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International audience; The behavior of nanoparticles in solution is largely dominated by their shape and interaction potential. Despite considerable progress in the preparation of patchy and compartmentalized particles, access to nanoparticles with complex surface patterns and topographies remains limited. Here, we show that polyanionic brushes tethered to rod-like cellulose nanocrystals (CNCs) spontaneously develop a striped or helical topography through interpolyelectrolyte complexation with polycationic diblock copolymers. Using cryogenic transmission electron microscopy (cryo-TEM) and tomography (cryo-ET), we follow the complexation process and analyze the delicate 3D topography on the CNC surface. The described approach is facile and modular and can be extended to other block chemistries, nanoparticles, and surfaces, thereby providing a versatile platform toward surface-patterned particles with complex topographies and spatially arranged functional groups.

A classic paradigm of soft and extensible polymer materials is the difficulty of combining reversible elasticity with high fracture toughness, in particular for moduli above 1 MPa. Our recent discovery of multiple network acrylic elastomers opened a pathway to obtain precisely such a combination. We show here that they can be seen as true molecular composites with a well–cross-linked network acting as a percolating filler embedded in an extensible matrix, so that the stress–strain curves of a family of molecular composite materials made with different volume fractions of the same cross-linked network can be renormalized into a master curve. For low volume fractions (

The article is concerned with hybrid amorphous polymers synthesized basing on epoxy oligomer of diglycide aliphatic ester of polyethylene glycol that was cured by polyethylene polyamine and lithium perchlorate salt. Structural peculiarities of organic-inorganic polymer composites were studied by differential scanning calorimetry, wide-angle X-ray spectra, infrared spectroscopic, scanning electron microscopy, elemental analysis, and transmission and reflective optical microscopy. On the one hand, the results showed that the introduction of LiClO4 salt into epoxy polymer leads to formation of the coordinative metal-polymer complexes of donor-acceptor type between central Li+ ion and ligand. On the other hand, the appearance of amorphous microinclusions, probably of inorganic nature, was also found.

Core–shell structured poly(vinylidene fluoride)-grafted-barium titanate/(PVDF-g-BaTiO3) nanocomposites were prepared by surface-initiated reversible addition–fragmentation chain transfer (RAFT) of VDF from the surface of functionalized BaTiO3 nanoparticles. The ceramic fillers were first surface-modified with xanthate functions to further allow the RAFT grafting of VDF. A series of structured core shells were synthesized by tuning the feed [initiator functionalized nanoparticles]0 : [monomer]0 ratio, varying from 3 to 5, 10 and 20 wt%. Fourier transform infrared spectroscopy (FTIR), high resolution magic angle spinning (HRMAS) NMR and thermogravimetric analysis (TGA) confirmed the successful surface functionalization of the ceramic filler and the grafting of the PVDF shell onto the surface of the BaTiO3 cores. Transmission electron microscopy results revealed that BaTiO3 nanoparticles are covered by thin shells of PVDF, with thickness varying from 2.2 to 5.1 nm, forming a core–shell structure. HRMAS 19F indicated a grafting of 39–50 units of VDF. X-ray diffraction measurements together with FTIR measurements revealed that PVDF was present in the α form. Thermal properties also indicated that the addition of a small amount of the BaTiO3 filler to the PVDF matrix increased the melting temperature from 168 °C for neat PVDF to 173 °C for PVDF-g-BaTiO3 (20 wt%) and decreased the crystallinity of PVDF from 47% to 21%.

International audience; We report on the self-assembly behavior of poly(2-methyl-2-oxazoline)–block–poly(2-octyl-2-oxazoline) comprising different terminal perfluoroalkyl fragments in aqueous solutions. As reported previously [Eur. Polym. J., 2017, 88, 645-655] such polyphiles can form a plethora of nanostructures depending of the composition and on the way of preparation. Here we report, for the first time, detailed information on the internal structure of the nanoparticles resulting from the self-assembly of these copolymers. Small-angle neutron and x-ray scattering (SANS/SAXS) experiments unambiguously prove the existence of polymersomes, wormlike micelles and their aggregates in aqueous solution. It is shown that increasing content of fluorine in the poly(2-oxazoline) copolymers results in a morphological transition from bilayered or multi-layered vesicles to wormlike micelles for solutions prepared by direct dissolution.In contrast, nanoparticles prepared by dialysis of a polymer solution in a non-selective organic solvent against water are characterized by SAXS method. The internal structure of the nanoparticles could be assessed by fitting of the scattering data, revealing complex core-double shell architecture of spherical symmetry. Additionally, long range ordering is identified for all studied nanoparticles due to the crystallization of the poly(2-octyl-2-oxazoline) segments inside the nanoparticles.

International audience; Porous cellulose matrices were prepared via cellulose dissolution in 8 wt% NaOH-water, physical gelation and chemical cross-linking with epichlorohydrin (ECH), coagulation in water and lyophilisation. Cellulose and cross-linker concentration were varied. The behaviour of gels upon coagulation and the swelling of cryogels in water were analysed. An anomalous high swelling at cross-linker concentration around stoichiometric molar ratio with cellulose was observed. Cellulose cryogel morphology, crystallinity and density were studied. The influence of chemical cross-linking on cellulose swelling was explained by suggesting that ECH acts as a spacer preventing cellulose chains tight packing during coagulation. Cellulose was loaded with a model drug, procaine hydrochloride, and the kinetics of its release was investigated.

The potential of self-assembled nanoparticles (NPs) containing the fine tunable pH-responsive properties of the hydrophobic poly[2-(diisopropylamino)ethyl methacrylate] (PDPA) core and the protein repellence of the hydrophilic poly[N-(2-hydroxypropyl)methacrylamide] (PHPMA) shell for in vitro cytostatic activity has been explored on cancer cells. The amphiphilic diblock copolymer poly[N-(2-hydroxypropyl)methacrylamide]-b-poly[2-(diisopropylamino)ethyl methacrylate] (PHPMA-b-PDPA) synthesized by a reversible addition–fragmentation chain transfer (RAFT) technique allows for excellent control of the polymer chain length for methacrylamides. The PHPMA-b-PDPA block copolymer dissolved in an organic solvent (ethanol/dimethylformamide) undergoes nanoprecipitation in phosphate buffer saline (PBS, pH [similar] 7.4) and self-assembles into regular spherical NPs after solvent elimination. The NPs’ structure was characterized in detail by dynamic (DLS), static (SLS) and electrophoretic (ELS) light scattering, small angle X-ray scattering (SAXS), and cryo-transmission electron microscopy (cryo-TEM). The PHPMA chains prevented the fouling of proteins resulting in a remarkable stability of the NPs in serum. On decreasing pH the hydrophobic PDPA block becomes protonated (hydrophilised) in a narrow range of pH (6.51 < pH < 6.85; ΔpH [similar] 0.34) resulting in the fast disassembly of the NPs and chemotherapeutic drug release in a simulated acidic environment in endosomal and lysosomal compartments. A minimal amount of drug was released above the threshold pH of 6.85. The in vitro cytotoxicity studies showed an important increase in the activity of the NPs loaded with drug compared to the free drug. The particle\'s size below the cut-off size of the leaky pathological vasculature (less than 100 nm), the excellent stability in serum and the ability to release a drug at the endosomal pH with concomitant high cytotoxicity make them suitable candidates for cancer therapy, namely for treatment of solid tumours exhibiting high tumor accumulation of NPs due to the Enhanced Permeability and Retention (EPR) effect.

The assembly of donor–acceptor molecules via charge transfer (CT) interactions gives rise to highly ordered nanomaterials with appealing electronic properties. Here, we present the synthesis and bulk co-assembly of pyrene (Pyr) and naphthalenediimide (NDI) functionalized oligodimethylsiloxanes (oDMS) of discrete length. We tune the donor–acceptor interactions by connecting the pyrene and NDI to the same oligomer, forming a heterotelechelic block molecule (NDI-oDMSPyr), and to two separate oligomers, giving Pyr and NDI homotelechelic block molecules (Pyr-oDMS and NDI-oDMS). Liquid crystalline materials are obtained for binary mixtures of Pyr-oDMS and NDI-oDMS, while crystallization of the CT dimers occurred for the heterotelechelic NDI-oDMS-Pyr block molecule. The synergy between crystallization and phase-segregation coupled with the discrete length of the oDMS units allows for perfect order and sharp interfaces between the insulating siloxane and CT layers composed of crystalline CT dimers. We were able to tune the lamellar domain spacing and donor–acceptor CT interactions by applying pressures up to 6 GPa on the material, making the system promising for soft-material nanotechnologies. These results demonstrate the importance of the molecular design to tune the CT interactions and stability of a CT material., A robust, soft material held together by charge transfer interactions is developed. The nanostructure dimensions and material properties can be tuned by molecular design or pressure.

11 p.-7 fig.-1 tab.1 graph. abst., Dynamic binding events are key to arrive at functionality in nature, and these events are often governed by electrostatic or hydrophobic interactions. Synthetic supramolecular polymers are promising candidates to obtain biomaterials that mimic this dynamicity. Here, we created four new functional monomers based on the benzene-1,3,5-tricarboxamide (BTA) motif. Choline or atropine groups were introduced to obtain functional monomers capable of competing with the cell wall of Streptococcus pneumoniae for binding of essential choline-binding proteins (CBPs). Atropine-functionalized monomers BTA-Atr and BTA-Atr3 were too hydrophobic to form homogeneous assemblies, while choline-functionalized monomers BTA-Chol and BTA-Chol3 were unable to form fibers due to charge repulsion. However, copolymerization of BTA-Chol3 with non-functionalized BTA-(OH)3 yielded dynamic fibers, similar to BTA-(OH)3. These copolymers showed an increased affinity toward CBPs compared to free choline due to multivalent effects. BTA-based supramolecular copolymers are therefore a versatile platform to design bioactive and dynamic supramolecular polymers with novel biotechnological properties., The authors acknowledge the financial support from the Dutch Ministry of Education, Culture and Science (Gravity program 024.001.035), the ERC Advanced Grant (SYNMAT─788618), the Gravitation Program “Materials Driven Regeneration”, funded by the Netherlands Organization for Scientific Research (024.003.013), and the Agencia Estatal de Investigacion AEI/FEDER-EU-10.13039/501100011033- and Ministerio de Ciencia e Innovación, Spain (PID2019-105126RB-I00)

[Abstract] The use of supramolecular polymers to construct functional biomaterials is gaining more attention due to the tunable dynamic behavior and fibrous structures of supramolecular polymers, which resemble those found in natural systems, such as the extracellular matrix. Nevertheless, to obtain a biomaterial capable of mimicking native systems, complex biomolecules should be incorporated, as they allow one to achieve essential biological processes. In this study, supramolecular polymers based on water-soluble benzene-1,3,5-tricarboxamides (BTAs) were assembled in the presence of hyaluronic acid (HA) both in solution and hydrogel states. The coassembly of BTAs bearing tetra(ethylene glycol) at the periphery (BTA-OEG4) and HA at different ratios showed strong interactions between the two components that led to the formation of short fibers and heterogeneous hydrogels. BTAs were further covalently linked to HA (HA-BTA), resulting in a polymer that was unable to assemble into fibers or form hydrogels due to the high hydrophilicity of HA. However, coassembly of HA-BTA with BTA-OEG4 resulted in the formation of long fibers, similar to those formed by BTA-OEG4 alone, and hydrogels were produced with tunable stiffness ranging from 250 to 700 Pa, which is 10-fold higher than that of hydrogels assembled with only BTA-OEG4. Further coassembly of BTA-OEG4 fibers with other polysaccharides showed that except for dextran, all polysaccharides studied interacted with BTA-OEG4 fibers. The possibility of incorporating polysaccharides into BTA-based materials paves the way for the creation of dynamic complex biomaterials. The authors acknowledge the ICMS Animation Studio for providing the artwork. S.V.-A. and G.M. acknowledge the funding received by Gravitation Program “Materials Driven Regeneration,” funded by the Netherlands Organization for Scientific Research (024.003.013). J.M. acknowledges a Marie Skłodowska-Curie postdoctoral fellowship (794016) for financial support. G.M. acknowledges the funding received by the Swiss National Science Foundation (SNSF “Early PostDoc Mobility” P2EZP2-178435). R.C. acknowledges TA Instruments for providing the DHR-3 rheometer under the Young Distinguished Rheologist Award instrument grant. S.S. and E.W.M acknowledge the European Research Council (H2020-EU.1.1., SYNMAT project, ID 788618). Netherlands Organisation for Scientific Research; 024.003.013 Swiss National Science Foundation; P2EZP2-178435

Supramolecular copolymers formed by the noncovalent synthesis of multiple components expand the complexity of functional molecular systems. However, varying the composition and microstructure of copolymers through tuning the interactions between building blocks remains a challenge. Here, we report a remarkable discovery of the temperature-dependent supramolecular copolymerization of the two chiral monomers 4,4′,4″-(1,3,5-triazine-2,4,6-triyl)tribenzamide (S-T) and 4,4′,4″-(benzene-1,3,5-triyl)tribenzamide (S-B). We first demonstrate in the homopolymerization of the two individual monomers that a subtle change from the central triazine to benzene in the chemical structure of the monomers significantly affects the properties of the resulting homopolymers in solution. Homopolymers formed by S-T exhibit enhanced stability in comparison to S-B. More importantly, through a combination of spectroscopic analysis and theoretical simulation, we reveal the complex process of copolymerization: S-T aggregates into homopolymers at elevated temperature, and upon slow cooling S-B gradually intercalates into the copolymers, to finally give copolymers with almost 80% alternating bonds at 10 °C. The formation of the predominantly alternating copolymers is plausibly contributed by preferred heterointeractions between triazine and benzene cores in S-T and S-B, respectively, at lower temperatures. Overall, this work unravels the complexity of a supramolecular copolymerization process where an intermediate heterointeraction (higher than one homointeraction and lower than the other homointeraction) presents and proposes a general method to elucidate the microstructures of copolymers responsive to temperature changes.

For many years, fullerene derivatives have been the main n-type material of organic electronics and optoelectronics. Recently, fullerene derivatives functionalized with ethylene glycol (EG) side chains have been showing important properties such as enhanced dielectric constants, facile doping and enhanced self-assembly capabilities. Here, we have prepared field-effect transistors using a series of these fullerene derivatives equipped with EG side chains of different lengths. Transport data show the beneficial effect of increasing the EG side chain. In order to understand the material properties, full structural determination of these fullerene derivatives has been achieved by coupling the X-ray data with molecular dynamics (MD) simulations. The increase in transport properties is paired with the formation of extended layered structures, efficient molecular packing and an increase in the crystallite alignment. The layer-like structure is composed of conducting layers, containing of closely packed C60 balls approaching the inter-distance of 1 nm, that are separated by well-defined EG layers, where the EG chains are rather splayed with the chain direction almost perpendicular to the layer normal. Such a layered structure appears highly ordered and highly aligned with the C60 planes oriented parallel to the substrate in the thin film configuration. The order inside the thin film increases with the EG chain length, allowing the systems to achieve mobilities as high as 0.053 cm2 V−1 s−1. Our work elucidates the structure of these interesting semiconducting organic molecules and shows that the synergistic use of X-ray structural analysis and MD simulations is a powerful tool to identify the structure of thin organic films for optoelectronic applications., The synergistic use of X-ray scattering and molecular dynamics simulations reveals the structure–property relationships of [60]fullerene derivatives with oligoethylene–glycol side chains.

International audience; Anionic polymerization initiated by cyclodextrins suffers from a poor solubility of those derivatives in standard polymerization solvents. The possibility to perform ethylene oxide polymerization initiated by monofunctional initiators (allyl alcohol, 2-methoxyethanol) by living ring opening polymerization in DMF, a good solvent for any CD derivative, was demonstrated by SEC, 1H and 13C NMR analyses. The study was extended to the use of native CD as initiator, leading to the synthesis of ill-defined structures, explained by the reactivity scale of the various hydroxyl functions. Two selectively modified CD derivatives are then used to synthesize a new family of star-shaped poly(ethylene oxide) polymers with CD core, having 14 or 21 arms. The polymerization was found to be living and DOSY experiments confirmed the well-defined structures for the synthesized star-polymers.

Molecular doping makes possible tunable electronic properties of organic semiconductors, yet a lack of control of the doping process narrows its scope for advancing organic electronics. Here, we demonstrate that the molecular doping process can be improved by introducing a neutral radical molecule, namely nitroxyl radical (2,2,6,6-teramethylpiperidin-i-yl) oxyl (TEMPO). Fullerene derivatives are used as the host and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazoles (DMBI-H) as the n-type dopant. TEMPO can abstract a hydrogen atom from DMBI-H and transform the latter into a much stronger reducing agent DMBI•, which efficiently dopes the fullerene derivative to yield an electrical conductivity of 4.4 S cm-1. However, without TEMPO, the fullerene derivative is only weakly doped likely by a hydride transfer following by an inefficient electron transfer. This work unambiguously identifies the doping pathway in fullerene derivative/DMBI-H systems in the presence of TEMPO as the transfer of a hydrogen atom accompanied by electron transfer. In the absence of TEMPO, the doping process inevitably leads to the formation of less symmetrical hydrogenated fullerene derivative anions or radicals, which adversely affect the molecular packing. By adding TEMPO we can exclude the formation of such species and, thus, improve charge transport. In addition, a lower temperature is sufficient to meet an efficient doping process in the presence of TEMPO. Thereby, we provide an extra control of the doping process, enabling enhanced thermoelectric performance at a low processing temperature.

Microplastic pollution in soils is an emerging topic in the scientific community, with researchers striving to determine the occurrence and the impact of microplastics on soil health, ecology, and functionality. However, information on the microplastic contamination of soils is limited because of a lack of suitable analytical methods. Because micro‐Fourier‐transform infrared spectroscopy (µ‐FTIR), next to Raman spectroscopy, is one of the few methods that allows the determination of the number, polymer type, shape, and size of microplastic particles, the present study addresses the challenge of purifying soil samples sufficiently to allow a subsequent µ‐FTIR analysis. A combination of freeze‐drying, sieving, density separation, and a sequential enzymatic‐oxidative digestion protocol enables removal of the mineral mass (>99.9% dry wt) and an average reduction of 77% dry weight of the remaining organic fraction. In addition to visual integrity, attenuated total reflectance FTIR, gel permeation chromatography, and differential scanning calorimetry showed that polyamide, polyethylene, polyethylene terephthalate, and polyvinyl chloride in the size range of 100 to 400 µm were not affected by the approach. However, biodegradable polylactic acid showed visible signs of degradation and reduced molecular weight distribution after protease treatment. Nevertheless, the presented purification protocol is a reliable and robust method to purify relatively large soil samples of approximately 250 g dry weight for spectroscopic analysis in microplastic research and has been shown to recover various microplastic fibers and fragments down to a size of 10 µm from natural soil samples. Environ Toxicol Chem 2021;00:1–14. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC., A novel purification sequence for natural soil samples undergoing microplastic analysis. image, Ministry for Environment, Climate Protection and Energy of Baden Württemberg, German Federal Ministry of Education and Research (BMBF) http://dx.doi.org/10.13039/501100002347, German Research Foundation (DFG) http://dx.doi.org/10.13039/501100001659

A simple method to fabricate polymer nanocomposites with single-walled carbon nanotubes is reported, in which the nanotubes were reacted with poly(L-lysine) by using high-speed vibration milling. The nanocomposites obtained were characterized by Fourier transform infrared (FT-IR), UV-Vis spectroscopy, and thermogravimetric methods. The morphology as well as the dispersion of the carbon nanotubes were determined by scanning and transmission electron microscopy.

While the impact of compositional parameters such as block length and ionic content on the micellization of (polymeric) amphiphiles is widely investigated, the influence of monomer sequence has received far less attention until recently. Here, we report the synthesis of two sequence-controlled polyurethane ionomers (PUIs) prepared via a stepwise coupling-deprotection strategy, and compare their solution association in aqueous-organic mixtures. The two PUIs are highly similar in mass and overall composition, yet differ markedly in the sequence of building blocks. PUI-A2 comprises a polytetrahydrofuran (pTHF) block connected to an alternation of isophorone diamine (IPDA) and dimethylolpropionic acid (DMPA) units that together are also arranged in a blockwise manner. The result is a macromolecular structure with a comparatively hydrophobic tail (pTHF) and a hydrophilic headgroup, which structure is reminiscent of those of traditional surfactants, albeit much larger in size. PUI-S2 instead resembles a bolaamphiphilic architecture with a pTHF midblock connected on either end to a singly charged segment comprising DMPA and IPDA. We detect micellization below a threshold cosolvent volume fraction (Csolv) of 0.4 in aqueous-organic mixtures with tetrahydrofuran (THF), ethanol, and isopropyl alcohol. We use scattering tools to compare the aggregation number (Nagg) and hydrodynamic radius (Rh) of PUI-S2 and PUI-A2 micelles. Irrespective of the solvent composition, we observe in the micellar window of Csolv < 0.4, lower Nagg for PUI-S2 micelles compared to PUI-A2, which we attribute to packing restraints associated with its bolaamphiphilic architecture. The increase in micellar size with increasing Csolv is much more pronounced for PUI-S2 than for PUI-A2. The micellar mass decreases with increasing Csolv for both PUIs; the effect is modest for PUI-S2 compared to PUI-A2 and is not observed in the most apolar cosolvent studied (THF). Upon the approach of the micellization boundary Csolv ≈ 0.4, both types of PUI micelles become less compact in structure, as (in most cases) PUIs are released and as micellar dimensions increase.

Discrete block co-oligomers (BCOs) assemble into highly ordered nanostructures, which adopt a variety of morphologies depending on their environment. Here, we present a series of discrete oligodimethylsiloxane-oligoproline (oDMS-oPro) BCOs with varying oligomer lengths and proline end-groups, and study the nanostructures formed in both bulk and solution. The conjugation of oligoprolines to apolar siloxanes permits a study of the aggregation behavior of oligoproline moieties in a variety of solvents, including a highly apolar solvent like methylcyclohexane. The apolar solvent is more reminiscent of the polarity of the siloxane bulk, which gives insights into the supramolecular interactions that govern both bulk and solution assembly processes of the oligoproline. This extensive structural characterization allows the bridging of the gap between solution and bulk assembly. The interplay between the aggregation of the oligoproline block and the phase segregation induced by the siloxane drives the assembly. This gives rise to disordered, micellar microstructures in apolar solution and crystallization-driven lamellar nanostructures in the bulk. While most di- and triblock co-oligomers adopt predictable morphological features, one of them, oDMS15-oPro6-NH2, exhibits pathway complexity leading to gel formation. The pathway selection in the complex interplay between aggregation and phase segregation gives rise to interesting material properties., Journal of the American Chemical Society, 143 (10), ISSN:0002-7863, ISSN:1520-5126

In the flourishing field of soft robotics, strategies to embody communication and collective motion are scarce. Here we report the synchronized oscillations of thin plastic actuators by an approach reminiscent of the synchronized motion of pendula and metronomes. Two liquid crystalline network oscillators fuelled by light influence the movement of one another and display synchronized oscillations in-phase and anti-phase in a steady state. By observing entrainment between the asymmetric oscillators we demonstrate the existence of coupling between the two actuators. We qualitatively explain the origin of the synchronized motion using a theoretical model and numerical simulations, which suggest that the motion can be tuned by the mechanical properties of the coupling joint. We thus anticipate that the complex synchronization phenomena usually observed in rigid systems can also exist in soft polymeric materials. This enables the use of new stimuli, featuring an example of collective motion by photo-actuation.

Moving from homogeneous water-splitting photocatalytic systems to photoelectrochemical devices requires the preparation and evaluation of novel p -type transparent conductive photoelectrode substrates. We report here on the sensitization of polystyrene- block -poly-(2-vinylpyridine) (PS- b -P2VP) diblock copolymer-templated NiO films with an organic push–pull dye. The potential of these new templated NiO film preparations for photoelectrochemical applications is compared with NiO material templated by F108 triblock copolymers. We conclude that NiO films are promising materials for the construction of dye-sensitized photocathodes to be inserted into photoelectrochemical (PEC) cells. However, a combined effort at the interface between materials science and molecular chemistry, ideally funded within a Global Artificial Photosynthesis Project, is still needed to improve the overall performance of the photoelectrodes and progress towards economically viable PEC devices.

The copolymerization of cyano (nitrile) monomers and a fluoroalkylmethacrylate is used to develop new dielectric polymers containing C‐CN and C‐F substituents. Methacrylonitrile (MAN), acrylonitrile (AN) and methylvinylidene cyanide (MVCN) were chosen as cyano monomers. 2,2,2-Trifluoroethyl methacrylate (MATRIF) was used as a fluorinated comonomer. The copolymers based on cyano monomers such as AN, MAN or MVCN, and MATRIF comonomers were synthesized by radical process initiated by AIBN. The yields of the copolymerizations were ranging between 40 and 60%. These copolymers were characterized by 1 H, 13 C, 19 F NMR and IR spectroscopy which showed that the percentages of incorporation of AN and MAN in the copolymers were 45%. However, only 5% of MVCN was incorporated into poly(MVCN-co-MATRIF) copolymer. Thermogravimetric analyses showed that the thermal decomposition occurred from 200, 230 or 240 8C for copolymers of MVCN, MAN or AN, respectively, and indicated that the process of degradation depends on the nature of cyano monomer. # 2006 Elsevier B.V. All rights reserved.

Dynamic covalent bonds in a polymer network lead to plasticity, reshapability, and potential recyclability at elevated temperatures in combination with solvent-resistance and better dimensional stability at lower temperatures. Here we report a simple one-step procedure for the catalyst-free preparation and intramolecularly catalyzed stress-relaxation of dynamic polyester networks. The procedure is based on the coupling of branched OH-end functional polyesters (functionality ≥ 3) by pyromellitic dianhydride (PMDA) or 2,5-bis(methoxy-carbonyl) benzenesulfonic acid resulting in ester linkages with, respectively, a COOH or a SO3H group in a position ortho to the ester bond. This approach leads to an efficient external catalyst-free dynamic polyester network, in which the topology rearrangements occur via a dissociative mechanism involving anhydrides. The SO3H-containing network is particularly interesting, as it shows the fastest stress relaxation and does not suffer from unwanted additional transesterification reactions, as was observed in the COOH-containing network.

Controlling the reciprocity between chemical reactivity and supramolecular structure is a topic of great interest in the emergence of molecular complexity. In this work, we investigate the effect of a covalent reaction as a trigger to depolymerize a supramolecular assembly. We focus on the impact of an in situ thiol–ene reaction on the (co)polymerization of three derivatives of benzene-1,3,5-tricarboxamide (BTA) monomers functionalized with cysteine, hexylcysteine, and alkyl side chains: Cys-BTA, HexCys-BTA, and a-BTA. Long supramolecular polymers of Cys-BTA can be depolymerized into short dimeric aggregates of HexCys-BTAvia the in situ thiol–ene reaction. Analysis of the system by time-resolved spectroscopy and light scattering unravels the fast dynamicity of the structures and the mechanism of depolymerization. Moreover, by intercalating the reactive Cys-BTA monomer into an unreactive inert polymer, the in situ thiol–ene reaction transforms the intercalator into a sequestrator and induces the depolymerization of the unreactive polymer. This work shows that the implementation of reactivity into supramolecular assemblies enables temporal control of depolymerization processes, which can bring us one step closer to understanding the interplay between non-covalent and covalent chemistry., We report on the controlled depolymerization of supramolecular 1D polymers into well-defined dimers triggered by a covalent reaction on the side chains of the monomer.

One of the great challenges in polymer chemistry is to achieve discrete and sequence-defined synthetic polymers that fold in defined conformations and form well-defined three-dimensional structures. Here, we present our progress to arrive at functional, sequence-defined and discrete oligomers by selecting a synthetic approach based on oligo-l-glutamamides. We introduce a solution-based iterative approach and start with an orthogonally protected l-glutamic acid derivative with an alkene or alkyne side chain. Using subsequent deprotection, activation and coupling steps, discrete, sequence-defined octamers were prepared with alkene or alkyne pendants at defined positions. Benzene-1,3,5-Tricarboxamide (BTA) was selected as the supramolecular motif and decyl side chains for enhancing solubility. Full functionalization of the octamer was achieved with subsequent Cu(i)-catalyzed alkyne-Azide and thiol-ene "click"chemistry, affording octamers with two BTA motifs at pre-defined positions. The octamers show a strong propensity to form hydrogen bonds in bulk as evidenced by infrared spectroscopy. In dilute solution, intermolecular aggregation of the amides present in the backbone and/or BTAs is observed. Our work shows that the iterative method serves as an reliable strategy for the synthesis of functionalized sequence-defined, discrete oligomers comprising side chain supramolecular motifs, although further optimizations are required.

Methodology of using megavolt electrons for investigation of the functionality of thin polymer films of polycyanurates (PCN) is described. The relevance of research is determined by the prospects of using films as a functional basis for improvement of track-etched technologies of nanoporous nuclear filters, where ionizing radiation is used in most of technological stages of their production. Functionality control is the main criterion for the qualification of films on the suitability for production of nuclear filters on their base. Development of megavolt electrons radiation methods is promising for monitoring the functionality of filters. Radiation technologies are universal and able to provide maximum information content on investigations of the characteristics of materials to qualify them for suitability of practical use. To control the functionality of the films, the methodology for research and testing of thin polymer films using powerful electron beams of 1-2 MeV has been developed. The features of these methods and the results of their application at the control of functionality and for the qualification of the films based on crosslinked polycyanurates, synthesized by in situ polycyclotrimerization of dicyanate ester of bisphenol E in the presence of dimethylphthalate (DMPh) of the composition PCN/DMPh=70/30 wt.%, on the suitability for production of nanoporous track membranes are discussed. Key words: electron beams, nuclear membranes, thermostable polycyanurates, radiation stability, functional testing.

High electrical conductivity is a prerequisite for improving the performance of organic semiconductors for various applications and can be achieved through molecular doping. However, often the conductivity is enhanced only up to a certain optimum doping concentration, beyond which it decreases significantly. We combine analytical work and Monte Carlo simulations to demonstrate that carrier-carrier interactions can cause this conductivity decrease and reduce the maximum conductivity by orders of magnitude, possibly in a broad range of materials. Using Monte Carlo simulations, we disentangle the effect of carrier-carrier interactions from carrier-dopant interactions. Coulomb potentials of ionized dopants are shown to decrease the conductivity, but barely influence the trend of conductivity versus doping concentration. We illustrate these findings using a doped fullerene derivative for which we can correctly estimate the carrier density at which the conductivity maximizes. We use grazing-incidence wide-angle X-ray scattering to show that the decrease of the conductivity cannot be explained by changes to the microstructure. We propose the reduction of carrier-carrier interactions as a strategy to unlock higher-conductivity organic semiconductors.

By enchaining a small fraction of chiral monomer units, the helical sense of a dynamic polymer constructed from achiral monomer units can be disproportionately biased. This phenomenon, known as the sergeants-and-soldiers (S&S) effect, has been found to be widely applicable to dynamic covalent and supramolecular polymers. However, it has not been exemplified with a supramolecular polymer that features multiple helical states. Herein, we demonstrate the S&S effect in the context of the temperature-controlled supramolecular copolymerization of chiral and achiral biphenyl tetracarboxamides in alkanes. The one-dimensional helical structures presented in this study are unique because they exhibit three distinct helical states, two of which are triggered by coassembling with monomeric water that is codissolved in the solvent. The self-assembly pathways are rationalized using a combination of mathematical fitting and simulations with a thermodynamic mass-balance model. We observe an unprecedented case of an "abnormal" S&S effect by changing the side chains of the achiral soldier. Although the molecular structure of these aggregates remains elusive, the coassembly of water is found to have a profound impact on the helical excess.

Dynamic covalent networks are a class of polymeric materials that combine the merits of classical thermosets and thermoplastics, in terms of mechanical properties and reprocessability, in one material. Various dynamic covalent chemistries have thus been implemented in polymeric materials with recent interests shifting toward chemistries that would allow rearrangements in network topology without the aid of external catalysts. Here we introduce transesterification in phosphate triesters as a new dynamic covalent chemistry in polymeric networks. A simple one-step synthetic strategy has been utilized to synthesize polytetrahydrofuran networks with phosphate triester cross-links. The materials showed finite viscous flow at elevated temperatures via transesterification at the cross-links without externally added catalyst. This approach provides an easy method for cross-linking OH-end-functionalized polyethers and has the potential for general use with other OH-functionalized polymers.

Squaraine dyes are well known for their strong absorption in the visible regime. Reports on chiral squaraine dyes are, however, scarce. To address this gap, we here report two novel chiral squaraine dyes and their achiral counterparts. The presented dyes are aggregated in solution and in thin films. A detailed chiroptical study shows that thin films formed by co‐assembling the chiral dye with its achiral counterpart exhibit exceptional photophysical properties. The circular dichroism (CD) of the co‐assembled structures reaches a maximum when just 25 % of the chiral dye are present in the mixture. The solid structures with the highest relative CD effect are achieved when the chiral dye is used solely as a director, rather than the structural component. The chiroptical data are further supported by selected spin‐filtering measurements using mc‐AFM. These findings provide a promising platform for investigating the relationship between the dissymmetry of a supramolecular structure and emerging material properties rather than a comparison between a chiral molecular structure and an achiral counterpart., Helicity control: An unexpected outcome of the co‐assembly of achiral squaraine dye a‐SQ‐1 with its chiral counterpart S ‐SQ‐1 is reported. A maximum in optical activity is observed in the supramolecular aggregates of a 3:1 mixture with a‐SQ‐1 as the major component. Intriguingly, the highest spin‐selective electron transport is observed for this mixing ratio as well, illustrating the direct relationship between optical activity and spin‐selective electron transport.

The optical properties of two sets of donor-acceptor-donor molecules with terminal bithiophene donor units and a central diketopyrrolopyrrole (DPP) acceptor unit are studied. The two sets differ in the alkyl chains on the DPP, which are either branched at the α-carbon (3-pentyl) (1-4) or linear (n-hexyl) (5-8). Within each set, the molecules differ by the absence or presence of n-hexyl chains on the terminal thiophene rings in the 3′, 4′, or 5′ positions. While in solution, the optical spectra differ only subtly; they differ dramatically in the solid state. In contrast to 5-8, 1-4 are nonplanar as a consequence of the sterically demanding 3-pentyl groups, which inhibit π-stacking of the DPP units. Using the crystal structures of 2 (brick layer stacking) and 6 (slipped stacking), we quantitatively explain the solid state absorption spectra. By computing the molecular transition charge density and solving the dispersion relation, the optical absorption of the molecules in the crystal is predicted and in agreement with experiments. For 2, a single resonance frequency is obtained, while for 6 two transitions are seen, with the lower-energy transition being less intense. The results demonstrate how subtle changes in substitution exert large effects in optical properties.

The ‘phonon-glass electron-crystal’ concept has triggered most of the progress that has been achieved in inorganic thermoelectrics in the past two decades. Organic thermoelectric materials, unlike their inorganic counterparts, exhibit molecular diversity, flexible mechanical properties and easy fabrication, and are mostly ‘phonon glasses’. However, the thermoelectric performances of these organic materials are largely limited by low molecular order and they are therefore far from being ‘electron crystals’. Here, we report a molecularly n-doped fullerene derivative with meticulous design of the side chain that approaches an organic ‘PGEC’ thermoelectric material. This thermoelectric material exhibits an excellent electrical conductivity of >10 S cm−1 and an ultralow thermal conductivity of, Achieved high thermoelectric figure of merit (ZT) in organic thermoelectric materials remains a challenge due to their low packing order and poor host/dopant miscibility. Here, the authors report side chain-engineered n-doped fullerene derivatives with record ZT >0.3 for organic thermoelectrics.

Phase-transfer exchange of pristine organic ligands for inorganic ones is essential for the integration of colloidal quantum dots (CQDs) in optoelectronic devices. This method results in a colloidal dispersion (ink) which can be directly deposited by various solution-processable techniques to fabricate conductive films. For PbS CQDs capped with methylammonium lead iodide ligands (MAPbI3), the most commonly employed solvent is butylamine, which enables only a short-term (hours) colloidal stability and thus brings concerns on the possibility of manufacturing CQD devices on a large scale in a reproducible manner. In this work, we studied the stability of alternative inks in two highly polar solvents which impart long-term colloidal stability of CQDs: propylene carbonate (PC) and 2,6-difluoropyridine (DFP). The aging and the loss of the ink’s stability were monitored with optical, structural, and transport measurements. With these solvents, PbS CQDs capped with MAPbI3 ligands retain colloidal stability for more than 20 months, both in dilute and concentrated dispersions. After 17 months of ink storage, transistors with a maximum linear mobility for electrons of 8.5 × 10–3 cm2/V s are fabricated; this value is 17% of the one obtained with fresh solutions. Our results show that both PC- and DFP-based PbS CQD inks offer the needed shelf life to allow for the development of a CQD device technology. ISSN:1944-8244 ISSN:1944-8252

Introducing solubilizing α‐branched alkyl chains on a poly(diketopyrrolopyrrole‐alt‐terthiophene) results in a dramatic change of the structural, optical, and electronic properties compared to the isomeric polymer carrying β‐branched alkyl side chains. When branched at the α‐position the alkyl substituent creates a steric hindrance that reduces the tendency of the polymer to π–π stack and endows the material with a much higher solubility in common organic solvents. The wider π–π stacking and reduced tendency to crystallize, evidenced from grazing‐incidence wide‐angle X‐ray scattering, result in a wider optical band gap in the solid state. In solar cells with a fullerene acceptor, the α‐branched isomer affords a higher open‐circuit voltage, but an overall lower power conversion efficiency as a result of a too well‐mixed nanomorphology. Due its reduced π–π stacking, the α‐branched isomer fluoresces and affords near‐infrared light‐emitting diodes emitting at 820 nm., Branching out: α‐Branched alkyl side chains avoid aggregation of polydiketopyrrolopyrroles and permit processing organic solar cells and light‐emitting diodes from benign solvents.

Understanding cell/material interactions is essential to design functional cell‐responsive materials. While the scientific literature abounds with formulations of biomimetic materials, only a fraction of them focused on mechanisms of the molecular interactions between cells and material. To provide new knowledge on the strategies for materials/cell recognition and binding, supramolecular benzene‐1,3,5‐tricarboxamide copolymers bearing benzoxaborole moieties are anchored on the surface of human erythrocytes via benzoxaborole/sialic‐acid binding. This interaction based on both dynamic covalent and non‐covalent chemistries is visualized in real time by means of total internal reflection fluorescence microscopy. Exploiting this imaging method, we observe that the functional copolymers specifically interact with the cell surface. An optimal fiber affinity towards the cells as a function of benzoxaborole concentration demonstrates the crucial role of multivalency in these cell/material interactions., Drawn to the blood: When benzene‐1,3,5‐tricarboxamide 1D fibers are decorated with benzoxaborole moieties, a dynamic interaction with human red blood cells is induced via the adaptive covalent reaction between boronic acids and cell sialic acids. Total internal reflection fluorescence microscopy is exploited as a powerful tool to allow real‐time imaging of cells/fiber binding, revealing the multivalency of this interaction.

Supramolecular polymers are known to form strong and resilient hydrogels which can take up large amounts of water while exhibiting ease of processing and self-healing. They also possess similarities with networks of biological macromolecules. The combination of these features makes supramolecular polymers ideal candidates for studying mechanisms and consequences of self-assembly, which are relevant to biological materials. At the same time, this renders investigations of mixed hydrogels based on different supramolecular compounds necessary, since this substantially widens their applicability. Here, we address unusual viscoelastic properties of a class of binary hydrogels made by mixing fibrillar supramolecular polymers that are formed from two compounds: 1,3,5-benzene-tricarboxamide decorated with aliphatic chains terminated by tetra(ethylene glycol) (BTA) and a 20 kg/mol telechelic poly(ethylene glycol) decorated with the same hydrogen bonding BTA motif on both ends (BTA-PEG-BTA). Using a suite of experimental and simulation techniques, we find that the respective single-compound-based supramolecular systems form very different networks which exhibit drastically different rheology. More strikingly, mixing the compounds results in a non-monotonic dependence of modulus and viscosity on composition, suggesting a competition between interactions of the two compounds, which can then be used to fine-tune the mechanical properties. Simulations offer insight into the nature of this competition and their remarkable qualitative agreement with the experimental results is promising for the design of mixed hydrogels with desired and tunable properties. Their combination with a sensitive dynamic probe (here rheology) offer a powerful toolbox to explore the unique properties of binary hydrogel mixtures., A two-component hydrogel system, comprising two different supramolecular molecules based on the same hydrogen bonding motif, is shown to exhibit a non-monotonic dependence of modulus and viscosity on composition. This binary hydrogel consists of fibrillar supramolecular polymers formed from two compounds, 1,3,5-benzene-tricarboxamide decorated with aliphatic chains terminated by tetra(ethylene glycol) (BTA) and a 20 kg/mol telechelic poly(ethylene glycol) decorated with the same hydrogen bonding BTA motif on both ends (BTA-PEG-BTA). The powerful combination of rheometric and cryo-TEM experiments with simulations provides detailed insights into the origin of the observed behavior, which is the competition between the dynamic interactions of the two compounds. The coarse-grained model used in simulations implies a universal validity of these findings for a variety of different chemical compounds. It is concluded that interactions between not only the single associating units, but also their changing organization in space with changing relative composition, play a crucial role in the emerging mechanics of binary and multicomponent gels, and therefore have implications in understanding and tailoring the viscoelastic properties of biological networks or designing mixed hydrogels with desired properties.

International audience; We leverage the attractive properties of a high χ-low N BCP, i.e. poly(styrene)-block-poly(2-fluoro ethyl methylacrylate) (PS-b-P2FEMA) and illustrate its utility for next-generation nano-manufacturing. The synthesis, physical characterization and thin film self-assembly of a series of lamellar and cylindrical PS-b-P2FEMA BCPs is delineated. PS-b-P2FEMA BCPs with total molecular weights ranging from 7 kg mol -1 to 22 kg mol -1 were synthesized using reversible-addition-fragmentation chain-transfer (RAFT) polymerization. Temperature resolved small angle X-ray scattering (SAXS) measurements revealed a large χ value (0.13@ 150°C) for PS-b-P2FEMA. Solvo-thermal vapor annealing of PS-b-P2FEMA films produced highly oriented fingerprint patterns in as short as 60 seconds. Lamellar period sizes ranged from 25.9 nm down to 14.2 nm with feature sizes as small as 7 nm observed. We also demonstrate the integration feasibility of PS-b-P2FEMA BCPs through alumina hardmask formation using sequential infiltration synthesis. The highly favorable characteristics of the P2FEMA based BCPs detailed here provide a versatile material option to the current library of available BCPs for sub-10 nm nanolithography.

Incorporation of isolated metal centers into well-organized nanostructures is a promising route in the development of the next generation of chemical, magnetic and electronic devices. In this work, a layer-by-layer protocol to grow highly ordered thin films of metal-decorated organic-inorganic cage-like polyhedral oligomeric silsesquioxane (POSS) is introduced. The key strategy is to use metal ions (Cu2+ or Fe3+) as linker for the amino-functionalized cage-like POSS, which are self-assembled between arachidic acid layers during Langmuir–Schaefer deposition. The Langmuir–Schaefer films are examined by X-ray photoelectron spectroscopy, X-ray diffraction, grazing incidence wide-angle X-ray scattering and extended X-ray absorption fine structure in order to understand how the coordination of metal ions influences the structure in the course of the layer-by-layer formation of the films.

Hybrid organic–inorganic perovskite solar cells have recently emerged as one of the most promising low-cost photovoltaic technologies. The remarkable progress of perovskite photovoltaics is closely related to advances in interfacial engineering and development of charge selective interlayers. Herein, we present the synthesis and characterization of a fused azapolyheteroaromatic small molecule, namely anthradi-7-azaindole (ADAI), with outstanding performance as a hole-transporting layer in perovskite solar cells with inverted architecture. Its molecular arrangement, induced by hydrogen-bond-directed self-assembly, favors a suitable morphology of the perovskite layer, reducing the effects of recombination as revealed by light intensity dependence, photoluminescence, and electroluminescence studies.

The high reaction rate of the 'click-to-release' reaction between allylic substituted trans-cyclooctene and tetrazine has enabled exceptional control over chemical and biological processes. Here we report the development of a new bioorthogonal cleavage reaction based on trans-cyclooctene and tetrazine with up to 3 orders of magnitude higher reactivity compared to the parent reaction, and 4 to 6 orders higher than other cleavage reactions. In this new pyridazine elimination mechanism, wherein the roles a reversed, a trans-cyclooctene activator reacts with a tetrazine that is substituted with a methylene-linked carbamate, leading to an 1,4-elimination of the carbamate and liberation of an amine. Through a series of mechanistic studies, we identified the 2,5-dihydropyridazine tautomer as the releasing species and found factors that govern its formation and subsequent fragmentation. The bioorthogonal utility was demonstrated by the selective cleavage of a tetrazine-linked antibody-drug conjugate by trans-cyclooctenes, affording efficient drug liberation in plasma and cell culture. Finally, the parent and the new reaction were compared at low concentration, showing that the use of a highly reactive trans-cyclooctene as activator leads to a complete reaction with antibody-drug conjugate in seconds vs. hours for the parent system. We believe that this new reaction may allow markedly reduced click-to-release reagent doses in vitro and in vivo and could expand the application scope to conditions wherein the trans-cyclooctene has limited stability.

Hybrid organic-inorganic perovskites allow the synthesis of high-quality, nanostructured semiconducting films via easily accessible solution-based techniques. This has allowed tremendous development in optoelectronic applications, primarily solar cells and light-emitting diodes. Allowed by the ease of access to nanostructure, chirality has recently been introduced in semiconducting perovskites as a promising way to obtain advanced control of charge and spin and for developing circularly polarized light sources. Circular polarization of photoluminescence (CPL) is a powerful tool to probe the electronic structure of materials. However, CPL in chiral perovskites has been scarcely investigated, and a study in bulk thin films and at room temperature is still missing. In this work, we fabricate bromine-based chiral perovskites by using a bulky chiral organic cation mixed with CsBr, resulting in Ruddlesden-Popper perovskite thin films. We measure CPL on these films at room temperature and, by using unpolarized photoexcitation, we record a degree of circular polarization of photoluminescence in the order of 10-3 and provide a full spectral characterization of CPL. Our results show that chirality is imparted on the electronic structure of the semiconductor; we hypothesize that the excess in polarization of emitted light originates from the charge in the photogenerated Wannier exciton describing an orbit in a symmetry-broken environment. Furthermore, our experiments allow the direct measurement of the magnetic dipole moment of the optical transition, which we estimate to be ≥0.1 μB. Finally, we discuss the implications of our findings on the development of chiral semiconducting perovskites as sources of circularly polarized light.

Narrowly dispersed, 10 micron-sized, liquid crystalline elastomer polymer actuators were first prepared via thiol–ene dispersion polymerization and then embedded and stretched in a polyvinyl alcohol film, followed by photopolymerization of the residual acrylate groups. Prolate micro spheroids in which the mesogens are aligned parallel to the long axis were obtained and showed reversible thermally driven actuation owing to nematic to isotropic transition of the liquid crystal molecules. The particles were also compressed to form disk-shaped oblate microactuators in which the mesogens are aligned perpendicular to the short axis, demonstrating that the reported method is a versatile method to fabricate liquid crystal elastomer microactuators with programmable properties.

Multiresponsive polymers that can respond to several external stimuli are promising materials for a manifold of applications. Herein, a facile method for the synthesis of triple‐responsive (pH, temperature, CO2) poly(N,N‐diethylaminoethyl methacrylamide) by a post‐polymerization amidation of poly(methyl methacrylate) (PMMA) is presented. Combined with trivalent counterions ([Fe(CN)6]3−) both an upper and lower critical solution temperature (UCST/LCST)‐type phase behavior can be realized at pH 8 and 9. PMMA and PMMA‐based block copolymers are readily accessible by living anionic and controlled radical polymerization techniques, which opens access to various responsive polymer architectures based on the developed functionalization method. This method can also be applied on melt‐processed bulk PMMA samples to introduce functional, responsive moieties at the PMMA surface., Making PMMA responsive: PMMA can be converted into a triple‐responsive polymer, being responsive to temperature, pH and CO2 gas, by a quantitative post‐polymerization amidation with N,N‐diethylethylenediamine. This will open access to a large variety of responsive macromolecular architectures, because this method can be applied to PMMA and PMMA‐based block copolymers, being easily accessible by living anionic or controlled radical polymerization (see scheme).

Despite numerous reports on nucleated supramolecular polymerization, the molecular origin of the properties of these supramolecular polymers remains overlooked. Here, the formation of fibers formed by self-assembly of N,N′,N′′-tris(alkoxybenzyl)benzene-1,3,5-tricarboxamides (benzyl-BTAs) has been studied using both simulations and experimental techniques. The simulations show that the fibers exhibit a dynamic behavior with stacking defects that appear and propagate differently depending on the BTA molecular structure. To validate theoretical results, a library of eight benzyl-BTAs has been synthesized to compare their supramolecular polymerizations both in the bulk and in apolar solvents. We show that the molecular organization of monomers and dynamics of supramolecular polymers strongly depend on the number and position of the alkoxy substituents on peripheral phenyl rings. By combining theoretical results with experimental measurements, we elucidate the likely role of competitive hydrogen bonding between the central amides and peripheral ether moieties on the stacking behavior of BTAs and the dynamics of structural defects in supramolecular polymers. Our findings open up new design rules for these dynamic materials., MFJM and ARAP thank E.W. (Bert) Meijer for stimulating discussions, Elisabeth Weyandt for providing several aldehyde starting materials, and acknowledge financial support from NWO (TOP-PUNT Grant 10018944) and the Dutch Ministry of Education, Culture and Science (Gravitation program 024.001.035). RMR, HSC, JB and JMF acknowledge the Ministerio de Ciencia Innovación y Universidades (Spain) for funding through the Ramón y Cajal Program (RYC-2013-12570) and Proyectos I+D+i (CTQ2015-66869-P). HSC is grateful for a FPU fellowship from Ministerio de Educación Cultura y Deporte (Spain). The collaboration between Eindhoven and Mons is supported by the Fonds de la Recherche Scientifique – FNRS and the Fonds Wetenschappelijk Onderzoek under EOS Project No. 30650939. Computational resources have been provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by the Fonds de la Recherche Scientifique de Belgique (F.R.S.-FNRS) under Grant No. 2.5020.11 and by the Wallonia Region.

Supramolecular systems are intrinsically dynamic and sensitive to changes in molecular structure and external conditions. Because of these unique properties, strategies to control polymer length, composition, comonomer sequence, and morphology have to be developed for sufficient control over supramolecular copolymerizations. We designed photoresponsive, mono acyl hydrazone functionalized benzene-1,3,5-tricarboxamide (m-BTA) monomers that play a dual role in the coassembly with achiral alkyl BTAs (a-BTA). In the E isomer form, the chiral m-BTA monomers intercalate into stacks of a-BTA and dictate the chirality of the helices. Photoisomerization to the Z isomer transforms the intercalator into a chain capper, allowing dynamic shortening of chain length in the supramolecular aggregates. We combine optical spectroscopy and light-scattering experiments with theoretical modeling to show the reversible decrease in length when switching from the E to Z isomer of m-BTA in the copolymer with inert a-BTA. With a mass-balance thermodynamic model, we gain additional insights into the composition of copolymers and length distributions of the species over a broad range of concentrations and mixing ratios of a-BTA/m-BTA. Moreover, the model was used to predict the impact of an additive (chain capper and intercalator) on the chain length over a range of concentrations, showing a remarkable amplification of efficiency at high concentrations. By employing a stimuli-responsive comonomer in a mostly inert polymer, we can cooperatively amplify the effect of the switching and obtain photocontrol of polymer length. Moreover, this dynamic decrease in chain length causes a macroscopic gel-to-sol phase transformation of the copolymer gel, although 99.4% of the organogel is inert to the light stimulus.

International audience; This work presents a straightforward strategy to introduce highly dynamic and adaptable cross-links into common epoxy resin formulations. For this, an oligomeric amine-based curing agent containing vinylogous urethane (VU) bonds was developed. This novel polyfunctional amine curing agent can be used as a drop-in solution for existing epoxy resin technologies, resulting in transparent, rigid, and, at the same time, highly reprocessable catalyst-free epoxy vitrimers. The oligomeric VU-curing agents are prepolymerized via a straightforward condensation reaction between acetoacetates extended with different classical amine monomers and epoxy hardeners. It is found that vitrimer properties can be readily introduced into these epoxy formulations by converting

Self-assembled monolayers (SAMs) are widely used to engineer the surface properties of metals. The relatively simple and versatile chemistry of metal-thiolate bonds makes thiolate SAMs the preferred option in a range of applications, yet fragility and a tendency to oxidize in air limit their long-term use. Here, we report the formation of thiol-free self-assembled mono- and bilayers of glycol ethers, which bind to the surface of coinage metals through the spontaneous chemisorption of glycol ether-functionalized fullerenes. As-prepared assemblies are bilayers presenting fullerene cages at both the substrate and ambient interface. Subsequent exposure to functionalized glycol ethers displaces the topmost layer of glycol ether-functionalized fullerenes, and the resulting assemblies expose functional groups to the ambient interface. These layers exhibit the key properties of thiolate SAMs, yet they are stable to ambient conditions for several weeks, as shown by the performance of tunnelling junctions formed from SAMs of alkyl-functionalized glycol ethers. Glycol ether-functionalized spiropyrans incorporated into mixed monolayers lead to reversible, light-driven conductance switching. Self-assemblies of glycol ethers are drop-in replacements for thiolate SAMs that retain all of their useful properties while avoiding the drawbacks of metal-thiolate bonds.

Achieving long-range order with surface-supported supramolecular assemblies is one of the pressing challenges in the prospering field of non-covalent surface functionalization. Having access to defect-free on-surface molecular assemblies will pave the way for various nanotechnology applications. Here we report the synthesis of two libraries of naphthalenediimides (NDIs) symmetrically functionalized with long aliphatic chains (C28 and C33) and their self-assembly at the 1-phenyloctane/highly oriented pyrolytic graphite (1-PO/HOPG) interface. The two NDI libraries differ by the presence/absence of an internal double bond in each aliphatic chain (unsaturated and saturated compounds, respectively). All molecules assemble into lamellar arrangements, with the NDI cores lying flat and forming 1D rows on the surface, while the carbon chains separate the 1D rows from each other. Importantly, the presence of the unsaturation plays a dominant role in the arrangement of the aliphatic chains, as it exclusively favors interdigitation. The fully saturated tails, instead, self-assemble into a combination of either interdigitated or non-interdigitated diagonal arrangements. This difference in packing is spectacularly amplified at the whole surface level and results in almost defect-free self-assembled monolayers for the unsaturated compounds. In contrast, the monolayers of the saturated counterparts are globally disordered, even though they locally preserve the lamellar arrangements. The experimental observations are supported by computational studies and are rationalized in terms of stronger van der Waals interactions in the case of the unsaturated compounds. Our investigation reveals the paramount role played by internal double bonds on the self-assembly of discrete large molecules at the liquid/solid interface.

Mechanoresponsive polymers with intense red emission are highly desirable in view of the strong penetrability and high resolution of red luminescence. Herein we introduce the sensitized luminescence of rare-earth Eu(III) complexes into the mechanochemiluminescence from polymeric dioxetane in a covalent way. By controlling the energy-Transfer process from mechanically broken dioxetane to the Eu(III) center, bright red emission from transparent poly(methyl acrylate) films was achieved for the first time. Importantly, mechanoluminescence sensitivity is greatly improved, enabling the location and timing of bond scission with high resolution. A sensitive stretchable device with the polymer film as an emissive layer was fabricated by a facile surface-engineering method, which can emit patterned red light upon deformation. This sensitized mechanoluminescence design thus expands the useful space of luminescent stress probes.

Multi-component systems often display convoluted behavior, pathway complexity and coupled equilibria. In recent years, several ways to control complex systems by manipulating the subtle balances of interaction energies between the individual components have been explored and thereby shifting the equilibrium between different aggregate states. Here we show the enantioselective chain-capping and dilution-induced supramolecular polymerization with a Zn2+-porphyrin-based supramolecular system when going from long, highly cooperative supramolecular polymers to short, disordered aggregates by adding a monotopic Mn3+-porphyrin monomer. When mixing the zinc and manganese centered monomers, the Mn3+-porphyrins act as chain-cappers for Zn2+-porphyrin supramolecular polymers, effectively hindering growth of the copolymer and reducing the length. Upon dilution, the interaction between chain-capper and monomers weakens as the equilibria shift and long supramolecular polymers form again. This dynamic modulation of aggregate morphology and length is achieved through enantioselectivity in the aggregation pathways and concentration-sensitive equilibria. All-atom and coarse-grained molecular simulations provide further insights into the mixing of the species and their exchange dynamics. Our combined experimental and theoretical approach allows for precise control of molecular self-assembly and chiral discrimination in complex systems., Controlling multicomponent systems is difficult due to convoluted behavior, pathway complexity, and coupled equilibria. Here the authors showed modulation of aggregate morphology in a zinc porphyrin-based supramolecular system via judicious capping with a manganese porphyrin monomer, in which the monomer’s chirality can influence the supramolecular behavior.

Fire resistant coatings have been proven as an efficient way to improve fire safety in three aspects: reducing the Heat Release Rate (HRR), delaying the ignition time and preventing heat transfer. Herein, a SiO2 based polymeric composite coating with a lower thermal conductivity and brilliant fire resistance was developed. Isocyanate and sodium silicate could form the final Si-O-Si network structure by polymerization. Compared to the wood without coating, the coated wood shows a significantly increase in limit oxygen index (LOI), has reached 48.0 vol% in the test. As for the cone calorimetry test, coated wood shows a 55.3% decrease in the first peak Heat Release Rate (pHRR) and the Total Heat Release (THR) obtains fire-resistant standard. After exposed to butane flame for 30 mins, the coated wood could still maintain its structural integrity with only 180℃ on the non-exposed side. The commercial standard test of the coating was also investigated. To better understand what role does the polyurea play in the system, a theoretical calculation was done during the research to discuss the interaction between the silica and polyurea. As a fast brush-formed coating, it exhibits a great potential in the field of fire-resistant materials, and may broaden the application prospects of wood.