An optical calcium sensor is fabricated based on a cholesteric liquid crystalline (CLC) polymer containing benzoic acid metal binding sites. A chiral imprinted CLC polymer is made which is subsequently treated with KOH to yield a responsive green reflecting film. On investigation of various metal ions, the polymer film shows a high optical response, and selectivity for calcium ions, which is related to the preorganized binding sites in the ordered liquid crystalline phase, leading to a blue reflecting film. The photonic polymer film is sensitive to Ca²⁺ within the physiologically relevant concentration range of 10⁻⁴ to 10⁻² m. Measurement of total calcium concentration in serum is also investigated using the film. The optical responses of normal serum and samples mimicking hypocalcemia and hypercalcemia can be clearly distinguished, providing a cheap, battery-free, and easy-to-use alternative for calcium determination in clinical diagnostics.

Stimuli-responsive materials based on interpenetrating liquid crystal-hydrogel polymer networks are fabricated. These materials consist of a cholesteric liquid crystalline network that reflects color and an interwoven poly(acrylic acid) network that provides a humidity and pH response. The volume change in the cross-linked hydrogel polymer results in a dimensional alteration in the cholesteric network as well, which, in turn, leads to a color change yielding a dual-responsive photonic material. Furthermore a patterned coating having responsive and static interpenetrating polymer network areas is produced that changes both its surface topography and color.

An efficient and selective porous nanostructured polymer adsorbent is prepared from smectic liquid crystals. The adsorption study is performed by using hydrophilic dyes as water pollutants. The anionic pore interior of the nanoporous polymer is able to selectively adsorb cationic methylene blue over anionic methyl orange. Even zwitter ionic rhodamine B could hardly be adsorbed due to the presence of the anionic group in this dye. The confined pore dimensions allow size selective adsorption; a 4^th generation cationic dendrimer is not able to diffuse into the nanometer sized pores. The porous nature of the polymer provides easy and fast accessibility of all adsorption sites. Stoichiometric ion exchange is obtained, which equates to an adsorption capacity of nearly 1 gram of methylene blue per 1 gram adsorbent. A competitive Langmuir adsorption constant and pseudo second order rate constant are determined. The adsorbent and adsorbate could both be retrieved after acid treatment of the polymer.

This work describes the fabrication, characterization, and modelling of liquid crystalline polymer network films with a multiple patterned 3D nematic director profile, a stimuli-responsive material that exhibits complex mechanical actuation under change of temperature or pH. These films have a discrete alternating striped or checkerboard director profile in the plane, and a 90-degree twist through the depth of the film. When actuated via heating, the striped films deform into accordion-like folds, while the film patterned with a checkerboard microstructure buckles out-of-plane. Furthermore, striped films are fabricated so that they also deform into an accordion shaped fold, by a change of pH in an aqueous environment. Three-dimensional finite element simulations and elasticity analysis provide insight into the dependence of shape evolution on director microstructure and the sample's aspect ratio.

A printable hydrogen-bonded cholesteric liquid crystal (CLC) polymer film is described, which can be used as a sensor for detection of gaseous trimethylamine (TMA). In this optical sensor the virgin CLC polymer network reflects green light. When anhydrous TMA gas penetrates the film, disruption of the hydrogen bonds occurs, with the simultaneous formation of carboxylate salts. The consequent reduction of the molecular order causes the green reflecting CLC film to become colorless. However, exposure to TMA in water-saturated nitrogen gas results in a red reflecting film. Due to the hygroscopic nature of the polymer salt that is formed by TMA, water vapor which is present in the environment is absorbed by the films. This leads to swelling of the film, resulting in an increase in pitch size and therefore a red shift of the reflection band. Interestingly, after exposure to ambient conditions, restoration of the green reflecting film takes place, showing that the sensor can be used multiple times. In a proof of principle experiment, it was shown that these CLC films can be used as optical sensors to detect volatile amines, that are produced by decaying fish.

The effect of the ortho alkylation of perylene bisimides on the alignment and self-assembly properties has been studied. It was found that the dichroic properties of perylene bisimides in a liquid crystal host can be reversed with a single synthetic step by ortho alkylation. Furthermore, a solvent-induced growth of ultralong organic n-type semiconducting fibrils from non-ortho-alkylated perylene bisimide was observed. Ortho substitution of the perylene bisimide core alters the mode of fibrillar growth, leading to isotropic crystallization.

An optical and irreversible temperature sensor (e.g., a time-temperature integrator) is reported based on a mechanically embossed chiral-nematic polymer network. The polymer consists of a chemical and a physical (hydrogen-bonded) network and has a reflection band in the visible wavelength range. The sensors are produced by mechanical embossing at elevated temperatures. A relative large compressive deformation (up to 10%) is obtained inducing a shift to shorter wavelength of the reflection band (>30 nm). After embossing, a temperature sensor is obtained that exhibits an irreversible optical response. A permanent color shift to longer wavelengths (red) is observed upon heating of the polymer material to temperatures above the glass transition temperature. It is illustrated that the observed permanent color shift is related to shape memory in the polymer material. The films can be printed on a foil, thus showing that these sensors are potentially interesting as time-temperature integrators for applications in food and pharmaceutical products.

Chiral induction and amplification in surface-confined supramolecular monolayers are investigated at the liquid–solid interface. Scanning tunneling microscopy (STM) proves that achiral molecules can self-assemble into globally chiral patterns through a variety of approaches, including induction by chiral solvents or by a novel chiral amplification method. Our study demonstrates the aptness of both approaches, which have already been applied to (supramolecular) polymers in solution, to create chiral supramolecular monolayers at the liquid–solid interface.

Fluorescent nanoparticles based on π-conjugated small molecules and polymers are two different classes of π-conjugated systems that have attracted much interest. To date, both emerging classes have only been studied separately and showed no clear differences in their properties. Herein these nanoparticles are compared on the basis of a fluorene co-polymer and its corresponding small molecule. Both systems formed nanoparticles with the same diameter, whereas the fluorescence properties clearly differed. In case of the polymer the fluorescence diminished, whereas for the small molecules the fluorescence increased. In addition, the capability of encapsulation and release of a hydrophobic dye from the fluorescent nanoparticles was studied. For the polymer system, encapsulation was highly efficient and no release was observed, whereas for the small molecule system encapsulation was less efficient and release of the dye was observed. These studies show a clear difference between small molecules and polymers which has important implications for the design of fluorescent nanoparticles.

Herein, we describe the preparation of patterned photoresponsive hydrogels by using a facile method. This polymer-network hydrogel coating consists of N-isopropylacrylamide (NIPAAM), cross-linking agent tripropylene glycol diacrylate (TPGDA), and a new photochromic spiropyran monoacrylate. In a pre-study, a linear NIPAAM copolymer (without TPGDA) that contained the spiropyran dye was synthesised, which showed relatively fast photoswitching behaviour. Subsequently, the photopolymerisation of a similar monomer mixture that included TPGDA afforded freestanding hydrogel polymer networks. The light-induced isomerisation of protonated merocyanine into neutral spiropyran under slightly acidic conditions resulted in macroscopic changes in the hydrophilicity of the entire polymer film, that is, shrinkage of the hydrogel. The degree of shrinkage could be controlled by changing the chemical composition of the acrylate mixture. After these pre-studies, a hydrogel film with spatially modulated cross-link density was fabricated through polymerisation-induced diffusion, by using a patterned photomask. The resulting smooth patterned hydrogel coating swelled in slightly acidic media and the swelling was higher in the regions with lower cross-linking densities, thus yielding a corrugated surface. Upon exposure to visible light, the surface topography flattened again, thus showing that a hydrogel coating could be created, the topography of which could be controlled by light irradiation.

Fluorescent, cell-permeable, organic nanoparticles based on self-assembled π-conjugated oligomers with high absorption cross-sections and high quantum yields have been developed. The nanoparticles are generated with a tuneable density of amino groups for charge-mediated cellular uptake by a straightforward self-assembly protocol, which allows for control over size and toxicity. The results show that a single amino group per ten oligomers is sufficient to achieve cellular uptake. The non-toxic nanoparticles are suitable for both one- and two-photon cellular imaging and flow cytometry, and undergo very efficient cellular uptake.

Funktionelle organische Materialien sind von großem Interesse für eine Vielzahl von Anwendungen. Um funktionelle Eigenschaften gezielt einstellen zu können, benötigt man wohldefinierte hierarchisch geordnete supramolekulare Materialien. Die Selbstorganisation von Flüssigkristallen hat sich als ein extrem nützliches Werkzeug für die Entwicklung nanostrukturierter Materialien bewährt. Wir wählen das anschauliche Beispiel photopolymerisierbarer wasserstoffverbrückter Mesogene, um zu zeigen, dass eine breite Vielfalt funktioneller Materialien aus einem relativ einfachen Satz von Bausteinen hergestellt werden kann. Durch Umsetzung dieser Verbindungen mit anderen reaktiven Mesogenen können nematische, chirale nematische und smektische oder kolumnare flüssigkristalline Phasen gebildet werden, die als Aktuatoren, Sensoren, responsive Reflektoren und nanoporöse Membranen genutzt werden können.

The self-assembly of two enantiomerically pure hexa(oligo (p-phenylene vinylene))-substituted benzenes having 24 stereocenters was studied in pure methylcyclohexane (MCH) and in a mixture of MCH/toluene (4:1). Irrespective of the solvent a cooperative supramolecular polymerization mechanism was determined for these star-shaped molecules by using temperature-dependent CD and UV/Vis spectroscopy. Quite remarkably, a transition from one helical supramolecular state (A) to a second more thermodynamically stable supramolecular helical assembly (B) was observed. The rate of the AB transition was strongly dependent on the nature of the solvent; being faster in the solvent mixture than in pure MCH. By using size exclusion chromatography we could relate the increased rate to a decreased stability of the supramolecular A state in the solvent mixture. Next, we mixed the two enantiomerically pure hexa-substituted benzene derivatives in a so-called majority-rules experiment, which lead to the anitcipated chiral amplification in the A state. More importantly it appeared that the AB transition was significantly hampered in these mixed systems. Furthermore, the absence of chiral amplification in the B state revealed the formation of separated enantiomerically pure assemblies. Therefore, by using a wide variety of spectroscopic and chromatographic techniques we determined the influence of solvent and enantiomeric purity on the transition between different supramolecular states.

Functional organic materials are of great interest for a variety of applications. To obtain precise functional properties, well-defined hierarchically ordered supramolecular materials are crucial. The self-assembly of liquid crystals has proven to be an extremely useful tool in the development of well-defined nanostructured materials. We have chosen the illustrative example of photopolymerizable hydrogen-bonding mesogens to show that a wide variety of functional materials can be made from a relatively simple set of building blocks. Upon mixing these compounds with other reactive mesogens, nematic, chiral nematic, and smectic or columnar liquid-crystalline phases can be formed that can be applied as actuators, sensors and responsive reflectors, and nanoporous membranes, respectively.

π-Conjugated molecules are interesting components to prepare fluorescent nanoparticles. From the use of polymer chains that form small aggregates in water to the self-assembly of small chromophoric segments into highly ordered structures, the preparation of these materials allows to develop systems with applications as sensors or biolabels. The potential functionalization of the nanoparticles can lead to specific probing. This progress report describes the recent advances in the preparation of such emittive organic nanoparticles.

To study the supramolecular polymerisation mechanisms of a self-assembling system, concentration- and temperature-dependent measurements can both be used to probe the transition from the molecular dissolved state to the aggregated state. In this report, both methods are evaluated to determine their effectiveness in identifying and quantifying the self-assembly mechanism for isodesmic and cooperative self-assembling systems. It was found that for a rapid and unambiguous determination of the self-assembly mechanism and its thermodynamic parameters, temperature-dependent measurements are more appropriate. These studies allow the acquisition of a large data set leading to an accurate determination of the self-assembly mechanism and quantification of the different thermodynamic parameters that describe the supramolecular polymerisation. For a comprehensive characterisation, additional concentration-dependent measurements can be performed.

Fluorene-based π-conjugated polymers and oligomers combine several advantageous properties that make them well-suited candidates for applications in organic optoelectronic devices and chemical sensors. This review highlights strategies to synthesize these materials and to tune their absorption and emission colors. Furthermore, methods to control their supramolecular organization will be discussed. In many cases, a delicate interplay between the chemical structure and the processing conditions are found, resulting in a high sensitivity of both structural features and optical properties. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4215–4233, 2009

Supramolecular complexes consisting of a single-stranded oligothymine (dTn) as the host template and an array of guest molecules equipped with a complementary diaminotriazine hydrogen-bonding unit have been studied with electrospray-ionization mass spectrometry (ESI-MS). In this hybrid construct, a supramolecular stack of guest molecules is hydrogen bonded to dTn. By changing the hydrogen-bonding motif of the DNA host template or the guest molecules, selective hydrogen bonding was proven. We were able to detect single-stranded-DNA (ssDNA)–guest complexes for strands with lengths of up to 20 bases, in which the highest complex mass detected was 15 kDa; these complexes constitute 20-component self-assembled objects. Gas-phase breakdown experiments on single- and multiple-guest–DNA assemblies gave qualitative information on the fragmentation pathways and the relative complex stabilities. We found that the guest molecules are removed from the template one by one in a highly controlled way. The stabilities of the complexes depend mainly on the molecular weight of the guest molecules, a fact suggesting that the complexes collapse in the gas phase. By mixing two different guests with the ssDNA template, a multicomponent dynamic library can be created. Our results demonstrate that ESI-MS is a powerful tool to analyze supramolecular ssDNA complexes in great detail.

Five fluorene-based co-oligomers have been prepared to study their self-assembly in a wide range of concentrations, from dilute solutions to the solid state. Subtle changes to the chemical structures, introduced to tune the emission colours over the entire visible range, induce strong differences in aggregation behaviour. Only two of the fluorescent co-oligomer derivatives self-assemble to form soluble fibrils from which fluorescent organogels emerge at higher concentrations. In contrast, the other compounds form precipitates. Mixed fluorescent co-oligomer systems exhibit partial energy transfer, which allows the creation of white-light-emitting gels. Finally, a mechanism for the hierarchical self-assembly of this class of materials is proposed based on experimental results and molecular modelling calculations.

We demonstrate by using vibrational circular dichroism (VCD) spectroscopy that it is possible to investigate the chirality of a supramolecular polymeric system in relatively dilute solutions. Chiral C₃-symmetrical discotic molecules, based on a trialkylbenzene-1,3,5-carboxamide, form supramolecular columnar stacks with a right-handed helical structure in solution due to intermolecular hydrogen bonds. The handedness of the supramolecular chirality is determined using electronic spectroscopy measurements. Under dilute conditions (at 10⁻³ M concentrations), it was also possible to probe the hydrogen bonding moieties with IR and VCD spectroscopy on these self-assembled structures. In combination with density functional theory (DFT) calculations, we could verify the preference for a right-handed chirality in the helical stacks and the nonplanar orientation of the carbonyl groups present in the molecule. This chiral arrangement is in agreement with the structure determined for a related benzene-1,3,5-tricarboxamide by X-ray diffraction. Chirality, 2008. © 2008 Wiley-Liss, Inc.

A melamine derivative has been covalently equipped with two oligo(para-phenylenevinylene) (OPV) chromophores. This procedure yields a bifunctional molecule with two hydrogen-bonding arrays available for complementary binding to perylene bisimide derivatives. Depending on the solvent, hydrogen-bonded trimers, tetramers, and dimers on a graphite surface are observed for pure OPV–melamine by using scanning tunneling microscopy (STM). Upon the addition of perylene bisimide, linear tapes of perylene bisimide, 12-membered rosettes that consist of alternating hydrogen-bonded OPV–melamine and perylene bisimide moieties are visualized. These results provide direct evidence for the possible modes of hydrogen bonding within a supramolecular co-assembly in solution. Subsequently, the optical properties of pure OPV–melamine and co-assemblies with a perylene bisimide derivative were characterized in solution. In an apolar solvent, OPV–melamine self-assembles into chiral superstructures. Disassembly into molecularly dissolved species is reversibly controlled by concentration and temperature. Complementary hydrogen bonding to a perylene bisimide derivative in an apolar solvent yields multicomponent, π-stacked dye assemblies of enhanced stability that are characterized by fluorescence quenching of the constituent chromophores. Titration experiments reveal that a mixture of hydrogen-bonded oligomers is present in solution, rather than a single discrete assembly. The solution experiments are consistent with the STM results, which revealed various supramolecular assemblies. Our system is likely not to be optimally programmed to obtain a discrete co-assembled structure in quantitative yield.