29 research outputs found
Stability of dibromo-dipyrromethene complexes coordinated with B, Zn, and Cd in solutions of various acidities
The spectral luminescent properties of dipyrromethenates halogenated with bromine on both ends of the long axis and coordinated using boron fluoride, zinc, or cadmium in neutral ethanol and acidified with hydrochloric acid solutions were studied. The constants of the acidβbase equilibrium of the complexes in the proton-donor solvents in the ground and excited states was determined. The mechanisms of complex protonation were discussed, depending on the structure of the compounds. The electronic structures of the neutral and protonated compounds were modeled and analyzed based on the quantum-chemical method. The structures and spectral-luminescence properties were calculated using the SMD model of ethanol solvent using the TD-DFT theory with the B3LYP functional and the composite def2-SVP/def2-TZVP/def2-TZVPP_ECP basis sets, depending on the atomic number of the elements
Structure and formation of luminescent centers in light-up Ag cluster-based DNA probes
Fluorescent beacons based on silver (Ag) clusters for DNA/RNA detection represent a new type of turn-on probe that fluoresces upon hybridization to target nucleobase sequences. Physicalβchemical mechanisms of their fluorescence activation still remain poorly understood. We studied in detail the fluorescence activation of dark Ag clusters induced by interactions of AgβDNA complexes with different DNA sequences. In all cases, the final result depends neither on the location of the precursors (dark clusters) nor on their spectral properties. The reaction of fluorescence activation is a process similar to the growth of fluorescent silver clusters on dsDNA matrices. In both cases, reactants are dark clusters and two adjacent DNA strands. The latter form a double-stranded template for cluster nucleation. We found the optimized structure of a green fluorescent Ag4+2 cluster assembled on a C3/C3 DNA dimer in two different ssDNA pairs using QM modeling. The calculated absorption spectra match nicely the experimental ones, which proves the optimized structures. We conclude that apparent fluorescence activation in the studied systems results from reassembling Ag clusters on the new dsDNA template formed upon hybridization with the target. The suggested mechanism of βfluorescence activationβ offers a way to design new light-up DNA probes. Two DNA strands making up the dsDNA template providing a high yield of bright Ag clusters can be used as the halves with the βstickβ tails hybridizing with the base sequence of the target DNA. In this way, we have designed a light-up Ag cluster probe for Ξ²-actin mRNA
Luminescence Solvato- and Vapochromism of Alkynyl-Phosphine Copper Clusters
The reaction of [Cu(NCMe)4][PF6] with aromatic acetylenes HC2R and triphosphine 1,1,1-tris(diphenylphosphino)methane in the presence of NEt3 results in the formation of hexanuclear Cu(I) clusters with the general formula [Cu6(C2R)4{(PPh2)3CH}2][PF6]2 (R = 4-X-C6H4 (1-5) and C5H4N (6); X = NMe2 (1), OMe (2), H (3), Ph (4), CF3 (5)). The structural motif of the complexes studied consists of a Cu6 metal core supported by two phosphine ligands and stabilized by Ο- and Ο-coordination of the alkynyl fragments (together with coordination of pyridine nitrogen atoms in cluster 6). The solid state structures of complexes 2-6 were determined by single crystal XRD analysis. The structures of the complexes in solution were elucidated by (1)H, (31)P, (1)H-(1)H COSY NMR spectroscopy, and ESI mass spectrometry. Clusters 1-6 exhibit moderately strong phosphorescence in the solid state with quantum yields up to 17%. Complexes 1-5 were found to form solvates (acetone, acetonitrile) in the solid state. The coordination of loosely bound solvent molecules strongly affects emission characteristics and leads to solvato- and vapochromic behavior of the clusters. Thus, solvent-free and acetonitrile solvated forms of 3 demonstrate contrasting emission in orange (615 nm) and blue (475 nm) regions, respectively. The computational studies show that alkynyl-centered IL transitions mixed with those of MLCT between the Cu6 metal core and the ligand environment play a dominant role in the formation of excited states and can be considerably modulated by weakly coordinating solvent molecules leading to luminescence vapochromism.This research has been supported by St. Petersburg State University Research Grant 0.37.169.2014, and Russian Foundation for Basic Research Grants 13-03-00970, 14-03-32077, and 13-03-12411. Academy of Finland (Grant 268993/2013, I.O.K), University of Eastern Finland (strategic fundingβRussianβFinnish collaborative project), is also gratefully acknowledged. The work was carried out using equipment of the Analytical Center of Nano- and Biotechnologies of SPbSPU with financial support of the Ministry of Education and Science of Russian Federation; Centers for Magnetic Resonance, X-ray Diffraction Studies, Chemical Analysis and Materials Research, Optical and Laser Materials Research; and Computer Center of St. Petersburg State University
Statistical Method to Describe Molecular Spectra
The method to reproduce optical spectra by statistical treatment of quantum-mechanical calculations of energy states and photophysical properties in molecular conformers obtained during molecular-dynamical simulation was developed. Polycyclic organic molecules in solvents under thermo-dynamical conditions were considered. This technique was employed to build the first absorption band of estradiol, benzene, and anthracene. Increasing of the spectral intensity in benzene under temperature growth was demonstrated for the lowest excited state. Anthracene emission spectrum was built as well.ΠΡΠ΅Π΄Π»ΠΎΠΆΠ΅Π½ ΠΌΠ΅ΡΠΎΠ΄ Π΄Π»Ρ Π²ΠΎΡΠΏΡΠΎΠΈΠ·Π²Π΅Π΄Π΅Π½ΠΈΡ ΠΎΠΏΡΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΠΏΠ΅ΠΊΡΡΠΎΠ² ΡΡΠ°ΡΠΈΡΡΠΈΡΠ΅ΡΠΊΠΎΠΉ ΠΎΠ±ΡΠ°Π±ΠΎΡΠΊΠΎΠΉ ΠΊΠ²Π°Π½ΡΠΎΠ²ΠΎ-ΠΌΠ΅Ρ
Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΠ°ΡΡΠ΅ΡΠΎΠ² ΡΠ½Π΅ΡΠ³Π΅ΡΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΠΎΡΡΠΎΡΠ½ΠΈΠΉ ΠΈ ΡΠΎΡΠΎΡΠΈΠ·ΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΠ²ΠΎΠΉΡΡΠ² Π² ΠΌΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½ΡΡ
ΠΊΠΎΠ½ΡΠΎΡΠΌΠ΅ΡΠ°Ρ
, ΠΏΠΎΠ»ΡΡΠ΅Π½Π½ΡΡ
Π² ΡΠ΅ΡΠ΅Π½ΠΈΠ΅ ΠΌΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½ΠΎ-Π΄ΠΈΠ½Π°ΠΌΠΈΡΠ΅ΡΠΊΠΎΠΉ ΡΠΈΠΌΡΠ»ΡΡΠΈΠΈ. ΠΠ±ΡΡΠΆΠ΄Π΅Π½Ρ Π½Π΅ΠΊΠΎΡΠΎΡΡΠ΅ ΠΏΠΎΠ»ΠΈΡΠΈΠΊΠ»ΠΈΡΠ΅ΡΠΊΠΈΠ΅ ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΠ΅ ΠΌΠΎΠ»Π΅ΠΊΡΠ»Ρ Π² ΡΠ°ΡΡΠ²ΠΎΡΠ°Ρ
ΠΏΡΠΈ ΡΠ°Π·Π»ΠΈΡΠ½ΡΡ
ΡΠ΅ΡΠΌΠΎΠ΄ΠΈΠ½Π°ΠΌΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΠΎΡΡΠΎΡΠ½ΠΈΡΡ
. ΠΠ°Π½Π½ΡΠΉ ΠΌΠ΅ΡΠΎΠ΄ Π±ΡΠ» ΠΏΡΠΈΠΌΠ΅Π½Π΅Π½ Π΄Π»Ρ ΠΏΠΎΡΡΡΠΎΠ΅Π½ΠΈΡ ΠΏΠ΅ΡΠ²ΡΡ
ΠΏΠΎΠ»ΠΎΡ ΠΏΠΎΠ³Π»ΠΎΡΠ΅Π½ΠΈΡ ΡΡΡΡΠ°Π΄ΠΈΠΎΠ»Π°, Π±Π΅Π½Π·ΠΎΠ»Π° ΠΈ Π°Π½ΡΡΠ°ΡΠ΅Π½Π°. ΠΡΠΎΠ΄Π΅ΠΌΠΎΠ½ΡΡΡΠΈΡΠΎΠ²Π°Π½ΠΎ ΡΠ²Π΅Π»ΠΈΡΠ΅Π½ΠΈΠ΅ ΡΠΏΠ΅ΠΊΡΡΠ°Π»ΡΠ½ΠΎΠΉ ΠΈΠ½ΡΠ΅Π½ΡΠΈΠ²Π½ΠΎΡΡΠΈ Π±Π΅Π½Π·ΠΎΠ»Π° Ρ ΡΠΎΡΡΠΎΠΌ ΡΠ΅ΠΌΠΏΠ΅ΡΠ°ΡΡΡΡ Π΄Π»Ρ Π½ΠΈΠ·ΡΠ΅Π³ΠΎ Π²ΠΎΠ·Π±ΡΠΆΠ΄Π΅Π½Π½ΠΎΠ³ΠΎ ΡΠΎΡΡΠΎΡΠ½ΠΈΡ. Π’Π°ΠΊΠΆΠ΅ ΠΏΠΎΡΡΡΠΎΠ΅Π½ ΡΠΏΠ΅ΠΊΡΡ ΠΈΠ·Π»ΡΡΠ΅Π½ΠΈΡ Π°Π½ΡΡΠ°ΡΠ΅Π½Π°
The Influence of Thermodynamical Conditions on the Photophysical Properties of Cyanoantracene
Semi-empirical Quantum-Chemical calculations of the photophysical molecular properties of cyanoanthracene and surrounding argon cell under different thermodynamical conditions were performed using the MD DL_POLY code. Photophysical scheme of the lowest energy levels and transition probabilities was plotted for the individual molecule. Vibrational profiles of the long-wave absorption electronic band and the first excited Frank-Condon singlet state with fluorescent live-times of the oscillating molecule were obtained. Based on the theoretical results, experimental spectroscopic data have been interpreted.ΠΡΠΎΠ²Π΅Π΄Π΅Π½Ρ ΠΏΠΎΠ»ΡΡΠΌΠΏΠΈΡΠΈΡΠ΅ΡΠΊΠΈΠ΅ ΠΊΠ²Π°Π½ΡΠΎΠ²ΠΎ-Ρ
ΠΈΠΌΠΈΡΠ΅ΡΠΊΠΈΠ΅ ΡΠ°ΡΡΠ΅ΡΡ ΡΠΎΡΠΎΡΠΈΠ·ΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΠ²ΠΎΠΉΡΡΠ² ΡΠΈΠ°Π½ΠΎΠ°Π½ΡΡΠ°ΡΠ΅Π½Π° Π² ΡΡΠ΅ΠΉΠΊΠΈ Ρ Π°ΡΠ³ΠΎΠ½ΠΎΠ²ΡΠΌ ΡΠ°ΡΡΠ²ΠΎΡΠΈΡΠ΅Π»Π΅ΠΌ ΠΏΡΠΈ ΡΠ°Π·Π»ΠΈΡΠ½ΡΡ
ΡΠ΅ΡΠΌΠΎΠ΄ΠΈΠ½Π°ΠΌΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΡΠ»ΠΎΠ²ΠΈΡΡ
. ΠΡΠΏΠΎΠ»ΡΠ·ΠΎΠ²Π°Π½ MD DL_POLY ΠΏΠ°ΠΊΠ΅Ρ. ΠΠΎΡΡΡΠΎΠ΅Π½Π° ΡΠΎΡΠΎΡΠΈΠ·ΠΈΡΠ΅ΡΠΊΠ°Ρ ΡΡ
Π΅ΠΌΠ° Π½ΠΈΠ·ΡΠΈΡ
ΡΡΠΎΠ²Π½Π΅ΠΉ Ρ Π²Π΅ΡΠΎΡΡΠ½ΠΎΡΡΡΠΌΠΈ ΠΏΠ΅ΡΠ΅Ρ
ΠΎΠ΄ΠΎΠ² Π΄Π»Ρ ΠΈΠ·ΠΎΠ»ΠΈΡΠΎΠ²Π°Π½Π½ΠΎΠΉ ΠΌΠΎΠ»Π΅ΠΊΡΠ»Ρ. ΠΠΎΠ»ΡΡΠ΅Π½Ρ ΠΊΠΎΠ»Π΅Π±Π°ΡΠ΅Π»ΡΠ½ΡΠ΅ ΠΏΡΠΎΡΠΈΠ»ΠΈ Π΄Π»ΠΈΠ½Π½ΠΎΠ²ΠΎΠ»Π½ΠΎΠ²ΠΎΠΉ ΡΠ»Π΅ΠΊΡΡΠΎΠ½Π½ΠΎΠΉ ΠΏΠΎΠ»ΠΎΡΡ ΠΏΠΎΠ³Π»ΠΎΡΠ΅Π½ΠΈΡ ΠΈ ΠΏΠ΅ΡΠ²ΠΎΠ³ΠΎ Π²ΠΎΠ·Π±ΡΠΆΠ΄Π΅Π½Π½ΠΎΠ³ΠΎ Π€ΡΠ°Π½ΠΊ-ΠΠΎΠ½Π΄ΠΎΠ½ΠΎΠ²ΡΠΊΠΎΠ³ΠΎ ΡΠΈΠ½Π³Π»Π΅ΡΠ½ΠΎΠ³ΠΎ ΡΠΎΡΡΠΎΡΠ½ΠΈΡ Ρ ΡΡΠ΅ΡΠΎΠΌ ΡΠ»ΡΠΎΡΠ΅ΡΡΠ΅Π½ΡΠ½ΠΎΠ³ΠΎ Π²ΡΠ΅ΠΌΠ΅Π½ΠΈ ΠΆΠΈΠ·Π½ΠΈ Π΄Π»Ρ ΠΎΡΡΠΈΠ»Π»ΠΈΡΡΡΡΠ΅ΠΉ ΠΌΠΎΠ»Π΅ΠΊΡΠ»Ρ. ΠΠ°Π½Π° ΠΈΠ½ΡΠ΅ΡΠΏΡΠ΅ΡΠ°ΡΠΈΡ ΡΠΊΡΠΏΠ΅ΡΠΈΠΌΠ΅Π½ΡΠ°Π»ΡΠ½ΡΡ
ΡΠΏΠ΅ΠΊΡΡΠΎΡΠΊΠΎΠΏΠΈΡΠ΅ΡΠΊΠΈΡ
Π΄Π°Π½Π½ΡΡ