Synthesis, surface profile, nonlinear reflective index and photophysical properties of curcumin compound

ABSTRACT For tire designers, rubber friction is a topic of pronounced practical importance. Thus, development of a rubber–road contact model is of great interest. In this research, to predict the effectiveness of the tread compound in a tire as it interacts with the pavement, the physics-based multiscale rubber-friction theories developed by B. Persson and M. Klüppel were studied. The strengths of each method were identified and incorporated into a consolidated model that is more comprehensive and proficient than any single, existing, physics-based approach. In the present work, the friction coefficient was estimated for a summer tire tread compound sliding on sandpaper. The inputs to the model were the fractal properties of the rough surface and the dynamic viscoelastic modulus of rubber. The sandpaper-surface profile was measured accurately using an optical profilometer. Two-dimensional parameterization was performed using one-dimensional profile measurements. The tire tread compound was characterized via dynamic mechanical analysis. To validate the friction model, a laboratory-based, rubber-friction test that could measure the friction between a rubber sample and any arbitrary rough surface was designed and built. The apparatus consisted of a turntable, which can have the surface characteristics of choice, and a rubber wheel in contact with the turntable. The wheel speed, as well as the turntable speed, could be controlled precisely to generate the arbitrary values of longitudinal slip at which the dynamic coefficient of friction was measured. The correlation between the simulation and the experimental results was investigated.

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

10.26434/chemrxiv.11798568.v2 ◽

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>

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Theoretical Framework of 1,3-Thiazolium-5-Thiolates Mesoionic Compounds: Exploring the Nature of Photophysical Properties and Molecular Nonlinearity

10.26434/chemrxiv.12063261 ◽

2020 ◽

Author(s):

Zeyu Liu ◽

Shugui Hua ◽

Tian Lu ◽

Ziqi Tian

Keyword(s):

Optical Properties ◽

Rational Design ◽

Rayleigh Scattering ◽

Function Analysis ◽

Theoretical Calculations ◽

Photophysical Properties ◽

Optical Nonlinearity ◽

Nonlinear Properties ◽

Photoelectric Performance ◽

Wave Function Analysis

Inspired by a previous experimental study on the first-order hyperpolarizabilities of 1,3-thiazolium-5-thiolates mesoionic compounds using Hyper-Rayleigh scattering technique, we theoretically investigated the UV-Vis absorption spectra and every order polarizabilities of these mesoionic molecules. Based on the fact that the photophysical and nonlinear properties observed in the experiment can be perfectly replicated, our theoretical calculations explored the essential characteristics of the optical properties of the mesoionic compounds with different electron-donating groups at the level of electronic structures through various wave function analysis methods. The influence of the electron-donating ability of the donor on the optical properties of the molecules and the contribution of the mesoionic ring moiety to their optical nonlinearity are clarified, which have not been reported by any research so far. This work will help people understand the nature of optical properties of mesoionic-based molecules and provide guidance for the rational design of molecules with excellent photoelectric performance in the future.

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Exploration of Bis(Arylimidazole) Iridium Picolinate Complexes

10.26434/chemrxiv.5331460.v1 ◽

2017 ◽

Cited By ~ 1

Author(s):

Aron Huckaba ◽

sadig aghazada ◽

iwan zimmermann ◽

giulia grancini ◽

natalia gasilova ◽

...

Keyword(s):

Cyclic Voltammetry ◽

Photophysical Properties ◽

Structure Property ◽

Aryl Group ◽

Ligand Modification ◽

Property Relationship ◽

Structure Property Relationship

The straightforward synthesis and photophysical properties of a new series of heteroleptic Iridium (III) bis(2-arylimidazole) picolinate complexes is reported. Each complex has been characterized by NMR, UV-Vis, cyclic voltammetry, and the emissive properties of each is described. By systematically modifying first the cyclometallating aryl group on the arylimidazole ligand and then the picolinate ligand, the ramifications of ligand modification in these complexes was better understood through the construction of a structure-property relationship.

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Exploration of Bis(Arylimidazole) Iridium Picolinate Complexes

10.26434/chemrxiv.5331460 ◽

2017 ◽

Author(s):

Aron Huckaba ◽

sadig aghazada ◽

iwan zimmermann ◽

giulia grancini ◽

natalia gasilova ◽

...

Keyword(s):

Cyclic Voltammetry ◽

Photophysical Properties ◽

Structure Property ◽

Aryl Group ◽

Ligand Modification ◽

Property Relationship ◽

Structure Property Relationship

The straightforward synthesis and photophysical properties of a new series of heteroleptic Iridium (III) bis(2-arylimidazole) picolinate complexes is reported. Each complex has been characterized by NMR, UV-Vis, cyclic voltammetry, and the emissive properties of each is described. By systematically modifying first the cyclometallating aryl group on the arylimidazole ligand and then the picolinate ligand, the ramifications of ligand modification in these complexes was better understood through the construction of a structure-property relationship.

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Probing the Structural Features and the Micro-heterogeneity of Various Deep Eutectic Solvents and their Water Dilutions by the Photophysical Behaviour of Two Fluorophores

10.26434/chemrxiv.13395683.v1 ◽

2020 ◽

Author(s):

Matteo Tiecco ◽

Irene Di Guida ◽

Pier Luigi Gentili ◽

Raimondo Germani ◽

Carmela Bonaccorso ◽

...

Keyword(s):

Hydrogen Bond ◽

Transient Absorption ◽

Photophysical Properties ◽

Deep Eutectic Solvents ◽

Structural Features ◽

Solvation Dynamics ◽

Structured Systems ◽

Reduced Viscosity ◽

Bond Network ◽

Fluorescent Molecules

<div><div><div><p>The structural features of a series of diverse Deep Eutectic Solvents (DESs) have been investigated and characterized by means of two fluorescent probes. The spectral and photophysical properties of the latter are strictly dependent on the experienced environment, so that they can provide insights into the polarity, viscosity, hydrogen-bond network, and micro-heterogeneity of the various DESs.</p><p>In fact, the investigated DESs exhibit a variety of properties with regards to their hydrophilicity, acidity, and hydrogen-bond ability, and these details were deeply probed by the two fluorescent molecules. The effect of the addition of water, which is a key strategy for tuning the properties of these structured systems, was also tested. In particular, the excited state dynamics of the probes, measured by femtosecond-resolved transient absorption, proved instrumental in understanding the changes in the structural properties of the DESs, namely reduced viscosity and enhanced heterogeneity, as the water percentage increases. Differences between the various DESs in terms of both local microheterogeneity and bulk viscosity also emerged from the peculiar multi-exponential solvation dynamics undergone by the excited states of the probes.</p></div></div></div>

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Probing the Structural Features and the Micro-heterogeneity of Various Deep Eutectic Solvents and their Water Dilutions by the Photophysical Behaviour of Two Fluorophores

10.26434/chemrxiv.13395683 ◽

2020 ◽

Author(s):

Matteo Tiecco ◽

Irene Di Guida ◽

Pier Luigi Gentili ◽

Raimondo Germani ◽

Carmela Bonaccorso ◽

...

Keyword(s):

Hydrogen Bond ◽

Transient Absorption ◽

Photophysical Properties ◽

Deep Eutectic Solvents ◽

Structural Features ◽

Solvation Dynamics ◽

Structured Systems ◽

Reduced Viscosity ◽

Bond Network ◽

Fluorescent Molecules

<div><div><div><p>The structural features of a series of diverse Deep Eutectic Solvents (DESs) have been investigated and characterized by means of two fluorescent probes. The spectral and photophysical properties of the latter are strictly dependent on the experienced environment, so that they can provide insights into the polarity, viscosity, hydrogen-bond network, and micro-heterogeneity of the various DESs.</p><p>In fact, the investigated DESs exhibit a variety of properties with regards to their hydrophilicity, acidity, and hydrogen-bond ability, and these details were deeply probed by the two fluorescent molecules. The effect of the addition of water, which is a key strategy for tuning the properties of these structured systems, was also tested. In particular, the excited state dynamics of the probes, measured by femtosecond-resolved transient absorption, proved instrumental in understanding the changes in the structural properties of the DESs, namely reduced viscosity and enhanced heterogeneity, as the water percentage increases. Differences between the various DESs in terms of both local microheterogeneity and bulk viscosity also emerged from the peculiar multi-exponential solvation dynamics undergone by the excited states of the probes.</p></div></div></div>

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A Unified Model for Photophysical and Electro-Optical Properties of Green Fluorescent Proteins

10.26434/chemrxiv.8772668.v1 ◽

2019 ◽

Author(s):

Chi-Yun Lin ◽

Matthew Romei ◽

Luke Oltrogge ◽

Irimpan Mathews ◽

Steven Boxer

Keyword(s):

Driving Force ◽

Fluorescent Protein ◽

Charge Transfer Band ◽

Photophysical Properties ◽

Polymethine Dyes ◽

Emission Rates ◽

Unified Framework ◽

Underlying Factor ◽

Green Fluorescent ◽

Protein Environment

Green fluorescent protein (GFPs) have become indispensable imaging and optogenetic tools. Their absorption and emission properties can be optimized for specific applications. Currently, no unified framework exists to comprehensively describe these photophysical properties, namely the absorption maxima, emission maxima, Stokes shifts, vibronic progressions, extinction coefficients, Stark tuning rates, and spontaneous emission rates, especially one that includes the effects of the protein environment. In this work, we study the correlations among these properties from systematically tuned GFP environmental mutants and chromophore variants. Correlation plots reveal monotonic trends, suggesting all these properties are governed by one underlying factor dependent on the chromophore's environment. By treating the anionic GFP chromophore as a mixed-valence compound existing as a superposition of two resonance forms, we argue that this underlying factor is defined as the difference in energy between the two forms, or the driving force, which is tuned by the environment. We then introduce a Marcus-Hush model with the bond length alternation vibrational mode, treating the GFP absorption band as an intervalence charge transfer band. This model explains all the observed strong correlations among photophysical properties; related subtopics are extensively discussed in Supporting Information. Finally, we demonstrate the model's predictive power by utilizing the additivity of the driving force. The model described here elucidates the role of the protein environment in modulating photophysical properties of the chromophore, providing insights and limitations for designing new GFPs with desired phenotypes. We argue this model should also be generally applicable to both biological and non-biological polymethine dyes.<br>

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