scholarly journals Time-resolved step scan FTIR spectroscopy and DFT investigation on triplet formation in peridinin–chlorophyll-a–protein from Amphidinium carterae at low temperature

2008 ◽  
Vol 22 (4) ◽  
pp. 235-250 ◽  
Author(s):  
Alberto Mezzetti ◽  
Riccardo Spezia
Keyword(s):  
Low Temperature ◽  
Dft Calculations ◽  
Ftir Spectroscopy ◽  
Spectral Feature ◽  
Point Of View ◽  
Time Resolved ◽  
Band Assignment ◽  
Photophysical Processes ◽  
Triplet Formation ◽  
Good Agreement

We have used time-resolved step-scan FTIR spectroscopy to investigate the process of triplet formation in the peridinin–chlorophyll-a–protein (PCP) at 100 K. Results have led to the identification of possible marker bands for peridinin (Per) and3Per. Band assignment has been carried out performing a DFT investigation on Per,3Per and on model molecules. The main spectral feature is a couple of bands at 1746 (negative) and 1719 (positive) cm–1. The assignment of these two bands to the lactonic C═O of Per in (respectively) its fundamental S0 and tripletT1state is based on: (1) comparison with FTIR spectra of isolated Per in literature; (2) good agreement with DFT calculations for Per and3Per; (3) the downshift of the band upon triplet formation as predicted by DFT calculations in Per and similar lactonic systems; (4) the kinetic of band disappearance, in agreement with literature data. Another possible band for Per in its fundamental state has been identified at 1523 cm–1.The results are in overall agreement with a recent step-scan FTIR study on PCP at 298 K (Alexandre et al.,Biophys. J. 93 (2007), 2118–2128) even though some small discrepancies emerge, probably related to the different temperature at which experiments were carried out. Further DFT calculations have been performed to rationalise these spectral discrepancies. From a methodological point of view, the work demonstrates the potential of a combined step-scan FTIR/DFT approach in the study of photophysical processes in proteins. Furthermore, it has been shown that, when small differential IR signals are concerned, nagging photothermal effects can interfere and can possibly lead to misleading interpretations.

scholarly journals Ozone Activation on TiO2 Studied by IR Spectroscopy and Quantum Chemistry

2021 ◽  
Vol 11 (16) ◽  
pp. 7683
Author(s):  
Timur Aminev ◽  
Irina Krauklis ◽  
Oleg Pestsov ◽  
Alexey Tsyganenko
Keyword(s):  
Ir Spectroscopy ◽  
Quantum Chemistry ◽  
Dft Calculations ◽  
Ftir Spectroscopy ◽  
Cluster Models ◽  
Vibration Band ◽  
Weakly Bound ◽  
Combination Band ◽  
Monodentate Complex ◽  
Good Agreement

The adsorption of different isotopic ozone mixtures on TiO2 at 77K was studied using FTIR spectroscopy and DFT calculations of cluster models. In addition to weakly bound ozone with band positions close to those of free or dissolved molecules, the spectrum of chemisorbed species was observed. The splitting of the ν1+3 combination band to eight maxima due to different isotopomers testified to the loss of molecule symmetry. The frequencies of all the isotopic modifications of the ozone molecules which form monodentate or bidentate complexes with four- or five-coordinated titanium atoms were calculated and compared with those of experimentally observed spectra. The four considered complexes adequately reproduced the splitting of the ν1+3 vibration band and the lowered anharmonism of chemisorbed O3. The energetically most favorable monodentate complex with four-coordinated titanium atoms showed good agreement with the observed spectra, although a large difference between the frequencies of ν1 and ν3 modes was found. For better coherence with the experiment, the interaction of the molecule with adjacent cations must be considered.

The promises and perfidy of cryomicroscopy and analysis

1994 ◽  
Vol 52 ◽  
pp. 382-383
Author(s):  
Patrick Echlin
Keyword(s):  
Low Temperature ◽  
High Energy ◽  
Short Paper ◽  
List Type ◽  
Time Resolved ◽  
Energy Beam ◽  
Cellular Analysis ◽  
Dissolved Ions ◽  
Embedding Medium ◽  
Low Temperature Microscopy

The unusual title of this short paper and its accompanying tutorial is deliberate, because the intent is to investigate the effectiveness of low temperature microscopy and analysis as one of the more significant elements of the less interventionist procedures we can use to prepare, examine and analyse hydrated and organic materials in high energy beam instruments. The promises offered by all these procedures are well rehearsed and the litany of petitions and responses may be enunciated in the following mantra.Vitrified water can form the perfect embedding medium for bio-organic samples.Frozen samples provide an important, but not exclusive, milieu for the in situ sub-cellular analysis of the dissolved ions and electrolytes whose activities are central to living processes.The rapid conversion of liquids to solids provides a means of arresting dynamic processes and permits resolution of the time resolved interactions between water and suspended and dissolved materials.The low temperature environment necessary for cryomicroscopy and analysis, diminish, but alas do not prevent, the deleterious side effects of ionizing radiation.Sample contamination is virtually eliminated.

Solvent Dependence of Structural Dynamics and Spin-flip Processes in 3,4,5-tri(9H-carbazole-9-yl)benzonitrile (ortho-3CzBN)

2020 ◽  
Author(s):  
Masaki Saigo ◽  
Kiyoshi Miyata ◽  
Hajime Nakanotani ◽  
Chihaya Adachi ◽  
Ken Onda
Keyword(s):  
Dft Calculations ◽  
Excited States ◽  
Structural Changes ◽  
Photophysical Properties ◽  
Delayed Fluorescence ◽  
Time Resolved ◽  
Thermally Activated Delayed Fluorescence ◽  
Thermally Activated ◽  
Solvent Dependence ◽  
Acetonitrile Solutions

We have investigated the solvent-dependence of structural changes along with intersystem crossing of a thermally activated delayed fluorescence (TADF) molecule, 3,4,5-tri(9H-carbazole-9-yl)benzonitrile (o-3CzBN), in toluene, tetrahydrofuran, and acetonitrile solutions using time-resolved infrared (TR-IR) spectroscopy and DFT calculations. We found that the geometries of the S1 and T1 states are very similar in all solvents though the photophysical properties mostly depend on the solvent. In addition, the time-dependent DFT calculations based on these geometries suggested that the thermally activated delayed fluorescence process of o-3CzBN is governed more by the higher-lying excited states than by the structural changes in the excited states.<br>

Pt-Pd Nanoalloy for the Unprecedented Activation of Carbon-Fluorine Bond at Low Temperature

2019 ◽  
Author(s):  
Raghu Nath Dhital ◽  
keigo nomura ◽  
Yoshinori Sato ◽  
Setsiri Haesuwannakij ◽  
Masahiro Ehara ◽  
...  
Keyword(s):  
Activation Energy ◽  
Low Temperature ◽  
Dft Calculations ◽  
Bond Activation ◽  
Mild Conditions ◽  
Selective Transformation ◽  
Rate Determining Step ◽  
Highly Active ◽  
Harsh Conditions ◽  
Reaction Profile

Carbon-Fluorine (C-F) bonds are considered the most inert organic functionality and their selective transformation under mild conditions remains challenging. Herein, we report a highly active Pt-Pd nanoalloy as a robust catalyst for the transformation of C-F bonds into C-H bonds at low temperature, a reaction that often required harsh conditions. The alloying of Pt with Pd is crucial to activate C-F bond. The reaction profile kinetics revealed that the major source of hydrogen in the defluorinated product is the alcoholic proton of 2-propanol, and the rate-determining step is the reduction of the metal upon transfer of the <i>beta</i>-H from 2-propanol. DFT calculations elucidated that the key step is the selective oxidative addition of the O-H bond of 2-propanol to a Pd center prior to C-F bond activation at a Pt site, which crucially reduces the activation energy of the C-F bond. Therefore, both Pt and Pd work independently but synergistically to promote the overall reaction

Photophysical properties of N719 and Z907 dyes, benchmark sensitizers for dye-sensitized solar cells, at room and low temperature

2021 ◽  
Vol 23 (10) ◽  
pp. 6182-6189
Author(s):  
Dariusz M. Niedzwiedzki
Keyword(s):  
Solar Cells ◽  
Low Temperature ◽  
Optical Spectroscopy ◽  
Room Temperature ◽  
Photophysical Properties ◽  
Dye Sensitized Solar Cells ◽  
Time Resolved ◽  
Dye Sensitized ◽  
Sensitized Solar Cells

Photophysical properties of N719 and Z907, benchmark Ru-dyes used as sensitizers in dye-sensitized solar cells, were studied by static and time-resolved optical spectroscopy at room temperature and 160 K.

scholarly journals Mechanistic insights for the photoredox organocatalytic fluorination of aliphatic carbons by anthraquinone using time-resolved and DFT studies

2017 ◽  
Vol 7 (4) ◽  
pp. 848-857 ◽  
Author(s):  
J. W. Kee ◽  
H. Shao ◽  
C. W. Kee ◽  
Y. Lu ◽  
H. S. Soo ◽  
...  
Keyword(s):  
Dft Calculations ◽  
Dft Studies ◽  
Time Resolved

Nanosecond TAS and DFT calculations reveal mechanistic insights for photoredox fluorination of aliphatic C–H bonds and evidence of an anthraquinone–Selectfluor® exciplex.

Formation of Pt decorated Ni–Pt nanocubes through low temperature atomic diffusion – time-resolved elemental analysis of nanoparticle formation

Nanoscale ◽  
2015 ◽  
Vol 7 (21) ◽  
pp. 9927-9934 ◽  
Author(s):  
A. Nagao ◽  
K. Higashimine ◽  
J. L. Cuya Huaman ◽  
T. Iwamoto ◽  
T. Matsumoto ◽  
...  
Keyword(s):  
Low Temperature ◽  
Elemental Analysis ◽  
Diffusion Time ◽  
Atomic Diffusion ◽  
Pt Catalysts ◽  
Time Resolved ◽  
Nanoparticle Formation ◽  
The Core ◽  
Temperature Diffusion

Low temperature diffusion of Pt atoms from the core to the corners and edges of the Ni cube results in the preparation of potential novel cage-structured Pt catalysts.

Structural Changes in the Schiff Base Region of Squid Rhodopsin upon Photoisomerization Studied by Low-Temperature FTIR Spectroscopy†

Biochemistry ◽  
2006 ◽  
Vol 45 (9) ◽  
pp. 2845-2851 ◽  
Author(s):  
Toru Ota ◽  
Yuji Furutani ◽  
Akihisa Terakita ◽  
Yoshinori Shichida ◽  
Hideki Kandori
Keyword(s):  
Schiff Base ◽  
Low Temperature ◽  
Ftir Spectroscopy ◽  
Structural Changes ◽  
Base Region

Structural Analysis of an Offshore Jacket Model Under Seismic Excitation

2008 ◽  
Author(s):  
Helder J. D. Correia ◽  
Anto´nio C. Mendes ◽  
Carlos A. F. S. Oliveira
Keyword(s):  
Point Of View ◽  
Shaking Table ◽  
Seismic Excitation ◽  
Model Structure ◽  
Structural Members ◽  
Jacket Structures ◽  
Reaction Forces ◽  
Nodal Displacements ◽  
Good Agreement

In the present work the action of earthquakes upon offshore jacket structures is analysed by means of ADINA software. Our case-study refers to an existing model structure, previously constructed at the Laboratory of Fluid Mechanics of UBI, which has been analysed from the hydrodynamic point of view — Mendes et al. [1, 2]. The seismic excitation will be imposed at the base of this model structure, with frequencies and amplitudes corresponding to actual earthquake conditions transposed to the model scale of 1:45. The FEM software is utilised to calculate the natural frequencies of the model and to obtain stresses at selected members, as well as their nodal displacements. Our purpose is to quantify maximum stresses occurring in critical structural members and to verify the survivability criterion. The predictions of the numerical model, in terms of the reaction forces at the base and acceleration at the top of the structure, are then correlated with the experimental measurements performed when the model structure is excited in an especially designed shaking table (Correia [3]), revealing a good agreement between both results.

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