore includes notable examples of rare negative photochromic systems, and we show that acylhydrazones are highly fatigue resistant and exhibit good quantum yields.

Comparison of five 2nd-generation supraglottic airway devices for airway management performed by novice military operators.

OBJECTIVES: Five different second-generation supraglottic airway devices, ProSeal LMA, Supreme LMA, i-gel, SLIPA, and Laryngeal Tube Suction-D, were studied. Operators were inexperienced users with a military background, combat lifesavers, nurses, and physicians. METHODS: This was a prospective, randomized, single-blinded study. Devices were inserted in the operating room in low light conditions after induction of general anesthesia. Primary outcome was successful insertion on the first attempt while secondary aims were insertion time, number of attempts, oropharyngeal seal pressure, ease of insertion, fibre optic position of device, efficacy of ventilation, and intraoperative trauma or regurgitation of gastric contents. RESULTS: In total, 505 patients were studied. First-attempt insertion success rate was higher in the Supreme LMA (96%), i-gel (87.9%), and ProSeal LMA (85.9%) groups than in the Laryngeal Tube Suction-D (80.6%) and SLIPA (69.4%) groups. Insertion time was shortest in the Supreme LMA (70.4 ± 32.5 s) and i-gel (74.4 ± 41.1 s) groups (p < 0.001). Oropharyngeal seal pressures were higher in the Laryngeal Tube Suction-D and ProSeal LMA groups than in other three devices. CONCLUSIONS: Most study parameters for the Supreme LMA and i-gel were found to be superior to the other three tested supraglottic airway devices when inserted by novice military operators.

Directional Dynamic Covalent Motion of a Carbonyl Walker on a Polyamine Track.

Invited for the cover of this issue is the group of Jean-Marie Lehn at the Université de Strasbourg (France). The image depicts the trend of the research activities pursued in our laboratory in Strasbourg over 50 years towards chemical systems, entities and processes, of increasing complexity. Read the full text of the article at 10.1002/chem.201500987.

Directional Dynamic Covalent Motion of a Carbonyl Walker on a Polyamine Track.

Controlled directional displacement of a molecular group has been achieved based on dynamic covalent motions implementing the reactional features of the imine bond. ortho-Carboxybenzaldehyde derivatives are able to form stable adducts with both primary and secondary amines as imines or as amino lactones, respectively, depending on the acidity of the medium. They may thus perform pH-driven intramolecular "walking" along a non-symmetric polyamine chain, in which an imine serves as the terminus under basic conditions on one end of the chain and a lactone formed on a secondary hydroxylamine nitrogen on the other end serves as the terminal site upon addition of acid. The displacement between the termini occurs stochastically through reversible change in valency at the carbon site of the carbonyl group between imine, aminal, iminium and amino lactone form. On the other hand, the directionality results from the stabilisation of the terminal products under given pH conditions. By its ability to undergo interconversion between C=N and O-C-N moieties, the ortho-carboxybenzaldehyde group extends the realm of dynamic covalent chemistry of imines to secondary amines and opens new perspectives in this field.

Dynamic covalent chemistry of bisimines at the solid/liquid interface monitored by scanning tunnelling microscopy.

Dynamic covalent chemistry relies on the formation of reversible covalent bonds under thermodynamic control to generate dynamic combinatorial libraries. It provides access to numerous types of complex functional architectures, and thereby targets several technologically relevant applications, such as in drug discovery, (bio)sensing and dynamic materials. In liquid media it was proved that by taking advantage of the reversible nature of the bond formation it is possible to combine the error-correction capacity of supramolecular chemistry with the robustness of covalent bonding to generate adaptive systems. Here we show that double imine formation between 4-(hexadecyloxy)benzaldehyde and different α,ω-diamines as well as reversible bistransimination reactions can be achieved at the solid/liquid interface, as monitored on the submolecular scale by in situ scanning tunnelling microscopy imaging. Our modular approach enables the structurally controlled reversible incorporation of various molecular components to form sophisticated covalent architectures, which opens up perspectives towards responsive multicomponent two-dimensional materials and devices.

Merging constitutional and motional covalent dynamics in reversible imine formation and exchange processes.

The formation and exchange processes of imines of salicylaldehyde, pyridine-2-carboxaldehyde, and benzaldehyde have been studied, showing that the former has features of particular interest for dynamic covalent chemistry, displaying high efficiency and fast rates. The monoimines formed with aliphatic α,ω-diamines display an internal exchange process of self-transimination type, inducing a local motion of either "stepping-in-place" or "single-step" type by bond interchange, whose rate decreases rapidly with the distance of the terminal amino groups. Control of the speed of the process over a wide range may be achieved by substituents, solvent composition, and temperature. These monoimines also undergo intermolecular exchange, thus merging motional and constitutional covalent behavior within the same molecule. With polyamines, the monoimines formed execute internal motions that have been characterized by extensive one-dimensional, two-dimensional, and EXSY proton NMR studies. In particular, with linear polyamines, nondirectional displacement occurs by shifting of the aldehyde residue along the polyamine chain serving as molecular track. Imines thus behave as simple prototypes of systems displaying relative motions of molecular moieties, a subject of high current interest in the investigation of synthetic and biological molecular motors. The motional processes described are of dynamic covalent nature and take place without change in molecular constitution. They thus represent a category of dynamic covalent motions, resulting from reversible covalent bond formation and dissociation. They extend dynamic covalent chemistry into the area of molecular motions. A major further step will be to achieve control of directionality. The results reported here for imines open wide perspectives, together with other chemical groups, for the implementation of such features in multifunctional molecules toward the design of molecular devices presenting a complex combination of motional and constitutional dynamic behaviors.

25,26,27,28-Tetra-propoxycalix[4]arene-5,17-dicarbonitrile.

In the title compound, C(42)H(46)N(2)O(4), both crystallographically independent mol-ecules display a 1,3-alternate conformation. Their crystal packing is stabilized by non-classical C-H⋯N hydrogen bonds. The dihedral angles between the planes of the aromatic rings and the mean plane through the methyl-ene C atoms bridging the aromatic rings are 78.10 (13), 80.74 (14), 81.89 (12) and 79.05 (14)° for the first mol-ecule, and 71.65 (11), 76.60 (13), 77.97 (14) and 74.76 (13)° for the second mol-ecule. Both mol-ecules have three C atoms of one prop-oxy chain disordered over two set of sites; the site-occupancy factors are 0.7/0.3 and 0.6/0.4, respectively.