Search results for "Spectroscopy"
showing 10 items of 10293 documents
DNA-binding of zinc(II) and nickel(II) salphen-like complexes extrapolated at 1 M salt concentration: Removing the ionic strength bias in physiologic…
2020
Abstract The DNA-binding of two salphen-like metal complexes of nickel(II) (1) and zinc(II) (2) was investigated in different ionic strength solutions by absorption spectroscopy. The data analysis allowed us to obtain the values of their extrapolated DNA-binding constant in physiological conditions, with DNA-binding strength in the order Ni > Zn, and to give relative weight to the electrostatic and non-electrostatic contributions to their DNA-interaction.
Reversible isomerization of metal nanoclusters induced by intermolecular interaction
2021
Most inorganic nanoparticles are directly surface-terminated (and -stabilized) by protecting ligands, which could greatly affect the atomic packing and physical/chemical properties of their inorganic cores. Here, we show that the intermolecular interactions between the adsorbed molecules and surface ligands can also affect the core structure of inorganic nanoparticles. Through the coupling/decoupling of cationic surfactants (cetyltrimethylammonium cations, CTA+) and anionic surface ligands (para-mercaptobenzoic acid, p-MBA) in the aqueous phase, we have achieved a reversible transformation between two isomers of [Au25(p-MBA)18]− nanoclusters. The interconversion process between the two isom…
Regio(ir)regular naphthalenediimide- and perylenediimide-bithiophene copolymers: How MO localization controls the bandgap
2016
Absorption spectra of regio(ir)regular naphthalenediimide (NDI)- and perylenediimide (PDI)-bithiophene (2T) donor/acceptor (D/A) copolymers are surprisingly similar despite cross-conjugation in the regioirregular structures. This result is traced back to largely localized frontier molecular orbitals (FMOs) as revealed by (time-dependent) DFT calculations. Interestingly, while the FMOs of the P(PDI-2T) copolymer are localized solely in the PDI units, they are predominantly localized in the respective D/A units of the P(NDI-2T) copolymer. The pronounced CT character of the lowest singlet state in P(NDI-2T) should give rise to a close lying CT triplet state, generating small singlet–triplet ga…
Dynamics behind the long-lived coherences of I2 in solid Xe.
2013
The absorption spectrum of I2 in solid Xe shows resolved zero-phonon lines and phonon side bands near the origin of the B←X transition (550-625 nm). The long-lived |B⟩⟨X| coherence in this energy range (T2 = 600 fs on average) emerges as vibrationally unrelaxed fluorescence in resonance Raman (RR) spectra. Upon excitation in the structureless continuum at 532 nm, the oscillatory RR progression exhibits electronic dephasing time of T2 = 150 fs. Two RR progressions with markedly different vibrational coherence on the X-state are observed. The main progression of sharp overtones (T221 ps) is assigned to molecules trapped in double-substitution sites. The minor progression, which shows dephasin…
Spectroscopic and electrochromical properties of metallophthalocyanines in silicate bulks and thin films prepared by the sol–gel method
2000
Abstract Magnesium phthalocyanine (MgPc) and praseodymium bisphthalocyanine (Pr(Pc) 2 ) have been entrapped in bulks and thin films of porous silicate xerogels prepared via the sol–gel method. The electronic absorption data obtained for the complexes immobilized in bulk sol–gel matrices indicate the formation of complex equilibria between their monomeric forms and respective agglomerates. Thin xerogel films doped with metallophthalocyanines and connecting two slides of transparent ITO electrodes display changes in the absorption spectra caused by varying of the applied voltage. These changes appear to be reversible in certain ranges of the applied voltages.
Protonation of the Biliverdin IXα Chromophore in the Red and Far-Red Photoactive States of a Bacteriophytochrome
2019
The tetrapyrrole chromophore biliverdin IXα (BV) in the bacteriophytochrome from Deinococcus radiodurans (DrBphP) is usually assumed to be fully protonated, but this assumption has not been systematically validated by experiments or extensive computations. Here, we use force field molecular dynamics simulations and quantum mechanics/molecular mechanics calculations with density functional theory and XMCQDPT2 methods to investigate the effect of the five most probable protonation forms of BV on structural stability, binding pocket interactions, and absorption spectra in the two photochromic states of DrBphP. While agreement with X-ray structural data and measured UV/vis spectra suggest that …
Structural and Dynamic Properties of the Homodimeric Hemoglobin from Scapharca inaequivalvis Thr-72→Ile Mutant: Molecular Dynamics Simulation, Low Te…
1998
AbstractMolecular dynamics simulations, low temperature visible absorption spectroscopy, and resonance Raman spectroscopy have been performed on a mutant of the Scapharca inaequivalvis homodimeric hemoglobin, where residue threonine 72, at the subunit interface, has been substituted by isoleucine. Molecular dynamics simulation indicates that in the Thr-72→Ile mutant several residues that have been shown to play a role in ligand binding fluctuate around orientations and distances similar to those observed in the x-ray structure of the CO derivative of the native hemoglobin, although the overall structure remains in the T state. Visible absorption spectroscopy data indicate that in the deoxy …
On the Low-Lying Excited States ofsym-Triazine-Based Herbicides
2005
We report a joint computational and luminescence study on the low-lying excited states of sym-triazines, namely, 1,3,5-triazine (1) and the ubiquitous herbicides atrazine [6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine (2)] and ametryn [6-methylthio-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine (3)]. Geometrical structures, energetics, and transition and state properties of I and 2 were computed at the TD-DFT, CASSCF, and CASPT2 levels of theory. The fluorescence and phosphorescence emission spectra, lifetimes, and fluorescence quantum yields were measured for the three compounds, and from these, the energies of the lowest excited states and their corresponding radiative rates…
Absorption spectrum of the and electronic transitions of ReF6
1999
Abstract The absorption spectra of the near-infrared and ultraviolet bands of ReF6 have been recorded with a commercial spectrophotometer. The vibronic assignments previously published by different authors are critically revised. A non-perturbative method has been used to calculate the linear Jahn–Teller levels for the ν5 mode in the ground electronic state. Some new vibronic parameter values are derived. The ν5 linear Jahn–Teller parameter in the X G′ g electronic state is found to be D5=0.103(9). The ultraviolet absorption spectrum has enabled us to determine relatively accurate values of the crystal-field (10Dq) and spin-orbit (ζd) parameters.
In-situ observation of beta-ray induced UV optical absorption in a-SiO2: radiation darkening and room temperature recovery
2006
International audience; We studied the optical absorption in the 3.0-6.2 eV range induced in bulk amorphous SiO2 by beta-ray irradiation up to similar to 1 MGy at room temperature. The induced absorption was measured in situ both during irradiation and in the post irradiation time. Our data evidence E', center as the main defect induced by irradiation and the partial decay of their absorption band at about 5.8 eV after irradiation. A quantitative analysis of the time evolution of the induced absorption shows that the transmission recovery observed after irradiation is compatible with the reaction of radiation-induced defects with H-related (H-2, H2O) species diffusing in the amorphous matrix