Wolfgang Schöfberger

Hydrogen-Bonded Organic Semiconductor Micro- And Nanocrystals: From Colloidal Syntheses to (Opto-)Electronic Devices

Organic pigments such as indigos, quinacridones, and phthalocyanines are widely produced industrially as colorants for everyday products as various as cosmetics and printing inks. Herein we introduce a general procedure to transform commercially available insoluble microcrystalline pigment powders into colloidal solutions of variously sized and shaped semiconductor micro- and nanocrystals. The synthesis is based on the transformation of the pigments into soluble dyes by introducing transient protecting groups on the secondary amine moieties, followed by controlled deprotection in solution. Three deprotection methods are demonstrated: thermal cleavage, acid-catalyzed deprotection, and amine-induced deprotection. During these processes, ligands are introduced to afford colloidal stability and to provide dedicated surface functionality and for size and shape control. The resulting micro- and nanocrystals exhibit a wide range of optical absorption and photoluminescence over spectral regions from the visible to the near-infrared. Due to excellent colloidal solubility offered by the ligands, the achieved organic nanocrystals are suitable for solution processing of (opto)electronic devices. As examples, phthalocyanine nanowire transistors as well as quinacridone nanocrystal photodetectors, with photoresponsivity values by far outperforming those of vacuum deposited reference samples, are demonstrated. The high responsivity is enabled by photoinduced charge transfer between the nanocrystals and the directly attached electron-accepting vitamin B2 ligands. The semiconducting nanocrystals described here offer a cheap, nontoxic, and environmentally friendly alternative to inorganic nanocrystals as well as a new paradigm for obtaining organic semiconductor materials from commercial colorants.

A Bifunctional Electrocatalyst for Oxygen Evolution and Oxygen Reduction Reactions in Water

Abstract Oxygen reduction and water oxidation are two key processes in fuel cell applications. The oxidation of water to dioxygen is a 4 H+/4 e− process, while oxygen can be fully reduced to water by a 4 e−/4 H+ process or partially reduced by fewer electrons to reactive oxygen species such as H2O2 and O2 −. We demonstrate that a novel manganese corrole complex behaves as a bifunctional catalyst for both the electrocatalytic generation of dioxygen as well as the reduction of dioxygen in aqueous media. Furthermore, our combined kinetic, spectroscopic, and electrochemical study of manganese corroles adsorbed on different electrode materials (down to a submolecular level) reveals mechanistic details of the oxygen evolution and reduction processes.

Photocatalytic Reduction of Artificial and Natural Nucleotide Co-factors with a Chlorophyll-Like Tin-Dihydroporphyrin Sensitizer

An efficient photocatalytic two-electron reduction and protonation of nicotine amide adenine dinucleotide (NAD+), as well as the synthetic nucleotide co-factor analogue N-benzyl-3-carbamoyl-pyridinium (BNAD+), powered by photons in the long-wavelength region of visible light (λirr > 610 nm), is demonstrated for the first time. This functional artificial photosynthetic counterpart of the complete energy-trapping and solar-to-fuel conversion primary processes occurring in natural photosystem I (PS I) is achieved with a robust water-soluble tin(IV) complex of meso-tetrakis(N-methylpyridinium)-chlorin acting as the light-harvesting sensitizer (threshold wavelength of λthr = 660 nm). In buffered aqueous solution, this chlorophyll-like compound photocatalytically recycles a rhodium hydride complex of the type [Cp*Rh(bpy)H]+, which is able to mediate regioselective hydride transfer processes. Different one- and two-electron donors are tested for the reductive quenching of the irradiated tin complex to initiate the secondary dark reactions leading to nucleotide co-factor reduction. Very promising conversion efficiencies, quantum yields, and excellent photosensitizer stabilities are observed. As an example of a catalytic dark reaction utilizing the reduction equivalents of accumulated NADH, an enzymatic process for the selective transformation of aldehydes with alcohol dehydrogenase (ADH) coupled to the primary photoreactions of the system is also demonstrated. A tentative reaction mechanism for the transfer of two electrons and one proton from the reductively quenched tin chlorin sensitizer to the rhodium co-catalyst, acting as a reversible hydride carrier, is proposed.

Spectroscopic STM Studies of Single Gold(III) Porphyrin Molecules

Low-temperature scanning tunneling microscopy, a well-established technique for single-molecule investigations in an ultrahigh vacuum environment, has been used to study the electronic properties of Au(III) 5,10,15,20-tetraphenylporphyrin (AuTPP) molecules on Au(111) at the submolecular scale. AuTPP serves as a model system for chemotherapeutically relevant Au(III) porphyrins. For the first time, real-space images and local scanning tunneling spectroscopy data of the frontier molecular orbitals of AuTPP are presented. A comparison with results from density functional theory reveals significant deviations from gas-phase behavior due to a non-negligible molecule/substrate interaction. We identify the oxidation state of the central metal ion in the adsorbed AuTPP as Au(3+).

Conformation of receptor adopted upon interaction with virus revealed by site-specific fluorescence quenchers and FRET analysis.

Human rhinovirus serotype 2 (HRV2) specifically binds to very-low-density lipoprotein receptor (VLDLR). Among the eight extracellular repeats of VLDLR, the third module (V3) has the highest affinity for the virus, and 12 copies of the genetically engineered concatamer V33333-His(6) were found to bind per virus particle. In the present study, ring formation of V33333-His(6) about each of the 12 5-fold symmetry axes on HRV2 was demonstrated by fluorescence resonance energy transfer (FRET) between donor and acceptor on N- and C-terminus, respectively. In particular, the N-terminus of V33333-His(6) was labeled with fluorescein, and the C-terminus with a new quencher which was bound to the His(6) tag with nanomolar affinity (K(d) approximately 10(-8) M) in the presence of 2 microM NiCl(2).

Quasi-epitaxial Metal-Halide Perovskite Ligand Shells on PbS Nanocrystals

Epitaxial growth techniques enable nearly defect free heterostructures with coherent interfaces, which are of utmost importance for high performance electronic devices. While high-vacuum technology-based growth techniques are state-of-the art, here we pursue a purely solution processed approach to obtain nanocrystals with eptaxially coherent and quasi-lattice matched inorganic ligand shells. Octahedral metal-halide clusters, respectively 0-dimensional perovskites, were employed as ligands to match the coordination geometry of the PbS cubic rock-salt lattice. Different clusters (CH3NH3+)(6-x)[M(x+)Hal6](6-x)- (Mx+ = Pb(II), Bi(III), Mn(II), In(III), Hal = Cl, I) were attached to the nanocrystal surfaces via a scalable phase transfer procedure. The ligand attachment and coherence of the formed PbS/ligand core/shell interface was confirmed by combining the results from transmission electron microscopy, small-angle X-ray scattering, nuclear magnetic resonance spectroscopy and powder X-ray diffraction. The lattice mismatch between ligand shell and nanocrystal core plays a key role in performance. In photoconducting devices the best performance (detectivity of 2 × 1011 cm Hz 1/2/W with > 110 kHz bandwidth) was obtained with (CH3NH3)3BiI6 ligands, providing the smallest relative lattice mismatch of ca. -1%. PbS nanocrystals with such ligands exhibited in millimeter sized bulk samples in the form of pressed pellets a relatively high carrier mobility for nanocrystal solids of ∼1.3 cm2/(V s), a carrier lifetime of ∼70 μs, and a low residual carrier concentration of 2.6 × 1013 cm-3. Thus, by selection of ligands with appropriate geometry and bond lengths optimized quasi-epitaxial ligand shells were formed on nanocrystals, which are beneficial for applications in optoelectronics.

Preserving charge and oxidation state of Au(III) ions in an agent-functionalized nanocrystal model system.

Supporting functional molecules on crystal facets is an established technique in nanotechnology. To preserve the original activity of ionic metallorganic agents on a supporting template, conservation of the charge and oxidation state of the active center is indispensable. We present a model system of a metallorganic agent that, indeed, fulfills this design criterion on a technologically relevant metal support with potential impact on Au(III)-porphyrin-functionalized nanoparticles for an improved anticancer-drug delivery. Employing scanning tunneling microscopy and -spectroscopy in combination with photoemission spectroscopy, we clarify at the single-molecule level the underlying mechanisms of this exceptional adsorption mode. It is based on the balance between a high-energy oxidation state and an electrostatic screening-response of the surface (image charge). Modeling with first principles methods reveals submolecular details of the metal–ligand bonding interaction and completes the study by providing an illustrative electrostatic model relevant for ionic metalorganic agent molecules, in general.

Reversible biofunctionalization of surfaces with a switchable mutant of avidin.

Label-free biosensors detect binding of prey molecules (″analytes″) to immobile bait molecules on the sensing surface. Numerous methods are available for immobilization of bait molecules. A convenient option is binding of biotinylated bait molecules to streptavidin-functionalized surfaces, or to biotinylated surfaces via biotin-avidin-biotin bridges. The goal of this study was to find a rapid method for reversible immobilization of biotinylated bait molecules on biotinylated sensor chips. The task was to establish a biotin-avidin-biotin bridge which was easily cleaved when desired, yet perfectly stable under a wide range of measurement conditions. The problem was solved with the avidin mutant M96H which contains extra histidine residues at the subunit-subunit interfaces. This mutant was bound to a mixed self-assembled monolayer (SAM) containing biotin residues on 20% of the oligo(ethylene glycol)-terminated SAM components. Various biotinylated bait molecules were bound on top of the immobilized avidin mutant. The biotin-avidin-biotin bridge was stable at pH ≥3, and it was insensitive to sodium dodecyl sulfate (SDS) at neutral pH. Only the combination of citric acid (2.5%, pH 2) and SDS (0.25%) caused instantaneous cleavage of the biotin-avidin-biotin bridge. As a consequence, the biotinylated bait molecules could be immobilized and removed as often as desired, the only limit being the time span for reproducible chip function when kept in buffer (2-3 weeks at 25 °C). As expected, the high isolectric pH (pI) of the avidin mutant caused nonspecific adsorption of proteins. This problem was solved by acetylation of avidin (to pI < 5), or by optimization of SAM formation and passivation with biotin-BSA and BSA.

Spectroscopic scanning tunneling microscopy studies of single surface-supported free-base corroles.

Corroles are versatile chemically active agents in solution. Expanding their applications toward surface-supported systems requires a fundamental knowledge of corrole–surface interactions. We employed the tip of a low-temperature scanning tunneling microscope as local probe to investigate at the single-molecule level the electronic and geometric properties of surface-supported free-base corrole molecules. To provide a suitable reference for other corrole-based systems on surfaces, we chose the archetypal 5,10,15-tris(pentafluorophenyl)corrole [H3(TpFPC)] as model system, weakly adsorbed on two surfaces with different interaction strengths. We demonstrate the nondissociative adsorption of H3(TpFPC) on pristine Au(111) and on an intermediate organic layer that provides sufficient electronic decoupling to investigate geometric and frontier orbital electronic properties of almost undisturbed H3(TpFPC) molecules at the submolecular level. We identify a deviating adsorption behavior of H3(TpFPC) compared to structurally similar porphyrins, characterized by a chiral pair of molecule–substrate configurations.

Cellular interfaces with hydrogen-bonded organic semiconductor hierarchical nanocrystals

Successful formation of electronic interfaces between living cells and semiconductors hinges on being able to obtain an extremely close and high surface-area contact, which preserves both cell viability and semiconductor performance. To accomplish this, we introduce organic semiconductor assemblies consisting of a hierarchical arrangement of nanocrystals. These are synthesised via a colloidal chemical route that transforms the nontoxic commercial pigment quinacridone into various biomimetic three-dimensional arrangements of nanocrystals. Through a tuning of parameters such as precursor concentration, ligands and additives, we obtain complex size and shape control at room temperature. We elaborate hedgehog-shaped crystals comprising nanoscale needles or daggers that form intimate interfaces with the cell membrane, minimising the cleft with single cells without apparent detriment to viability. Excitation of such interfaces with light leads to effective cellular photostimulation. We find reversible light-induced conductance changes in ion-selective or temperature-gated channels.Nanomaterials that form a bioelectronic interface with cells are fascinating tools for controlling cellular behavior. Here, the authors photostimulate single cells with spiky assemblies of semiconducting quinacridone nanocrystals, whose nanoscale needles maximize electronic contact with the cells.