How Peptides Dissociate in Plasmonic Hot Spots.

Plasmon-induced hot carriers enable dissociation of strong chemical bonds by visible light. This unusual chemistry has been demonstrated for several diatomic and small organic molecules. Here, the scope of plasmon-driven photochemistry is extended to biomolecules and the reactivity of proteins and peptides in plasmonic hot spots is described.

Plasmon-Driven Photocatalysis Leads to Products Known from E-beam and X-ray-Induced Surface Chemistry.

Plasmonic metal nanostructures can concentrate incident optical fields in nanometer-sized volumes, called hot spots. This leads to enhanced optical responses of molecules in such a hot spot but also to chemical transformations, driven by plasmon-induced hot carriers. Here, we employ tip-enhanced Raman spectroscopy (TERS) to study the mechanism of these reactions in situ at the level of a single hot spot.

Preparation of Well-Defined DNA Samples for Reproducible Nanospectroscopic Measurements.

Due to its well-defined topology and chemical structure, DNA could become a biological standard sample in the field of nanospectroscopy. Tip-enhanced Raman spectroscopy (TERS) provides new insights into individual DNA molecules immobilized on flat mica crystals. The high sensitivity of TERS is used to assess the chemical changes that appear in DNA upon different surface immobilization protocols.

Synthesis of a Two-Dimensional Covalent Organic Monolayer through Dynamic Imine Chemistry at the Air/Water Interface.

A two-dimensional covalent organic monolayer was synthesized from simple aromatic triamine and dialdehyde building blocks by dynamic imine chemistry at the air/water interface (Langmuir-Blodgett method). The obtained monolayer was characterized by optical microscopy, scanning electron microscopy, and atomic force microscopy, which unambiguously confirmed the formation of a large (millimeter range), unimolecularly thin aromatic polyimine sheet. The imine-linked chemical structure of the obtained monolayer was characterized by tip-enhanced Raman spectroscopy, and the peak assignment was supported by spectra simulated by density functional theory.

Minimally invasive characterization of covalent monolayer sheets using tip-enhanced Raman spectroscopy.

Synthetic covalent monolayer sheets and their subclass, two-dimensional polymers are of particular interest in materials science because of their special dimensionality which renders them very different from any bulk matter. However, structural analysis of such entities is rather challenging, and there is a clear need for additional analytical methods. The present study shows how tip-enhanced Raman spectroscopy (TERS) can be performed on monomer monolayers and the covalent sheets prepared from them by [4 + 4]-cycloaddition to explore rather complex structural and mechanistic issues.

Stiffness changes of tumor HEp2 cells correlates with the inhibition and release of TRAIL-induced apoptosis pathways.

Tumor necrosis factor (TNF)-related apoptosis inducing ligand (TRAIL) is a promising apoptotic agent that can selectively act on tumor cells. However, some cancer cells are resistant to TRAIL mediated apoptosis. In specific type of cells, sensitization by chemotherapeutic drugs may overcome the resistance to TRAIL induced apoptosis.