DNA-stabilized Ag nanoclusters, AgNCs, act as fluorescent labels for probing enzyme activities and their substrates. The effective quenching of AgNCs by H(2)O(2) enables the probing of H(2)O(2)-generating oxidases. This is demonstrated by following the glucose oxidase-stimulated oxidation of glucose through the enzyme-catalyzed formation of H(2)O(2). Similarly, the effective quenching of the AgNCs by quinones enabled the detection of tyrosinase through the biocatalyzed oxidation of tyrosine, dopamine, or tyramine to the respective quinone products. The sensitive probing of biocatalytic processes by the AgNCs was further implemented to follow bienzyme catalytic cascades involving alkaline phosphatase/tyrosinase and acetylcholine esterase/choline oxidase. The characterization of the alkaline phosphatase/tyrosinase cascade enabled the ultrasensitive detection of alkaline phosphatase (5 × 10(-5) units/mL) and the detection of o-phospho-l-tyrosine that is an important intracellular promoter and control growth factor.

DNA nanostructures acting as DNA machines are described. Specifically, DNA "walkers" assembled on nucleic acid scaffolds and triggered by fuel/antifuel strands are activated in solution or on surfaces, for example, electrodes or semiconductor CdSe/ZnS quantum dots (QDs). The DNA machines led to the switchable formation or dissociation of the hemin/G-quadruplex DNAzyme on the DNA scaffolds. This enabled the chemiluminescence, chemiluminescence resonance energy transfer (CRET), electrochemical, or photoelectrochemical transduction of the switchable states of the different DNA machines.

CONSPECTUS: Most robust functional organic materials are currently based on polymers. These materials exhibit high stability, but once formed they are difficult to modify, adapt to their environment, and recycle. Materials based on small molecules that are held together by noncovalent interactions can offer an alternative to conventional polymer materials for applications that require adaptive and stimuli-responsive features. However, it is challenging to engineer macroscopic noncovalent materials that are sufficiently robust for practical applications. This Account summarizes progress made by our group towards the development of noncovalent "aqua materials" based on well-defined organic molecules. These materials are uniquely assembled in aqueous media, where they harness the strength of hydrophobic and π−π interactions between large aromatic groups to achieve robustness. Despite their high stability, these supramolecular systems can dynamically respond to external stimuli. We discuss design principles, fundamental properties, and applications of two classes of aqua materials: (1) supramolecular gels and (2) nanocrystalline arrays. The materials were characterized by a combination of steady-state and time-resolved spectroscopic techniques, electrical measurements, molecular modeling, and high-resolution microscopic imaging, in particular cryogenic transmission electron microscopy (cryo-TEM) and cryogenic scanning electron microscopy (cryo-SEM). All investigated aqua materials are based on one key building block, perylene diimide (PDI). PDI exhibits remarkably stable intermolecular bonds, together with useful chemical and optoelectronic properties. PDI-based amphiphiles carrying poly(ethylene glycol) (PEG) were designed to form linear supramolecular polymers in aqueous media. These one-dimensional arrays of noncovalently linked molecules can entangle and form three-dimensional supramolecular networks, leading to soft gellike materials. Tuning the strength of interactions between fibers enables dynamic adjustment of viscoelastic properties and functional characteristics. Besides supramolecular gels, we show that simple PDI-based molecules can self-assemble in aqueous medium to form robust organic nanocrystals (ONCs). The mechanical and optoelectronic properties of ONCs are distinctly different from gel-phase materials. ONCs are excellent building blocks for macroscopic free-standing materials that can be used in dry state, unlike hydrogels. Being constructed from small molecules, ONC materials are easy to fabricate and recycle. High thermal robustness, good mechanical properties, and modular design render ONC materials versatile and suitable for a variety of applications. In the future, noncovalent aqua materials can become a sustainable alternative to conventional polymer materials. Examples from our research include stimuli-responsive and recyclable filtration membranes for preparative nanoparticle separation, water purification and catalysis, light-harvesting hydrogels for solar energy conversion, and nanocryst...

Telomeres are guanosine-rich nucleic-acid chains that fold, in the presence of K(+) ions and hemin, into the telomeric hemin/G-quadruplex structure, exhibiting horseradish peroxidase mimicking functions. The telomeric hemin/G-quadruplex structures catalyze the oxidation of thiols (e.g., l-cysteine) into disulfides (e.g., cystine). As l-cysteine stimulates the aggregation of Au nanoparticles (NPs), accompanied by absorbance changes from red (individual Au NPs) to blue (aggregated Au NPs), the process is implemented to quantitatively analyze the activity (content) of telomerase, a versatile biomarker for cancer cells. Telomerase extracted from 293T cancer cells catalyzes, in the presence of a dNTPs mixture and an appropriate primer probe, the telomerization process, leading to the generation of catalytic telomeric hemin/G-quadruplex chains that control the l-cysteine-mediated aggregation of Au NPs. The extent of aggregation is thus controlled by the concentration of telomerase. The method enabled the detection of telomerase with a detection limit of 27 cells/μL. The spectral changes accompanying the aggregation of Au NPs are further supported by transmission electron microscopy imaging.

Upon photoexcitation, self-assembled PDI nanocrystals (S1S0) in the form of rods of 70 nm width and 1 μm length are subject to a symmetry breaking charge separation (SBCS) as the first step in the singlet fission (SF) sequence. Hereby, the correlated pair of triplet excited states 1(T1T1) is formed with a quantum yield of 122%. Decoherence and triplet diffusion within the nanocrystals affords a long-lived, uncorrelated pair of triplet excited states (T1 + T1) with a quantum yield of 24%.