Amino acid-stabilized luminescent gold clusters for sensing pterin and its analogues.

Pteridines are important low molecular weight biomarkers used in the diagnostics of inflammation, oxidative stress, phenylketonuria, cancer, In this experimental study, we present a simple and selective approach to determine pteridines (pterin, leucopterin and folic acid) and nucleobase guanine concentration using luminescent gold clusters stabilized by aromatic amino acids. We synthesized several new gold clusters (AA-Au NCs) stabilized by various aromatic amino acids - 3,4-dihydroxy-L-phenylalanine (DOPA), L-tryptophan (Trp), L-tyrosine (Tyr) and L-phenylalanine (Phe), emitting in the violet-green spectral range. Their luminescence appeared to be sensitive to the presence of pterin, leucopterin, folic acid and guanine depending on the stabilizing matrix.

Excited States in Single-Stranded and i-Motif DNA with Silver Ions.

We have studied the excited states and structural properties for the complexes of cytosine (dC) chains with silver ions (Ag) in a wide range of the Ag to DNA ratio () and pH conditions using circular dichroism, steady-state absorption, and fluorescence spectroscopy along with the ultrafast fluorescence upconversion technique. We also calculated vertical electronic transition energies and determined the nature of the corresponding excited states in some models of the cytosine-Ag complexes. We show that (dC) chains in the presence of silver ions form a duplex stabilized by C-Ag-C bonds.

Interactions of deprotonated phenylalanine with gold Clusters: Theoretical study with prospects for amino acid detection.

Nanomaterials are widely used nowadays in industry and medicine. The specific properties of gold nanoclusters (Au NCs) are chemical stability, low cytotoxicity, low photobleaching, high sensitivity to the molecular environment. This set of properties allows to use Au NCs as nanosensors in bioimaging and diagnostics.

Rapid and selective colorimetric determination of L-DOPA in human serum with silver nanoparticles.

L-DOPA, or l-3,4-dihydroxyphenylalanine is an aromatic amino acid, which plays a significant role in human metabolism as a precursor of important neurotransmitters. We develop a fast and simple colorimetric method for the detection of L-DOPA in biological fluids. The method is based on the reduction of silver ions with L-DOPA and the subsequent formation of L-DOPA stabilized silver nanoparticles (Ag NPs).

Quantitative determination of albumin and immunoglobulin in human serum using gold nanoclusters.

In this experimental study, we developed a simple and selective approach to determine the concentrations of human serum albumin (HSA) and total amount of immunoglobulins (Ig) in real human serum (HS) sample using luminescent gold nanoclusters (Au NCs). In doing so, Au NCs were grown directly on the HS proteins without any sample pretreatment. We synthesized Au NCs on HSA and Ig and studied their photophysical properties.

Silver cluster interactions with Pterin: Complex structure, binding energies and spectroscopy.

Metal nanoclusters (NCs) are widely present today in biosensing, bioimaging, and diagnostics due to their small size, great biocompatibility, and sensitivity to the biomolecular environment. Silver (Ag) NCs often possess intense fluorescence, photostability, and low photobleaching, which is in high demand during the detection of organic molecules. Pterins are small compounds, which are used in medicine as biomarkers of oxidative stress, cardiovascular diseases, neurotransmitter synthesis, inflammation and immune system activation.

Silver Cluster Interactions with Tyrosine: Towards Amino Acid Detection.

Tyrosine (Tyr) is involved in the synthesis of neurotransmitters, catecholamines, thyroid hormones, etc. Multiple pathologies are associated with impaired Tyr metabolism. Silver nanoclusters (Ag NCs) can be applied for colorimetric, fluorescent, and surface-enhanced Raman spectroscopy (SERS) detection of Tyr.

Comparative study of gold and silver interactions with amino acids and nucleobases.

Metal nanoclusters (NCs) have gained much attention in the last decade. In solution, metal nanoclusters can be stabilized by proteins, and, thus, exhibit many advantages in biocatalysis, biosensing, and bioimaging. In spite of much progress in the synthesis of polypeptide-stabilized gold (Au) clusters, their structure, as well as amino acid-cluster and amino acid-Au interactions, remain poorly understood.

Exciton Absorption and Luminescence in i-Motif DNA.

We have studied the excited-state dynamics for the i-motif form of cytosine chains (dC), using the ultrafast fluorescence up-conversion technique. We have also calculated vertical electronic transition energies and determined the nature of the corresponding excited states in a model tetramer i-motif structure. Quantum chemical calculations of the excitation spectrum of a tetramer i-motif structure predict a significant (0.

tRNA as a stabilizing matrix for fluorescent silver clusters: photophysical properties and IR study.

In this experimental study fluorescent silver clusters on a tRNA matrix were synthesized for the first time. Two types of fluorescent complexes emitting in the green (550 nm) and red (635 nm) regions of the visible spectrum were obtained. Using FTIR spectroscopy, we identified possible binding sites for the clusters, which appeared to be within the helical regions of tRNA.

Silver cluster-amino acid interactions: a quantum-chemical study.

Binding of silver ion (Ag) and two atomic neutral silver cluster (Ag) with a set of amino acids has been studied using Density Functional Theory (DFT) and ab initio MP2 method. We show that binding energy with Ag is higher for deprotonated anionic amino acids. Cysteine, aspartic acid, and tyrosine with deprotonated side chain exhibit the highest binding energy (G) values among all the amino acids: - 30.

DNA as UV light-harvesting antenna.

The ordered structure of UV chromophores in DNA resembles photosynthetic light-harvesting complexes in which quantum coherence effects play a major role in highly efficient directional energy transfer. The possible role of coherent excitons in energy transport in DNA remains debated. Meanwhile, energy transport properties are greatly important for understanding the mechanisms of photochemical reactions in cellular DNA and for DNA-based artificial nanostructures.

DNA with Ionic, Atomic, and Clustered Silver: An XPS Study.

The rapidly developing field of bionanotechnology requires detailed knowledge of the mechanisms of interaction between inorganic matter and biomolecules. Under conditions different from those in an aqueous solution, however, the chemistry of these systems is elusive and may differ dramatically from their interactions in vitro and in vivo. Here, we report for the first time a photoemission study of a metal silver-DNA interface, formed in vacuo, in comparison with DNA-Ag and fluorescent DNA-Ag complexes formed in solution.

Ag-DNA Emitter: Metal Nanorod or Supramolecular Complex?

Ligand-stabilized luminescent metal clusters, in particular, DNA-based Ag clusters, are now employed in a host of applications such as sensing and bioimaging. Despite their utility, the nature of their excited states as well as detailed structures of the luminescent metal-ligand complexes remain poorly understood. We apply a new joint experimental and theoretical approach based on QM/MM-MD simulations of the fluorescence excitation spectra for three Ag clusters synthesized on a 12-mer DNA.

Noncanonical Stacking Geometries of Nucleobases as a Preferred Target for Solar Radiation.

Direct DNA absorption of UVB photons in a spectral range of 290-320 nm of terrestrial solar radiation is responsible for formation of cyclobutane pyrimidine dimers causing skin cancer. Formation of UVB-induced lesions is not random, and conformational features of their hot spots remain poorly understood. We calculated the electronic excitation spectra of thymine, cytosine, and adenine stacked dimers with ab initio methods in a wide range of conformations derived from PDB database and molecular dynamics trajectory of thymine-containing oligomer.

Fluorescent silver nanoclusters in condensed DNA.

We study the formation and fluorescent properties of silver nanoclusters encapsulated in condensed DNA nanoparticles. Fluorescent globular DNA nanoparticles are formed using a dsDNA-cluster complex and polyallylamine as condensing agents. The fluorescence emission spectrum of single DNA nanoparticles is obtained using tip-enhanced fluorescence microscopy.