Near-Infrared-II Cyanine/Polymethine Dyes, Current State and Perspective

The development of near-infrared-II (NIR-II) fluorescence imaging has implemented real-time detection of biological cells, tissues and body, monitoring the disease processes and even enabling the direct conduct of surgical procedures. NIR-II fluorescence imaging provides better imaging contrast and penetration depth, benefiting from the reducing photon scattering, light absorption and autofluorescence. The majority of current NIR-II fluorophores suffer from uncontrollable emission wavelength and low quantum yields issues, impeding the clinical translation of NIR-II bioimaging. By lengthening the polymethine chain, tailoring heterocyclic modification and conjugating electron-donating groups, cyanine dyes have been proved to be ideal NIR-II fluorophores with both tunable emission and brightness. However, a simpler and faster method for synthesizing NIR-II dyes with longer wavelengths and better stability still needs to be explored. This minireview will outline the recent progress of cyanine dyes with NIR-II emission, particularly emphasizing their pharmacokinetic enhancement and potential clinical translation.

Effect of Fluorescent Labels on DNA Affinity for Gold Nanoparticles

Fluorophore (FD) labeling is widely used for detection and quantification of various compounds bound to nanocarriers. The systems, composed of gold nanoparticles (GNPs) and oligonucleotides (ONs) labeled with FDs, have wide applications. Our work was aimed at a systemic study of how FD structure (in composition of ON-FDs) influenced the efficiency of their non-covalent associates’ formation with GNPs (ON-FD/GNPs). We examined ONs of different length and nucleotide composition, and corresponding ON-FDs (FDs from a series of xanthene, polymethine dyes; dyes based on polycyclic aromatic hydrocarbons). Methods: fluorometry, dynamic light scattering, high performance liquid chromatography, gel electrophoresis, molecular modeling and methods of thermodynamic and statistical analysis. We observed significant, differing several times, changes in surface density and Langmuir constant values of ON-FDs vs. ONs, evidence for the critical significance of FD nature for binding of ON-FDs with GNPs. Surface density of ON-FD/GNPs; hydrophobicity and total charge of ON or ON-FD; and charge and surface area of FDs were revealed as key factors determining affinity (Langmuir constant) of ON or ON-FDs for GNPs. These factors compose a specific set, which makes possible the highly reliable prediction of efficiency of ONs and ON-FDs binding with GNPs. The principal possibility of creating an algorithm for predictive calculation of efficiency of ONs and GNPs interaction was demonstrated. We proposed a hypothetical model that described the mechanism of contact interaction between negatively charged nano-objects, such as citrate-stabilized GNPs, and ONs or ON-FDs.

Oxonol dyes

Oxonol dyes are classified as anionic polymethine dyes, which cover a wide variety of structural types. The name of the class originates from the oxygen atoms which terminate each end of the polymethine chains that form the backbone of their structure. In technically useful dyes, these oxygen atoms tend to be substituents of heterocycles. The main technical application of water soluble oxonol dyes was in silver halide photography as filter dyes and antihalation dyes. Lipophilic oxonol dyes are used in bio-analysis and medical diagnostics to stain cells, bacteria or liposomes for example. Their main bioanalytical usage is in the determination of membrane potentials in eukaryotic cells and prokaryotic bacteria.

Merocyanine dyes

Merocyanine dyes belong to the class of neutral polymethine dyes, where one terminal component is typically found in cyanine dyes and the second obtained from an active methylene compound. The different electron acceptor/donator abilities of the two terminal components have a marked impact on the electronic structure of a merocyanine dye and its equilibrium structure and electronic spectra. Their first technical application was spectral sensitization in silver halide photography. Today they have numerous of applications in textile dyeing and as membrane potential sensitive fluorescent dyes.

Nature of Lowest Electron Transitions in Anionic Polymethine Dyes With Keto-Containing Terminal Groups

The complex quantum-chemical and spectral study of the anionic polymethine dyes with the simplest symmetrical terminal groups and with different length polymethine chain is performed. It was shown that these dyes produce the specific molecular orbitals positioned nearly the energy gap and located only within the terminal groups. By investigation of the absorption spectra, it was established that the typical highly intensive longwawelength spectral band is observed which are bathochromically shifted upon lengthening of the open conjugated chain; this polymethine band is connected with the electron transition between the frontier levels of the opposite symmetry. In the contrast, the local MOs take part in so-called quasi-local electron transitions involved also one the frontier orbital. The local transitions have small dipole moments and hence they do practically not appear in the absorption spectra, however, the local transitions cause the appearance of the non-deep minima in the spectra of the fluorescence excitation anisotropy.

High-efficiency polymethine dyes for passive Q-switch and mode locking of neodymium lasers

New polymethine dyes (PD) based on benzene [c, d] indole were synthesized. Their spectral and nonlinear optical characteristics in liquid and polymer media have been studied. It was found that the relaxation times τ of the excited state of the new PDs are approximately the same as those of the dye 3274y, which is widely used as a passive Q-switch of neodymium lasers with a generation lengthwave of 1.06 μm. The low sensitivity of τ to changes in the chemical structure of such PDs indicates that the main contribution to the deactivation of the excited state is made by the benzene [c, d] indole heterocycle. High values ​​of the cross section in the range of 1.05-1.08 μm at low relaxation times allow the studied PD to be easily bleached in lasers at low intensities (about 10 MW/cm2). It is established that the photostability of the new PD significantly exceeds that for the dye 3274y. This is because they contain a saturated six-membered ring in the polymethine chain, which is much less reactive than the corresponding five-membered ring of dye 3274u with respect to the photoinitiator of free radicals of UV irradiation. It is shown that the efficiency of Q-switching and mode locking of new passive laser shutters is higher than their analogues based on the dye 3274y.