Insight into Molecular Interactions of Two Methyl Benzoate Derivatives with Bovine Serum Albumin.

The nature and mechanisms of interaction between two selected methyl benzoate derivatives (methyl o-methoxy p-methylaminobenzoate-I and methyl o-hydroxy p-methylaminobenzoate-II) and model transport protein bovine serum albumin (BSA) was studied using steady-state and time-resolved spectroscopic techniques. In order to understand the role of Trp residue of BSA in the I-BSA and II-BSA interaction, the effect of free Trp amino acid on the both emission modes (LE-locally excited (I and II) and ESIPT-excited state intramolecular proton transfer (II)) was investigated as well. Experimental results show that the investigated interactions (with both BSA and Trp) are mostly conditioned by the ground and excited state complex formation processes. Both molecules form stable complexes with BSA and Trp (with 1:1 stoichiometry) in the ground and excited states. The binding constants were in the order of 104 M-1. The absorption- and fluorescence-titration experiments along with the time-resolved fluorescence measurements show that the binding of the I and II causes fluorescence quenching of BSA through the static mechanism, revealing a 1:1 interaction. The magnitude and the sign of the thermodynamic parameters, ΔH, ΔS, and ΔG, determined from van't Hoff relationship, confirm the predominance of the hydrogen-bonding interactions for the binding phenomenon. To improve and complete knowledge of methyl benzoate derivative-protein interactions in relation to supramolecular solvation dynamics, the time-dependent fluorescence Stokes' shifts, represented by the normalized spectral response function c(t), was studied. Our studies reveal that the solvation dynamics that occurs in subpicosecond time scale in neat solvents of different polarities is slowed down significantly when the organic molecule is transferred to BSA cavity.

Application of the Heavy-Atom Effect for (Sub)microsecond Thermally Activated Delayed Fluorescence and an All-Organic Light-Emitting Device with Low-Efficiency Roll-off.

The feature of abundant and environmentally friendly heavy atoms (HAs) like bromine to accelerate spin-forbidden transitions in organic molecules has been known for years. In combination with the easiness of incorporation, bromine derivatives of organic emitters showing thermally activated delayed fluorescence (TADF) emerge as a cheap and efficient solution for the slow reverse intersystem crossing (rISC) problem in such emitters and strong efficiency roll-off of all-organic light-emitting diodes (OLEDs). Here, we present a comprehensive photophysical study of a tri-PXZ-TRZ emitter reported previously and its hexabromo derivative showing a remarkable enhancement of rISC of up to 9 times and a short lifetime of delayed fluorescence of 2 µs. Analysis of the key molecular vibrations and TADF mechanism indicates almost compete blockage of the spin-flip transition between the charge-transfer states of different multiplicity 3CT → 1CT. In such a case, rISC as well as its enhancement by the HA is realized via the 3LE → 1CT transition, where 3LE is the triplet state localized on the same brominated phenoxazine donor involved in the formation of the 1CT state. Interestingly, the spin-orbit coupling (SOC) with two other 3LE states is negligible because they are localized on different donors and not involved in 1CT. We consider this as an example of an additional "localization" criterion that completes the well-known El Sayed rule on the different nature of states for nonzero SOC. The applicative potential of such a hexabromo emitter is tested in a "hyperfluorescent" system containing a red fluorescent dopant (tetraphenyldibenzoperiflanthene, DBP) as an acceptor of Förster resonance energy transfer, affording a narrow-band red-emitting system, with most of the emission in the submicrosecond domain. In fact, the fabricated red OLED devices show remarkable improvement of efficiency roll-off from 2-4 times depending on the luminance, mostly because of the increase of the rISC constant rate and the decrease of the overall delayed fluorescence lifetime thanks to the HA effect.

Spectroscopic studies on the supramolecular interactions of methyl benzoate derivatives with p-sulfocalix[6]arene macrocycles.

This paper is a continuation of our previous research and aims to further investigate and elucidate the nature and mechanisms of noncovalent supramolecular interactions between four methyl benzoate derivatives (I-IV), which are capable of exhibiting Twisted Intramolecular Charge Transfer (TICT) and/or Excited State Intramolecular Proton Transfer (ESIPT)-type behavior, and chemical and biological nanocavities. Photophysical and photochemical properties of molecules I-IV in aqueous solution in the presence of well-recognized macrocyclic host p-sulfocalix[6]arenes (SCA[6]) have been studied using steady-state, time-resolved and 1H NMR spectroscopic techniques. The changes in the ground- and excited-state spectroscopic characteristics (absorption and fluorescence spectra, time-resolved fluorescence spectra, fluorescence decay times and 1H NMR spectra) undergo significant modifications upon encapsulation of the investigated methyl benzoate derivative in the macromolecular cavity. For the two compounds (I and II), the interactions with the macrocycles with a hydrophobic SCA[6] cavity lead to the formation of stable inclusion complexes with 1:1 stoichiometry, both in the ground and excited state, while the stoichiometry of the III-SCA[6] and IV-SCA[6] complexes in the ground and excited states is 1:2. The values of the equilibrium constants have been determined from the spectroscopic data using Benesi-Hildebrand and nonlinear regression procedures. The location of the organic molecule inside the SCA[6] has been investigated by 1H NMR experiments. The changes in macrocyclic compound-induced NMR chemical shifts clearly indicate that the chemical structure of inclusion complexes is very different for methyl benzoate derivative-SCA[6] and methyl benzoate derivative-CB[7] systems. Finally, we have shown, using time-dependent fluorescence Stokes shift, that very fast solvation dynamics of pure water is markedly different from that of the confined water molecule in SCA[6] system.

Spectroscopic evidence of fluorescence by 1,8-diazafluoren-9-one aggregates-A prospective new ultrasensitive method for fingerprint trace detection.

Friction ridge analysis would not have been one of the most recognized branches of forensics without molecular spectroscopy. The phenomenon of fluorescence is used on daily basis to develop latent fingerprints and to enhance those that are visible. The idea behind the research was to discover selected spectroscopic properties of 1,8-diazafluoren-9-one (DFO) in various environments. This fluorescent compound has been routinely used for decades to develop latent fingerprints due to its numerous advantages, but to this day, it has not been well-understood. Analysis of absorption, fluorescence, and excitation spectra of DFO in ethanol at high dye concentration allowed identification of aggregates in the excited state. A significant influence of the dye concentration on the fluorescence spectra and on the fluorescence excitation spectra was found. In particular, dye-host aggregation was found to be much stronger in a polar solvent. DFO aggregates are strongly fluorescent in ethanol, as can be seen from the steady-state emission spectra. The impact of excitation wavelength on the effect of fingerprint detection is presented. A new reaction medium has been proposed, ethanol, which is nontoxic in relation to the currently used one, methanol. The existence in this medium of DFO aggregates in the excited state, which significantly influences the identification of amino acids present in fingerprint traces, was observed, emitting in a wide spectral range (green light).

Vibrationally Assisted Direct Intersystem Crossing between the Same Charge-Transfer States for Thermally Activated Delayed Fluorescence: Analysis by Marcus-Hush Theory Including Reorganization Energy.

Thermally activated delayed fluorescence (TADF) has recently become an extensively investigated phenomenon due to its high potential for application in organic optoelectronics. Currently, there is still lack of a model describing correctly basic photophysical parameters of organic TADF emitters. This article presents such a photophysical model describing the rates of intersystem crossing (ISC), reverse ISC (rISC), and radiative deactivation in various media and emphasizing key importance of molecular vibrations on the example of a popular TADF dye 9,10-dihydro-9,9-dimethyl-10-(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-acridine (DMAC-TRZ). The presented experimental and theoretical investigations prove that ISC and rISC can occur efficiently between the singlet and triplet states of the same charge-transfer nature (1CT and 3CT, respectively). In emitters with the orthogonal donor and acceptor fragments, such spin-forbidden 1CT ↔ 3CT transitions are activated by molecular vibrations. Namely, the change of dihedral angle between the donor and the acceptor affords reasonable spin-orbit coupling, which together with a small energy gap and reorganization energy enable 1CT ↔ 3CT transition rates reaching 1 × 107 s-1. Evidence of direct 1CT ↔ 3CT spin-flip and negligible role of a second triplet state, widely believed as a key parameter in the design of (r)ISC materials, change significantly the current understanding of TADF mechanism. In authors' opinion, photophysics, and molecular design principles of TADF emitters should be revised considering the importance of vibrationally enhanced 1CT ↔ 3CT transitions.

The Luminescence of 1,8-Diazafluoren-9-One/Titanium Dioxide Composite Thin Films for Optical Application.

The investigation of innovative label-free α-amino acids detection methods represents a crucial step for the early diagnosis of several diseases. While 1,8-diazafluoren-9-one (DFO) is known in forensic application because of the fluorescent products by reacting with the amino acids present in the papillary exudate, its application for diagnostic purposes has not been fully investigated. The stabilization of DFO over a transparent substrate allows its complexation with biomolecules for the detection of α-amino acids. In this study, DFO was immobilized into a titanium dioxide (TiO2) matrix for the fluorescence detection of glycine, as a target α-amino acid (a potential marker of the urogenital tract cancers). The DFO/TiO2 composite was characterized by atomic force microscopy, spectroscopic ellipsometry, fluorescence spectroscopy and fluorescence microscopy. The performed fluorescent studies indicate spectacular formation of aggregates at higher concentration. The measurements performed using various fluorescence and microscopic techniques together with the suitable analysis show that the aggregates are able to emit short-lived fluorescence.