scholarly journals Phosphorescence of protein-bound eosin and erythrosin. A possible probe for measurements of slow rotational mobility

1979 ◽  
Vol 183 (3) ◽  
pp. 561-572 ◽  
Author(s):  
P B Garland ◽  
C H Moore
Keyword(s):  
Triplet State ◽  
Ground State ◽  
Relaxation Times ◽  
Anisotropy Parameter ◽  
Delayed Fluorescence ◽  
Rotational Relaxation ◽  
Rotational Mobility ◽  
Long Wavelength ◽  
Radiative Transitions ◽  
Highly Sensitive

We used a pulsed dye laser working at 540 nm to excite triplet-state formation of eosin and erythrosin, either bound or unbound to bovine serum albumin, in aqueous solution anaerobically at pH 8 and 20-22 degrees C. Delayed emission from radiative transitions of the triplet state was readily detectable, both as delayed fluorescence and as red phosphorescence. Detection of the triplet state by measurement of phosphorescence at 645 nm upwards was at least 100-fold more sensitive than by absorbance measurements of ground-state depletion at 500 nm. When immobilized in poly(methyl methacrylate), the phosphorescence of eosin and erythrosin was polarized with an anisotropy parameter [Jablonski (1961) Z. Naturforsch. A16, 1-4] of about 0.25. The phosphorescence of erythrosin is sufficiently intense to be distinguishable from the long-wavelength end of fluorescence under conditions of continuous rather than pulsed excitation. Our observations suggest that phosphorescence depolarization of eosin or erythrosin probes could be used as a highly sensitive method of measuring rotational relaxation times in region from 10(-5) to 10(-3) s, such as those of the uniaxial rotation of membrane proteins.

The ground state (1A1) and the lowest triplet state (3B1) of the phenyl cation C6H5+ revisited

1997 ◽  
Vol 106 (18) ◽  
pp. 7541-7549 ◽  
Author(s):  
Jan Hrušák ◽  
Detlef Schröder ◽  
Suehiro Iwata
Keyword(s):  
Triplet State ◽  
Ground State ◽  
Phenyl Cation

scholarly journals P∩N Bridged Cu(I) Dimers Featuring Both TADF and Phosphorescence. From Overview towards Detailed Case Study of the Excited Singlet and Triplet States

Molecules ◽  
2021 ◽  
Vol 26 (11) ◽  
pp. 3415
Author(s):  
Thomas Hofbeck ◽  
Thomas A. Niehaus ◽  
Michel Fleck ◽  
Uwe Monkowius ◽  
Hartmut Yersin
Keyword(s):  
Quantum Yield ◽  
Decay Time ◽  
Relaxation Times ◽  
Lattice Relaxation ◽  
Photo Luminescence ◽  
Delayed Fluorescence ◽  
Spin Lattice Relaxation ◽  
Zero Field ◽  
Triplet States ◽  
Spin Lattice

We present an overview over eight brightly luminescent Cu(I) dimers of the type Cu2X2(P∩N)3 with X = Cl, Br, I and P∩N = 2-diphenylphosphino-pyridine (Ph2Ppy), 2-diphenylphosphino-pyrimidine (Ph2Ppym), 1-diphenylphosphino-isoquinoline (Ph2Piqn) including three new crystal structures (Cu2Br2(Ph2Ppy)3 1-Br, Cu2I2(Ph2Ppym)3 2-I and Cu2I2(Ph2Piqn)3 3-I). However, we mainly focus on their photo-luminescence properties. All compounds exhibit combined thermally activated delayed fluorescence (TADF) and phosphorescence at ambient temperature. Emission color, decay time and quantum yield vary over large ranges. For deeper characterization, we select Cu2I2(Ph2Ppy)3, 1-I, showing a quantum yield of 81%. DFT and SOC-TDDFT calculations provide insight into the electronic structures of the singlet S1 and triplet T1 states. Both stem from metal+iodide-to-ligand charge transfer transitions. Evaluation of the emission decay dynamics, measured from 1.2 ≤ T ≤ 300 K, gives ∆E(S1-T1) = 380 cm−1 (47 meV), a transition rate of k(S1→S0) = 2.25 × 106 s−1 (445 ns), T1 zero-field splittings, transition rates from the triplet substates and spin-lattice relaxation times. We also discuss the interplay of S1-TADF and T1-phosphorescence. The combined emission paths shorten the overall decay time. For OLED applications, utilization of both singlet and triplet harvesting can be highly favorable for improvement of the device performance.

Sulfamoyl nitrenes: singlet or triplet ground state?

2018 ◽  
Vol 54 (48) ◽  
pp. 6136-6139 ◽  
Author(s):  
Yan Lu ◽  
Hongmin Li ◽  
Manabu Abe ◽  
Didier Bégué ◽  
Huabin Wan ◽  
...  
Keyword(s):  
Triplet State ◽  
Ground State ◽  
Singlet State ◽  
Minimum Energy ◽  
Closed Shell ◽  
Low Energy ◽  
Energy Minimum ◽  
Triplet Ground State ◽  
Crossing Point

Two prototypical sulfamoyl nitrenes R2NS(O)2–N (R = H and Me) in the triplet state were generated via the closed-shell singlet state by passing a low-energy minimum energy crossing point (MECP).

scholarly journals Tuning Water Networks via Ionic Liquid/Water Mixtures

2020 ◽  
Vol 21 (2) ◽  
pp. 403 ◽  
Author(s):  
Archana Verma ◽  
John P. Stoppelman ◽  
Jesse G. McDaniel
Keyword(s):  
Ionic Liquid ◽  
Water Content ◽  
Relaxation Times ◽  
Water Structure ◽  
Lyotropic Liquid Crystals ◽  
Rotational Relaxation ◽  
Membrane Materials ◽  
Water Fraction ◽  
Pairwise Correlation ◽  
Dynamics Simulations

Water in nanoconfinement is ubiquitous in biological systems and membrane materials, with altered properties that significantly influence the surrounding system. In this work, we show how ionic liquid (IL)/water mixtures can be tuned to create water environments that resemble nanoconfined systems. We utilize molecular dynamics simulations employing ab initio force fields to extensively characterize the water structure within five different IL/water mixtures: [BMIM + ][BF 4 − ], [BMIM + ][PF 6 − ], [BMIM + ][OTf − ], [BMIM + ][NO 3 − ] and [BMIM + ][TFSI − ] ILs at varying water fraction. We characterize water clustering, hydrogen bonding, water orientation, pairwise correlation functions and percolation networks as a function of water content and IL type. The nature of the water nanostructure is significantly tuned by changing the hydrophobicity of the IL and sensitively depends on water content. In hydrophobic ILs such as [BMIM + ][PF 6 − ], significant water clustering leads to dynamic formation of water pockets that can appear similar to those formed within reverse micelles. Furthermore, rotational relaxation times of water molecules in supersaturated hydrophobic IL/water mixtures indicate the close-connection with nanoconfined systems, as they are quantitatively similar to water relaxation in previously characterized lyotropic liquid crystals. We expect that this physical insight will lead to better design principles for incorporation of ILs into membrane materials to tune water nanostructure.

Investigation of Rotational Relaxation by Double Resonance and Stark Switch Techniques

1980 ◽  
Vol 35 (8) ◽  
pp. 832-840
Author(s):  
W. Schrepp ◽  
H. Dreizler ◽  
A. Guarnieri
Keyword(s):  
Double Resonance ◽  
Relaxation Times ◽  
Experimental Methods ◽  
Rotational Relaxation ◽  
Triple Resonance ◽  
Static Electric Field ◽  
First Order ◽  
Four Levels ◽  
Relative Change

Abstract For the four rotational levels JK₋K₊ = 101, 110,212 and 221 of ethylene oxide all possible four level double resonance experiments for dipole allowed transitions have been performed to investigate collisional effects and to determine the relative change of signal intensity, η = ⊿I/I, due to high power pump radiation. The T1 and T2-relaxation times have been measured for all dipole allowed transitions within these four levels. A combination of the data obtained from both experimental methods allows the determination of rate and bath constants taking into account only first order dipolar transitions. No further restrictions have been used. This approximation is supported by a triple resonance experiment. In addition to the pure gas investigation in the absence of external fields, rotational relaxation has been studied in the presence of a static electric field and in a mixture with hydrogen.

scholarly journals Effect of Single-Ion Anisotropy on Magnetocaloric Properties of Frustrated Spin-s Ising Nanoclusters

2020 ◽  
Vol 6 (4) ◽  
pp. 56
Author(s):  
Mariia Mohylna ◽  
Milan Žukovič
Keyword(s):  
Ground State ◽  
Anisotropy Parameter ◽  
State Behavior ◽  
Abrupt Decrease ◽  
Experimental Realization ◽  
Plane Anisotropy ◽  
Adiabatic Demagnetization ◽  
Magnetocaloric Properties ◽  
Cluster Geometry ◽  
Favorable Conditions

Effects of a single-ion anisotropy on magnetocaloric properties of selected spin-s≥1 antiferromagnetic Ising clusters with frustration-inducing triangular geometry are studied by exact enumeration. It is found that inclusion of the single-ion anisotropy parameter D can result in a much more complex ground-state behavior, which is also reflected in a magnetocaloric effect (MCE) at finite temperatures. For negative D (easy-plane anisotropy) with increasing s, the ground-state magnetization as a function of the external field gradually shows increasing number of plateaus of various heights. Except for the cases of integer s with D<D0≤0, the first magnetization plateau is of non-zero height. This property facilitates an enhanced MCE in the adiabatic demagnetization process in the form of an abrupt decrease in temperature as the magnetic field vanishes to zero. The cooling rate can be considerably enhanced in the systems with larger s and D>0 (easy-axis anisotropy), albeit its dependence on these parameters is strongly dependent on the cluster geometry. From the studied systems more favorable conditions for observing a giant MCE were found in the 2CS cluster, consisting of two corner-sharing tetrahedra, the experimental realization of which could be technologically used for efficient refrigeration to ultra-low temperatures.

Löschung der Perylen-Fluoreszenz durch Ag+ -Ionen / Quenching of the Perylene Fluorescence by Ag+-Ions

1983 ◽  
Vol 38 (6) ◽  
pp. 698-700 ◽  
Author(s):  
H. Dreeskamp ◽  
A. Läufer ◽  
M. Zander
Keyword(s):  
Triplet State ◽  
Dynamic Process ◽  
Aromatic Compounds ◽  
Heavy Atom ◽  
Silver Ions ◽  
Intersystem Crossing ◽  
Fluid Solution ◽  
Long Wavelength ◽  
Wavelength Emission ◽  
Atom Effect

The fluorescence of perylene in fluid solution (λ0.0 = 440 nm) is quenched by silver ions in a dynamic process according to a Stern-Volmer kinetics (kq = 2 · 109 [1 • mol-1 · sec-1], in ethanol at 295 K). Simultaneously an unstructured long-wavelength emission (λmax ≈ 470 nm) appears which we assign to a perylene/Ag+ exciplex. A similar emission is observed when other polvcyclic aromatic compounds (PAC) are used, whose fluorescence as in the case of perylene is not easily quenched in an external heavy atom effect by iodopropane (kq ≦ 106). In these cases the excited PAC/Ag+ complex is long-lived enough to emit fluorescence since the intersystem crossing to the triplet system is slow due to the absence of an energetically favorable accepting triplet state

Trimethylenemethane. Experimental demonstration that the triplet state is the ground state

1976 ◽  
Vol 98 (18) ◽  
pp. 5726-5727 ◽  
Author(s):  
Robert J. Baseman ◽  
David W. Pratt ◽  
Mudan Chow ◽  
Paul Dowd
Keyword(s):  
Triplet State ◽  
Ground State ◽  
Experimental Demonstration
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