Advances and applications of dynamic surface-enhanced Raman spectroscopy (SERS) for single molecule studies.

Dynamic surface-enhanced Raman spectroscopy (SERS) is nowadays one of the most interesting applications of SERS, in particular for single molecule studies. In fact, it enables the study of real-time processes at the molecular level. This review summarizes the latest developments in dynamic SERS techniques and their applications, focusing on new instrumentation, data analysis methods, temporal resolution and sensitivity improvements, and novel substrates.

Versatility of the Templated Surface Assembly of Nanoparticles from Water-in-Oil Microemulsions in Equivalent Hybrid Nanostructured Films.

Water-in-oil microemulsions, as stable colloidal dispersions from quasi-ternary mixtures, have been used in diverse applications, including nanoreactors for confined chemical processes. Their use as soft templates not only includes nanomaterial synthesis but also the interfacial assembly of nanoparticles in hybrid nanostructures. Especially the hierarchical arrangement of different types of nanoparticles over a surface in filament networks constitutes an interesting bottom-up strategy for facile and tunable film coating.

Radiation and DNA Origami Nanotechnology: Probing Structural Integrity at the Nanoscale.

DNA nanotechnology has emerged as a groundbreaking field, using DNA as a scaffold to create nanostructures with customizable properties. These DNA nanostructures hold potential across various domains, from biomedicine to studying ionizing radiation-matter interactions at the nanoscale. This review explores how the various types of radiation, covering a spectrum from electrons and photons at sub-excitation energies to ion beams with high-linear energy transfer influence the structural integrity of DNA origami nanostructures.

Impact of Surface Enhanced Raman Spectroscopy in Catalysis.

Catalysis stands as an indispensable cornerstone of modern society, underpinning the production of over 80% of manufactured goods and driving over 90% of industrial chemical processes. As the demand for more efficient and sustainable processes grows, better catalysts are needed. Understanding the working principles of catalysts is key, and over the last 50 years, surface-enhanced Raman Spectroscopy (SERS) has become essential.

Plasmon-driven chemical transformation of a secondary amide probed by surface enhanced Raman scattering.

Plasmon-driven chemical conversion is gaining burgeoning interest in the field of heterogeneous catalysis. Herein, we study the reactivity of N-methyl-4-sulfanylbenzamide (NMSB) at nanocavities of gold and silver nanoparticle aggregates under plasmonic excitation to gain understanding of the respective reaction mechanism. NMSB is a secondary amide, which is a frequent binding motive found in peptides and a common coupling product of organic molecules and biomolecules.

Antibacterial Nanoplatelets via Crystallization-Driven Self-Assembly of Poly(l-lactide)-Based Block Copolymers.

Membrane-active antimicrobial materials are promising substances to fight antimicrobial resistance. Herein, crystallization-driven self-assembly (CDSA) is employed for the preparation of nanoparticles with different morphologies, and their bioactivity is explored. Block copolymers (BCPs) featuring a crystallizable and antimicrobial block were synthesized using a combination of ring-opening and photoiniferter RAFT polymerizations.

Watching a Single Enzyme at Work Using Single-Molecule Surface-Enhanced Raman Scattering and DNA Origami-Based Plasmonic Antennas.

The detection of a single-enzyme catalytic reaction by surfaced-enhanced Raman scattering (SERS) is presented by utilizing DNA origami-based plasmonic antennas. A single horseradish peroxidase (HRP) was accommodated on a DNA origami nanofork plasmonic antenna (DONA) containing gold nanoparticles, enabling the tracing of single-molecule SERS signals during the peroxide reduction reaction. This allows monitoring of the structure of a single enzymatic catalytic center and products under suitable liquid conditions.

Condensed Matter Systems Exposed to Radiation: Multiscale Theory, Simulations, and Experiment.

This roadmap reviews the new, highly interdisciplinary research field studying the behavior of condensed matter systems exposed to radiation. The Review highlights several recent advances in the field and provides a roadmap for the development of the field over the next decade. Condensed matter systems exposed to radiation can be inorganic, organic, or biological, finite or infinite, composed of different molecular species or materials, exist in different phases, and operate under different thermodynamic conditions.

From Bulk to Single Molecules: Surface-Enhanced Raman Scattering of Cytochrome C Using Plasmonic DNA Origami Nanoantennas.

Cytochrome C, an evolutionarily conserved protein, plays pivotal roles in cellular respiration and apoptosis. Understanding its molecular intricacies is essential for both academic inquiry and potential biomedical applications. This study introduces an advanced single-molecule surface-enhanced Raman scattering (SM-SERS) system based on DNA origami nanoantennas (DONAs), optimized to provide unparalleled insights into protein structure and interactions.

Unraveling the Complexity of DNA Radiation Damage Using DNA Nanotechnology.

Radiation cancer therapies use different ionizing radiation qualities that damage DNA molecules in tumor cells by a yet not completely understood plethora of mechanisms and processes. While the direct action of the radiation is significant, the byproducts of the water radiolysis, mainly secondary low-energy electrons (LEEs, <20 eV) and reactive oxygen species (ROS), can also efficiently cause DNA damage, in terms of DNA strand breakage or DNA interstrand cross-linking. As a result, these types of DNA damage evolve into mutations hindering DNA replication, leading to cancer cell death.

Nanoscale Hotspot-Induced Emitters in DNA Origami-Assisted Nanoantennas.

We report the observation of hotspot-induced emitters and photoluminescence enhancement of up to 42-fold from DNA origami-assisted plasmonic dimer nanoantennas upon excess polarized laser illumination. The presence of DNA and laser polarization alignment along the dimer axis are critical for the generation of bright emitters responsible for the observed PL increase. The emission spectrum reveals characteristic Raman peaks of amorphous carbon, suggesting the formation of carbon-based emitters in the nanoantenna due to the plasmonic hotspots at the longitudinal antenna resonance.

The Effect of Nanoparticle Composition on the Surface-Enhanced Raman Scattering Performance of Plasmonic DNA Origami Nanoantennas.

A versatile generation of plasmonic nanoparticle dimers for surface-enhanced Raman scattering (SERS) is presented by combining a DNA origami nanofork and spherical and nonspherical Au or Ag nanoparticles. Combining different nanoparticle species with a DNA origami nanofork to form DNA origami nanoantennas (DONAs), the plasmonic nanoparticle dimers can be optimized for a specific excitation wavelength in SERS. The preparation of such nanoparticle dimers is robust enough to enable the characterization of SERS intensities and SERS enhancement factors of dye-modified DONAs on a single dimer level by measuring in total several thousands of dimers from five different dimer designs, each functionalized with three different Raman reporter molecules and measured at four different excitation wavelengths.

Lab-on-a-DNA origami: nanoengineered single-molecule platforms.

DNA origami nanostructures are self-assembled into almost arbitrary two- and three-dimensional shapes from a long, single-stranded viral scaffold strand and a set of short artificial oligonucleotides. Each DNA strand can be functionalized individually using well-established DNA chemistry, representing addressable sites that allow for the nanometre precise placement of various chemical entities such as proteins, molecular chromophores, nanoparticles, or simply DNA motifs. By means of microscopic and spectroscopic techniques, these entities can be visualized or detected, and either their mutual interaction or their interaction with external stimuli such as radiation can be studied.

Efficient Purification of Cowpea Chlorotic Mottle Virus by a Novel Peptide Aptamer.

The cowpea chlorotic mottle virus (CCMV) is a plant virus explored as a nanotechnological platform. The robust self-assembly mechanism of its capsid protein allows for drug encapsulation and targeted delivery. Additionally, the capsid nanoparticle can be used as a programmable platform to display different molecular moieties.

Photothermomechanical Nanopump: A Flow-Through Plasmonic Sensor at the Fiber Tip.

Optical fibers equipped with plasmonic flow sensors at their tips are fabricated and investigated as photothermomechanical nanopumps for the active transport of target analytes to the sensor surface. The nanopumps are prepared using a bottom-up strategy: i.e.

Molecular states and spin crossover of hemin studied by DNA origami enabled single-molecule surface-enhanced Raman scattering.

The study of biologically relevant molecules and their interaction with external stimuli on a single molecular scale is of high importance due to the availability of distributed rather than averaged information. Surface enhanced Raman scattering (SERS) provides direct chemical information, but is rather challenging on the single molecule (SM) level, where it is often assumed to require a direct contact of analyte molecules with the metal surface. Here, we detect and investigate the molecular states of single hemin by SM-SERS.

Influence of Different Salts on the G-Quadruplex Structure Formed from the Reversed Human Telomeric DNA Sequence.

G-rich telomeric DNA plays a major role in the stabilization of chromosomes and can fold into a plethora of different G-quadruplex structures in the presence of mono- and divalent cations. The reversed human telomeric DNA sequence (5'-(GGG ATT); RevHumTel) was previously shown to have interesting properties that can be exploited for chemical sensing and as a chemical switch in DNA nanotechnology. Here, we analyze the specific G-quadruplex structures formed by RevHumTel in the presence of K, Na, Mg and Ca cations using circular dichroism spectroscopy (CDS) and Förster resonance energy transfer (FRET) based on fluorescence lifetimes.

About the mechanism of ultrasonically induced protein capsule formation.

In this paper, we propose a consistent mechanism of protein microcapsule formation upon ultrasound treatment. Aqueous suspensions of bovine serum albumin (BSA) microcapsules filled with toluene are prepared by use of high-intensity ultrasound following a reported method. Stabilization of the oil-in-water emulsion by the adsorption of the protein molecules at the interface of the emulsion droplets is accompanied by the creation of the cross-linked capsule shell due to formation of intermolecular disulfide bonds caused by highly reactive species like superoxide radicals generated sonochemically.

Microscopic Understanding of Reaction Rates Observed in Plasmon Chemistry of Nanoparticle-Ligand Systems.

Surface-enhanced Raman scattering (SERS) is an effective and widely used technique to study chemical reactions induced or catalyzed by plasmonic substrates, since the experimental setup allows us to trigger and track the reaction simultaneously and identify the products. However, on substrates with plasmonic hotspots, the total signal mainly originates from these nanoscopic volumes with high reactivity and the information about the overall consumption remains obscure in SERS measurements. This has important implications; for example, the apparent reaction order in SERS measurements does not correlate with the real reaction order, whereas the apparent reaction rates are proportional to the real reaction rates as demonstrated by finite-difference time-domain (FDTD) simulations.

Synthesis of nanostructured protein-mineral-microcapsules by sonication.

We propose a simple and eco-friendly method for the formation of composite protein-mineral-microcapsules induced by ultrasound treatment. Protein- and nanoparticle-stabilized oil-in-water (O/W) emulsions loaded with different oils are prepared using high-intensity ultrasound. The formation of thin composite mineral proteinaceous shells is realized with various types of nanoparticles, which are pre-modified with Bovine Serum Albumin (BSA) and subsequently characterized by EDX, TGA, zeta potential measurements and Raman spectroscopy.