Direct Measurements of Rate Constants and Activation Volumes for the Binding of H2, D2, N2, C2H4, and CH3CN to W(CO)3(PCy3)2:  Theoretical and Experimental Studies with Time-Resolved Step-Scan FTIR and UV−Vis Spectroscopy

2006 ◽  
Vol 128 (49) ◽  
pp. 15728-15741 ◽  
Author(s):  
David C. Grills ◽  
Rudi van Eldik ◽  
James T. Muckerman ◽  
Etsuko Fujita
Keyword(s):  
Rate Constants ◽  
Experimental Studies ◽  
Time Resolved ◽  
Direct Measurements ◽  
Vis Spectroscopy

scholarly journals Helmet Phthalocyaninato Iron Complex as a Primary Drier for Alkyd Paints

Materials ◽  
2021 ◽  
Vol 14 (5) ◽  
pp. 1220
Author(s):  
Jan Honzíček ◽  
Eliška Matušková ◽  
Štěpán Voneš ◽  
Jaromír Vinklárek
Keyword(s):  
Catalytic Performance ◽  
Mechanical Tests ◽  
Iron Complex ◽  
Kinetic Measurements ◽  
Time Resolved ◽  
Strong Activity ◽  
Vis Spectroscopy ◽  
Order Of Magnitude ◽  
Transparent Coatings ◽  
Time Resolved Infrared Spectroscopy

This study describes the catalytic performance of an iron(III) complex bearing a phthalocyaninato-like ligand in two solvent-borne and two high-solid alkyd binders. Standardized mechanical tests revealed strong activity, which appeared in particular cases at concentrations about one order of magnitude lower than in the case of cobalt(II) 2-ethylhexanoate, widespread used in paint-producing industry. The effect of the iron(III) compound on autoxidation process, responsible for alkyd curing, was quantified by kinetic measurements by time-resolved infrared spectroscopy and compared with several primary driers. Effect of the drier concentration on coloration of transparent coatings was determined by UV–Vis spectroscopy.

scholarly journals Ultrafast proton release reaction and primary photochemistry of phycocyanobilin in solution observed with fs-time-resolved mid-IR and UV/Vis spectroscopy

2021 ◽  
Author(s):  
Maximilian Theiß ◽  
Merten Grupe ◽  
Tilman Lamparter ◽  
Maria Andrea Mroginski ◽  
Rolf Diller
Keyword(s):  
Density Functional ◽  
Transient Absorption ◽  
Vibrational Analysis ◽  
Density Functional Theory Calculations ◽  
Chem Phys ◽  
Molecular Structures ◽  
Ir Absorption ◽  
Time Resolved ◽  
Time Constants ◽  
Vis Spectroscopy

AbstractDeactivation processes of photoexcited (λex = 580 nm) phycocyanobilin (PCB) in methanol were investigated by means of UV/Vis and mid-IR femtosecond (fs) transient absorption (TA) as well as static fluorescence spectroscopy, supported by density-functional-theory calculations of three relevant ground state conformers, PCBA, PCBB and PCBC, their relative electronic state energies and normal mode vibrational analysis. UV/Vis fs-TA reveals time constants of 2.0, 18 and 67 ps, describing decay of PCBB*, of PCBA* and thermal re-equilibration of PCBA, PCBB and PCBC, respectively, in line with the model by Dietzek et al. (Chem Phys Lett 515:163, 2011) and predecessors. Significant substantiation and extension of this model is achieved first via mid-IR fs-TA, i.e. identification of molecular structures and their dynamics, with time constants of 2.6, 21 and 40 ps, respectively. Second, transient IR continuum absorption (CA) is observed in the region above 1755 cm−1 (CA1) and between 1550 and 1450 cm−1 (CA2), indicative for the IR absorption of highly polarizable protons in hydrogen bonding networks (X–H…Y). This allows to characterize chromophore protonation/deprotonation processes, associated with the electronic and structural dynamics, on a molecular level. The PCB photocycle is suggested to be closed via a long living (> 1 ns), PCBC-like (i.e. deprotonated), fluorescent species.

scholarly journals Carbon nanostructure and reactivity of soot particles from non-intrusive methods based on UV-VIS spectroscopy and time-resolved laser-induced incandescence

Carbon ◽  
2021 ◽  
Author(s):  
Fabian P. Hagen ◽  
Daniel Kretzler ◽  
Thomas Häber ◽  
Henning Bockhorn ◽  
Rainer Suntz ◽  
...  
Keyword(s):  
Carbon Nanostructure ◽  
Time Resolved ◽  
Soot Particles ◽  
Vis Spectroscopy ◽  
Laser Induced Incandescence

scholarly journals Synthesis, Biomacromolecular Interactions, Photodynamic NO Releasing and Cellular Imaging of Two [RuCl(qn)(Lbpy)(NO)]X Complexes

Molecules ◽  
2021 ◽  
Vol 26 (9) ◽  
pp. 2545
Author(s):  
Luna Song ◽  
Hehe Bai ◽  
Chenyang Liu ◽  
Wenjun Gong ◽  
Ai Wang ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Confocal Imaging ◽  
Epr Spectra ◽  
Distorted Octahedral Geometry ◽  
Ionization Mass ◽  
Time Resolved ◽  
Pbr322 Dna ◽  
Vis Spectroscopy ◽  
No Release ◽  
Ft Ir

Two light-activated NO donors [RuCl(qn)(Lbpy)(NO)]X with 8-hydroxyquinoline (qn) and 2,2′-bipyridine derivatives (Lbpy) as co-ligands were synthesized (Lbpy1 = 4,4′-dicarboxyl-2,2′-dipyridine, X = Cl− and Lbpy2 = 4,4′-dimethoxycarbonyl-2,2′-dipyridine, X = NO3−), and characterized using ultraviolet–visible (UV-vis) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (1H NMR), elemental analysis and electrospray ionization mass spectrometry (ESI-MS) spectra. The [RuCl(qn)(Lbpy2)(NO)]NO3 complex was crystallized and exhibited distorted octahedral geometry, in which the Ru–N(O) bond length was 1.752(6) Å and the Ru–N–O angle was 177.6(6)°. Time-resolved FT-IR and electron paramagnetic resonance (EPR) spectra were used to confirm the photoactivated NO release of the complexes. The binding constant (Kb) of two complexes with human serum albumin (HSA) and DNA were quantitatively evaluated using fluorescence spectroscopy, Ru-Lbpy1 (Kb~106 with HSA and ~104 with DNA) had higher affinity than Ru-Lbpy2. The interactions between the complexes and HSA were investigated using matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF-MS) and EPR spectra. HSA can be used as a carrier to facilitate the release of NO from the complexes upon photoirradiation. The confocal imaging of photo-induced NO release in living cells was successfully observed with a fluorescent NO probe. Moreover, the photocleavage of pBR322 DNA for the complexes and the effect of different Lbpy substituted groups in the complexes on their reactivity were analyzed.

Visualization and Time-Resolved Particle Image Velocimetry Measurements of the Flow in the Tip Region of a Subsonic Compressor Rotor

2014 ◽  
Vol 137 (4) ◽  
Author(s):  
David Tan ◽  
Yuanchao Li ◽  
Ian Wilkes ◽  
Rinaldo L. Miorini ◽  
Joseph Katz
Keyword(s):  
Flow Rate ◽  
High Speed ◽  
Axial Compressor ◽  
Time Resolved ◽  
Tip Leakage ◽  
Compressor Rotor ◽  
Direct Measurements ◽  
Image Velocimetry ◽  
The One ◽  
And Behavior

A new optically index matched facility has been constructed to investigate tip flows in compressor-like settings. The blades of the one and a half stage compressor have the same geometry, but lower aspect ratio as the inlet guide vanes (IGVs) and the first stage of the low-speed axial compressor (LSAC) facility at NASA Glenn. With transparent blades and casings, the new setup enables unobstructed velocity measurements at any point within the tip region and is designed to facilitate direct measurements of effects of casing treatments on the flow structure. We start with a smooth endwall casing. High speed movies of cavitation and time-resolved PIV measurements have been used to characterize the location, trajectory, and behavior of the tip leakage vortex (TLV) for two flow rates, the lower one representing prestall conditions. Results of both methods show consistent trends. As the flow rate is reduced, TLV rollup occurs further upstream, and its initial orientation becomes more circumferential. At prestall conditions, the TLV is initially aligned slightly upstream of the rotor passage, and subsequently forced downstream. Within the passage, the TLV breaks up into a large number of vortex fragments, which occupy a broad area. Consequently, the cavitation in the TLV core disappears. With decreasing flow rate, this phenomenon becomes more abrupt, occurs further upstream, and the fragments occupy a larger area.

ChemInform Abstract: Direct Measurements of Formation Rate Constants of Allylic Radical from Hot Olefins Formed by Internal Conversion. Part 1.

ChemInform ◽  
1988 ◽  
Vol 19 (1) ◽  
Author(s):  
N. NAKASHIMA ◽  
N. IKEDA ◽  
N. SHIMO ◽  
K. YOSHIHARA
Keyword(s):  
Rate Constants ◽  
Internal Conversion ◽  
Formation Rate ◽  
Direct Measurements ◽  
Allylic Radical

scholarly journals Increasing the time resolution of single-molecule experiments with Bayesian inference

2017 ◽  
Author(s):  
Colin D. Kinz-Thompson ◽  
Ruben L. Gonzalez
Keyword(s):  
Bayesian Inference ◽  
Single Molecule ◽  
Time Resolution ◽  
Rate Constants ◽  
Computational Approach ◽  
Biomolecular Systems ◽  
Time Resolved ◽  
The Given ◽  
Kinetics Of ◽  
Resolution Data

AbstractMany time-resolved, single-molecule biophysics experiments seek to characterize the kinetics of biomolecular systems exhibiting dynamics that challenge the time resolution of the given technique. Here we present a general, computational approach to this problem that employs Bayesian inference to learn the underlying dynamics of such systems, even when they are much faster than the time resolution of the experimental technique being used. By accurately and precisely inferring rate constants, our Bayesian Inference for the Analysis of Sub-temporal-resolution Data (BIASD) approach effectively enables the experimenter to super-resolve the poorly resolved dynamics that are present in their data.

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