Specific Supramolecular Interactions Research Articles

Evaporation-Induced Self-Assembly of Small Peptide-Conjugated Silica Nanoparticles.

Self‐assembly processes guide disordered molecules or particles into long‐range organized structures due to specific supramolecular interactions among the building entities. Herein, we report a unique evaporation‐induced self‐assembly (EISA) strategy for four different silica nanoparticle systems obtained through peptide functionalization of the particle surface. First, covalent peptide‐silica coupling was investigated in detail, starting with the grafting of a single amino acid (L‐serine) and expanded to specific small peptides (up to four amino acids) and transferred to different particle types (MCM‐48‐type MSNs, solid nanoparticles, and newly developed virus‐like nanoparticles). These materials were investigated regarding their ability to undergo EISA, which was shown to be independent of particle type and amount of peptide anchored to their surface. This EISA‐based approach provides new possibilities for the design of future advanced drug delivery systems, engineered hierarchical sorbents, and nanocatalyst assemblies.

Evaporation‐Induced Self‐Assembly of Small Peptide‐Conjugated Silica Nanoparticles

AbstractSelf‐assembly processes guide disordered molecules or particles into long‐range organized structures due to specific supramolecular interactions among the building entities. Herein, we report a unique evaporation‐induced self‐assembly (EISA) strategy for four different silica nanoparticle systems obtained through peptide functionalization of the particle surface. First, covalent peptide‐silica coupling was investigated in detail, starting with the grafting of a single amino acid (L‐serine) and expanded to specific small peptides (up to four amino acids) and transferred to different particle types (MCM‐48‐type MSNs, solid nanoparticles, and newly developed virus‐like nanoparticles). These materials were investigated regarding their ability to undergo EISA, which was shown to be independent of particle type and amount of peptide anchored to their surface. This EISA‐based approach provides new possibilities for the design of future advanced drug delivery systems, engineered hierarchical sorbents, and nanocatalyst assemblies.

(Invited) Functional Additives for Halide Perovskites Tailored Deposition for Highly Efficient Light-Emitting and Photovoltaic Devices

The control over Organometal Halide Perovskites (OHPs) formation is a fundamental requirement foreseeing the exploitation of these outstanding, eclectic materials in optoelectronics. OHPs, extensively used in solar cells and light emitting diodes (PeLEDs) are deposited from solution on a target substrate and formed throughout a self-assembly process of their chemical precursors [1][2]. The resulting polycrystalline film shows often a far from ideal behaviour, due to unsuitable morphology and high defect density, direct consequences of a scarcely controllable assembly. We present here the exploitation of a tailored biopolymer, starch, as beneficial additional component of formamidinium (FA)- and methylammonium (MA)-based tri-iodide perovskite films. We prove how the macromolecule by establishing specific supramolecular interactions with OHPs precursors allows the deposition of an optimal film via single-step deposition method. Noticeably this is a fundamental technological advantage in comparison to standard multistep deposition approaches. Furthermore, it allows a fine tuning of i) solution viscosity (making it compatible with different large area deposition techniques), of ii) perovskite grain size and of iii) film thickness, parameters that all depends to the polymer:perovskite:solvent relative concentrations. Very importantly the presence of the biopolymer is also improving the stability of the polycrystalline film thanks to two fundamental properties. The polymer being an electronic insulator reduce the impact of the internal electric field over OHPs mobile ions; in addition the polymer is also permeable to ions (ionic conductor), thus by buffering those prevent ions migration/segregation across perovskite grains, one of the most important material degradation mechanism under device working conditions.We validated our approach by embedding these composites in photovoltaic (PV) and light-emitting (PeLED) devices. As result we obtained an inverted, planar, low-temperature processed solar cell showing a remarkable 17% efficiency [3] and a highly efficient LED (EQE of ~5%) exhibiting outstanding radiance values above 200 W/sr·m2 obtained at very high currents (about 1000 mA/cm2) which are among the highest reported radiances for NIR PeLEDs [4].

Real-time and in-situ intracellular ATP assay with polyimidazolium brush-modified nanopipette

The level and dynamics of adenosine 5-triphosphate (ATP) in single living cells are closely related to many kinds of important physiological and pathological processes. Herein, we report a nanosensor based on polyimidazolium brush (PimB)-modified nanopipette for intracellular ATP assay, which shows good selectivity, high spatiotemporal resolution and excellent stability. Both the specific supramolecular interaction between polyimidazolium and ATP, and the rationally tunable property of the ion transport at a confined nanopipette enable the selective assay of ATP even in complex intracellular environment. Moreover, the tiny tip ( ca. 300 nm) and the low polarized current (e.g., 1 nA) essentially make the as-prepared nanosensor safe to the living cells. The nanosensor is demonstrated to be useful for in-situ monitoring the basal ATP levels of chromaffin cells from wild-type mice and DJ-1 knockout mice, and for real-time monitoring the metabolism process of intracellular ATP.

Specific Supramolecular Interaction Regulated Entropically Favorable Assembly of Amphiphilic Macromolecules

This article reports molecular interaction driven aqueous assembly of supramolecularly engineered amphiphilic macromolecules to cylindrical structure. Each polymer contains a single hydrophobic trialkoxybenzamide-linked naphthalene diimide (NDI) chromophore at the chain terminal as the supramolecular structure directing unit (SSDU). Irrespective of the structure of the appended hydrophilic polymer, H-bonding promoted J-aggregation among the NDI chromophore leads to the formation of thermally stable spherical micelle (critical aggregation concentration: 0.01–0.03 mM) which reorganizes to cylindrical micelle after a few hours. The reorganization time can be regulated by pH in the case of the anionic polymer as it affects the dynamics. Isothermal titration calorimetric (ITC) studies reveal positive ΔS values for assembly of all the polymers, reflecting the self-assembly process is favored by the entropy factor similar to the elegant examples in the biological domain. In contrast, a small molecule analogue of...

Metal-enhanced fluorescence emission and quenching protection effect with a host–guest nanophotonic-supramolecular structure

The functionalization of the nanoparticle’s (NP) surface is one method for tuning their overall properties to fit targeted applications. We developed a nanosensor based on the specific supramolecular interactions between s-cyclodextrin (sCD) nanocavities and organic molecules of biological interests using the metal-enhanced fluorescence effect (MEF) as the detection signal. We grafted sCD, a typical macrocyclic host molecule that interacts specifically with different organic molecules and changes their physical properties (such as their fluorescence emission intensity), on gold NPs. To evaluate this nanosensor and the effect of the metallic core, we worked with a typical organic molecule, Rhodamine B (RhB), that has a strong association constant with sCD (5700 M − 1) and is well-known to be quenched in the presence of cyclodextrins (CDs). The results show that, by grafting sCD on gold NPs, it is possible to increase the sensitivity of RhB detection by 70%, 80%, and 294% when compared with solutions in (1) a phosphate buffer, (2) with sCD, and (3) with Au NPs, respectively. These results show that the use of a supramolecular system attached to a metallic NP can interact specifically with a dye to enhance its fluorescence emission through the MEF effect. Moreover, this type of nanosystem can overcome the quenching of the signal by the matrix, such in the case of RhB with CDs. Eventually, this concept could be extended to other dyes with different quenching effects. For this reason, this type of nanosensor system could be used in the future to protect and enhance the dye emission of fluorophores in different biological media.

Structural and Spectroscopic Properties of Assemblies of Self-Replicating Peptide Macrocycles.

Self-replication at the molecular level is often seen as essential to the early origins of life. Recently a mechanism of self-replication has been discovered in which replicator self-assembly drives the process. We have studied one of the examples of such self-assembling self-replicating molecules to a high level of structural detail using a combination of computational and spectroscopic techniques. Molecular Dynamics simulations of self-assembled stacks of peptide-derived replicators provide insights into the structural characteristics of the system and serve as the basis for semiempirical calculations of the UV–vis, circular dichroism (CD) and infrared (IR) absorption spectra that reflect the chiral organization and peptide secondary structure of the stacks. Two proposed structural models are tested by comparing calculated spectra to experimental data from electron microscopy, CD and IR spectroscopy, resulting in a better insight into the specific supramolecular interactions that lead to self-replication. Specifically, we find a cooperative self-assembly process in which β-sheet formation leads to well-organized structures, while also the aromatic core of the macrocycles plays an important role in the stability of the resulting fibers.

Hydrogen bond-directed assembly of silsesquioxanes cubes: synthesis of carboxylic acid POSS derivatives and the solid state structure of octa[2-(p-carboxyphenyl)ethyl] silsesquioxane

The octa[2-(p-carboxyphenyl)ethyl] and octa[2-(4-carboxy-1,1′-biphenyl)ethyl] silsesquioxane were synthesised under mild reaction conditions upon hydrogenolysis of the corresponding benzyl-ester derivatives. The octa[2-(p-carboxyphenyl)ethyl] silsesquioxane was shown to self-assemble upon formation of carboxylic acid dimers. The presence of eight carboxylic acid functional groups allowed to obtain an ordered silsesquioxane hybrid network. The X-ray crystal structures of the octa-ester and of the octa-acid were determined. The three-dimensional conformation of the ester provided an interpenetrated compact packing of the molecular building blocks without any specific supramolecular interaction. The two-dimensional character of the acid and the directionality of the hydrogen bond pattern of a dimer of acid led to the formation of hydrogen-bonded ribbons. It showed that functionalized silsesquioxane precursors capable of hydrogen bonding are of interest to generate nanostructured materials through self-organization processes. Moreover, the use of carboxylic acid groups is interesting not only because of their ability to form carboxyl dimer structures by hydrogen bonding but also because of their ability to form metal carboxylate derivatives that may lead to new organised hybrid metal organic silica frameworks.

Composite sPEEK-TPyP membranes development for portable applications

Composite membranes based on sulphonated Polyetheretherketone (sPEEK) and 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP) were developed for portable applications. A sulphonation degree of 65% and different loadings (0–5 wt%) of TPyP porphyrin were used. Spectroscopic studies (UV–Vis and fluorescence emission), ionic exchange capacity, water uptake, structural and morphological analyses were carried out. A good interaction between the filler and the polymer was found, probably due to specific supramolecular interactions among the nitrogenous atoms present in the periphery of the porphyrin ring and sulphonic groups of polymer. The membrane with the lowest loading (∼1 wt%) of TPyP, shows slightly lower water uptake and unaltered λ values than the reference membrane, resulting in quite unaltered proton conductivity also in anhydrous conditions. Electrochemical tests were performed in a PEFC 25 cm2 single cell at room temperature and anhydrous hydrogen/humidified air. A power density of 93 mW/cm2 was found in anhydrous conditions for sample with the lowest loading of TPyP.

Isomorphism in the structural chemistry of two-coordinate adducts of diphenyl(2-formylphenyl)phosphine and triphenylphosphine with gold(I) halides

Single crystal X-ray structure determinations are recorded for diphenyl(2-formylphenyl)phosphine gold(I) halides [Ph2(Ph-CHO)PAuX], X=Cl, Br and I, and for redeterminations of enhanced precision for triphenylphosphine gold(I) halides [Ph3PAuX], X=Cl, Br, I, and SCN0.91Br0.09. These complexes, other than [Ph2(Ph-CHO)PAuCl], together with a diverse array of other structures, crystallize as an isomorphous series in the orthorhombic space group P212121a=9.804(1)–11.906(3), b=11.771(2)–12.996(3) and c=12.871(1)–14.169(3)Å. In these complexes, introduction of the formyl group results in only minor differences between the conformations of the two phosphine ligands and the corresponding Au–P, Au–X, and Au–P–X bond lengths and angles. The crystal packings of [Ph3PAuX] for X=Cl, Br, I and of [Ph2(Ph-CHO)PAuX] for X=Br and I show that, while these structures are isomorphous, different supramolecular synthons may be present, suggesting global packing considerations are all-important rather than specific supramolecular interactions. This is borne out by the different packing found for the centrosymmetric [Ph2(Ph-CHO)PAuCl] structure. Crystallization of the mixed anion structure [Ph3PAuSCN0.91Br0.09] in the above P212121 lattice rather than the P21/c lattice reported for pure [Ph3PAuSCN] suggests that co-crystallization with bromide may impose constraints on packing considerations which favor crystallization in the P212121 lattice.

In Vitro and In Vivo Supramolecular Modification of Biomembranes Using a Lipidated Coiled‐Coil Motif

The molecular building blocks available in biological systems self-assemble into defined structures in an extremely controlled manner. These structures must be flexible and adaptive to the environment in order to carry out their function in a regulated manner. Therefore, nature uses multiple weak interactions (e.g. hydrogen bonding and van der Waals interactions) to act as the glue to hold these structures together. When many weak interactions cooperatively combine, relatively stable entities are produced, which retain the ability to respond to external stimuli such as fluctuations in ion concentration, pH, and temperature. For many years, nature has been a source of inspiration for supramolecular chemistry. Scientists typically follow the bottom-up approach and design relatively simple molecules which assemble into functional materials with well-defined properties. Recent progress has resulted in molecular systems that are responsive to multiple stimuli and are therefore highly controlled, emulating nature ever more closely. A relatively new development is the application of supramolecular constructs in in vitro and in vivo environments to directly study and influence biological processes in live cells. Chemically tailored systems can be integrated into cell membranes, for example. This enables the modification or regulation of cellular behavior through external artificial signals. There are two approaches for introducing chemical species into a cell membrane by supramolecular chemistry: 1) specific binding of guest molecules to membrane-anchored biomolecules such as native proteins and 2) nonspecific labeling of membranes with the aid of hydrophobic and electrostatic interactions or through a chemical crosslinker. Lipidated peptides are particularly good candidates for application in biological systems as their aggregation behavior can be controlled by carefully balancing the hydrophobicity of the anchor and the hydrophilicity of the cargo; this aids the incorporation of lipidated peptides into membranes. Here we describe the use of a coiled-coil motif as the peptide segment, a highly specific recognition system that can be introduced into live cells. The coiled-coil motif acts as molecular Velcro and can thus be used to link distinct molecular constructs. An example of the specific labeling of proteins through coiled-coil formation was recently supplied by Matsuzaki et al. Surface modification through the nonspecific binding of polymers to cell membranes has also been studied, for example by Ijiro et al. Lipid-grafted polymers adhere to cell membranes and could potentially act as a scaffold to which a wide range of functional moieties could be attached, thereby intervening in the chemistry of the cell. Furthermore, cationic graft copolymers have also been shown to interact electrostatically with cell membranes, resulting in chemically altered cell membranes. Although these examples illustrate that in vitro membrane functionalization is a highly rewarding strategy, there are currently no examples of efficient in vivo strategies. Therefore, it is our goal to transiently modify lipid membranes through specific supramolecular interactions in in vitro and in vivo environments. For this purpose, we use a pair of complementary coiled-coil-forming lipidated peptides (E and K peptides) to specifically introduce a noncovalent and bio-orthogonal recognition motif to biological membranes (Scheme 1). Here, we describe a generic supramolecular tool which allows us to rapidly and efficiently form coiled-coil motifs at the surface of biological membranes. This is of interest as a wide range of molecular constructs can be introduced to the surface of the cell in this way. Coiled-coil-forming peptides E [(EIAALEK)3] and K [(KIAALKE)3] [12] were first covalently conjugated to PEG12 spacers (PEG= polyethylene glycol). Subsequently, a cholesterol moiety was coupled to the pegylated peptides yielding CPE and CPK (Scheme 1A). The cholesterol moiety allows for the immediate insertion of the lipidated peptides into membranes through hydrophobic interactions and the PEG12 moiety was incorporated to aid efficient molecular recognition between the peptide segments E and K. Recently we showed that upon the addition of micellar solutions of either CPE or CPK to plain liposomes, the lipidated peptides spontaneously inserted into liposomal membranes. In the current study, CHO cell membranes (CHO=Chinese hamster ovary) and the skin of zebrafish embryos were modified with coiled-coil-forming peptides by the addition of a micellar solution of CPE or CPK, resulting in immediate incorporation of these amphiphiles into the membranes. Subsequently, the complementary peptide was added, result[*] M. Sc. H. R. Zope, M. Sc. F. Versluis, Dr. J. Voskuhl, Dr. A. Kros Soft Matter Chemistry, Leiden Institute of Chemistry Leiden University P.O. Box 9502, 2300 RA Leiden (The Netherlands) E-mail: a.kros@chem.leidenuniv.nl

Aptamer-based colorimetric sensing of acetamiprid in soil samples: Sensitivity, selectivity and mechanism

A simple and selective aptamer-based colorimetric method was developed for highly sensitive detection of acetamiprid, taking advantages of the sensitive target-induced colour changes that arisen from the interparticle plasmon coupling during the aggregation of Au nanoparticles (NPs). The results showed that the established method could be applied to detect acetamiprid in the linear range between 75nM to 7.5μM, with a low detection limit of 5nM. Meanwhile, by employing an “artificial antibody” acetamiprid-binding aptamer (ABA) as recognition element, highly selective and specific colorimetric visualization of acetamiprid was obtained. It indicated that pesticides which may coexist with acetamiprid could not interfere with the detection of acetamiprid even that had similar structure with acetamiprid, such as imidacloprid and chlorpyrifos. Mechanism study suggested that it could be attributed to the specific supramolecular interaction between ABA and acetamiprid, as well as the resulted target-binding event induced conformation changes of ABA from random coil to hairpin structure. The practical application of the colorimetric method was realized for detecting acetamiprid in real soil samples and monitoring its natural degradation process.

Thermomechanical behavior of hydrogen-bond based supramolecular poly(ε-caprolactone)-silica nanocomposites

Supramolecular polymer nanocomposites represent an attractive alternative to traditional polymers for advanced materials that exhibit stimuli-responsive and self-healing properties. Here, we investigate the effects of specific hydrogen bonding interactions between surface functionalized silica nanoparticles and ureidopyrimidinone (UPy) based hydrogen bonded supramolecular poly(e-caprolactone) in a supramolecular polymer nanocomposite. The effect of varying levels of nanoparticle UPy surface functionalization is considered. In addition to the anticipated improvements in Young's modulus (∼50%) and storage modulus (∼2×) with silica loading, increases in strain at breaking point (∼25%) with silica loading were observed and attributed to particle–matrix hydrogen bonding. However, increasing the extent of UPy surface functionality at a constant nanoparticle loading level led to a marked decrease in storage modulus relative to nanocomposites prepared with as-received silica nanoparticles. TEM investigation of these nanocomposites show an increase in nanoparticle aggregation. Nanoparticle aggregation provides both an explanation for the observed storage modulus reduction and evidence of particle–particle interactions. These results give interesting insight into the competing effects of specific supramolecular interactions in supramolecular polymer nanocomposite materials.

Chiral Triazolium Salts and Ionic Liquids: From the Molecular Design Vectors to Their Physical Properties through Specific Supramolecular Interactions

An exhaustive experimental study based on X-ray diffraction analysis, NMR, FTIR-ATR (attenuated total reflection), and Raman spectroscopy as well as theoretical calculations is reported in order to understand how the non-covalent intermolecular contacts are fundamental to explain structure-property relationships and allowing us to correlate a basic macroscopic property (i.e., the melting point, T(m)) with the structural variables of a family of enantiopure 1,4-dialkyl-1,2,4-triazolium salts. The effect of different structural vectors such as the ring size, the spatial disposition of the substituent, the substitution on the oxygen atom, the nature of the anion, or the N4 alkylation of the triazole on the intermolecular interactions of these chiral salts of a well-defined 3D structure is reported. The non-covalent intermolecular contacts mainly implicating the triazolium H3 proton are fundamental to explain structure-property relationships and, therefore, the physical properties of these new chiral salts, rather than simple anion-cation interactions. Overall, our findings highlight the importance of the specific supramolecular interactions for the understanding of the physical properties of triazolium salts and ionic liquids.

Reversible and Oriented Immobilization of Ferrocene-Modified Proteins

Adopting supramolecular chemistry for immobilization of proteins is an attractive strategy that entails reversibility and responsiveness to stimuli. The reversible and oriented immobilization and micropatterning of ferrocene-tagged yellow fluorescent proteins (Fc-YFPs) onto β-cyclodextrin (βCD) molecular printboards was characterized using surface plasmon resonance (SPR) spectroscopy and fluorescence microscopy in combination with electrochemistry. The proteins were assembled on the surface through the specific supramolecular host-guest interaction between βCD and ferrocene. Application of a dynamic covalent disulfide lock between two YFP proteins resulted in a switch from monovalent to divalent ferrocene interactions with the βCD surface, yielding a more stable protein immobilization. The SPR titration data for the protein immobilization were fitted to a 1:1 Langmuir-type model, yielding K(LM) = 2.5 × 10(5) M(-1) and K(i,s) = 1.2 × 10(3) M(-1), which compares favorably to the intrinsic binding constant presented in the literature for the monovalent interaction of ferrocene with βCD self-assembled monolayers. In addition, the SPR binding experiments were qualitatively simulated, confirming the binding of Fc-YFP in both divalent and monovalent fashion to the βCD monolayers. The Fc-YFPs could be patterned on βCD surfaces in uniform monolayers, as revealed using fluorescence microscopy and atomic force microscopy measurements. Both fluorescence microscopy imaging and SPR measurements were carried out with the in situ capability to perform cyclic voltammetry and chronoamperometry. These studies emphasize the repetitive desorption and adsorption of the ferrocene-tagged proteins from the βCD surface upon electrochemical oxidation and reduction, respectively.

Interactions of Calix[n]arenes with Nucleic Acids

DNA interaction with artificial binders is of great interest, especially in light of the broad range of possible biomedical applications. The growing understanding of replication, transcription and translation opened the path for new approaches to target pathological effects at a very early stage. Meanwhile, the competitive binding to nucleic acids by designed molecules, which, for example, block certain sequences for natural binders, such as transcription factors, has become a promising concept in the context of gene therapy. On the other extreme, the transport of nucleic acids over the cell membrane into the nucleus by transfection agents opens the possibility to reprogram protein biosynthesis within host cells. In the past decades several substance classes have been developed for a noncovalent specific DNA binding with predictable biological effects, such as peptide nucleic acids or polyamide ligands. Calixarenes have not received so much attention, although they consist of a compact aromatic core tuneable in size, and allow the introduction of cationic functionalities at their upper and lower rims. Formerly being utilized as receptor moieties due to the possibility of complexating guests in their cavities, calixarenes are now also used as molecular scaffolds for multivalent ligands and are, therefore, suitable tools for cooperative DNA complexation. This review surveys specific supramolecular interactions between calixarene derivatives and nucleic acids, with an emphasis on structural elements in the calixarenes and the biological consequences of their complex formation with DNA strands.

Specific Supramolecular Interactions between Zn2+-Salophen Complexes and Biologically Relevant Anions

Recognition of inorganic phosphates PO(4)(3-), P(2)O(7)(4-), and P(3)O(10)(5-) and nucleotides AMP(2-), ADP(3-), and ATP(4-) by Zn(2+)-salophen complexes 1 and 2 in ethanol was investigated by different spectroscopic techniques. (31)P NMR and mass spectrometry showed that anions of both series are bound by 1 and 2, while absorption and emission studies revealed that only nucleotides produce relevant changes in the spectral properties of the two hosts. (1)H NMR studies proved that the adenine aromatic group is involved in the complexation, thus pointing out the role of supramolecular ditopic receptors played by salophen derivatives toward this class of biologically relevant substrates. The lifetime of the photogenerated triplet state of the Zn(2+)-salophen compounds was measured by nanosecond laser flash photolysis, and the observed changes upon increasing the concentration of nucleotides allowed the identification of the formation of a 1:0.5 host/guest intermediate complex additionally to the formation of a 1:1 complex.

Molecular Printboards on Silicon Oxide: Lithographic Patterning of Cyclodextrin Monolayers with Multivalent, Fluorescent Guest Molecules

Three compounds bearing multiple adamantyl guest moieties and a fluorescent dye have been synthesized for the supramolecular patterning of beta-cyclodextrin (CD) host monolayers on silicon oxide using microcontact printing and dip-pen nanolithography. Patterns created on monolayers on glass were viewed by laser scanning confocal microscopy. Semi-quantitative analysis of the patterns showed that with microcontact printing approximately a single monolayer of guest molecules is transferred. Exposure to different rinsing procedures showed the stability of the patterns to be governed by specific supramolecular multivalent interactions. Patterns of the guest molecules created at CD monolayers were stable towards thorough rinsing with water, whereas similar patterns created on poly(ethylene glycol) (PEG) reference monolayers were instantly removed. The patterns on CD monolayers displayed long-term stability when stored under N(2), whereas patterns at PEG monolayers faded within a few weeks due to the diffusion of fluorescent molecules across the surface. Assemblies at CD monolayers could be mostly removed by rinsing with a concentrated CD solution, demonstrating the reversibility of the methodology. Patterns consisting of different guest molecules were produced by microcontact printing of one guest molecule and specific adsorption of a second guest molecule from solution to non-contacted areas, giving well-defined alternating assemblies. Fluorescent features of sub-micrometer dimensions were written using supramolecular dip-pen nanolithography.

Self-assembled chromophores for hybrid solar cells

One of the main problems encountered in the dye-photosensitization of wide band semiconductors which have potential use for low-cost hybrid solar cells is the non-specific aggregation of the dye molecules. This effect leads to strong quenching of the dye fluorescence and thus to low device efficiencies. We have designed and synthesized novel chromophores which self-assemble by specific supramolecular interactions forming nanostructures which are strongly fluorescent. Our fully synthetic molecules are mimics of the natural self-assembling bacteriochlorophylls c, d and e that form the light-harvesting apparatus of green photosynthetic bacteria. Our biomimetic approach has allowed us to prepare, in fairly large amounts, various self-assembling porphyrins and chlorins with tailored properties. We can control both the chirality and the optical properties through ordering the transition dipole moments of the chromophores within the self-assembled nanostructure. Very broad absorption spectra, beneficial for efficient light collection over almost the entire visible spectrum, characterize some of our assemblies. Upon anchoring the self-assembled chromophores onto nanocrystalline titania with different grain sizes the fluorescence is not quenched. This fact encourages us to fabricate hybrid devices and measure their photocurrent generation efficiencies.

Binary Encoding of Compound Libraries

The rapid identification of functional molecules that participate in specific supramolecular interactions is a major problem in the screening of compound libraries. The binary encoding developed by Still et al. allows the structure assignment of “active” compounds according to a simple encoding scheme, and is independent of the synthetic chemistry employed. The viability of this concept has already been demonstrated, but the advantages will first be fully realized with libraries of small organic molecules.