Luminescence of 5-Phenyltetrazole and its Derivatives Part III. Quantum Yields and Mean Lifetimes of Fluorescence

1984 ◽  
Vol 39 (10) ◽  
pp. 960-962
Author(s):  
I. Gryczyński ◽  
A. Kawski
Keyword(s):  
Rate Constants ◽  
Radiative Transition ◽  
Quantum Yields ◽  
Methyl Substituent ◽  
Methyl Derivatives ◽  
The Mean ◽  
Mean Lifetimes

Abstract Quantum yields and mean lifetimes of fluorescence have been measured of 5-phenyltetrazole and its three methyl derivatives, para-, meta- and ortho-methyl-5-phenyltetrazole. The rate constants, kF, of the radiative transition S1 → S0 have been deduced from these measurements. The mean lifetimes, τF, the quantum yields of fluorescence and the rate constants have been found to be clearly dependent on the position of the methyl substituent in the ring and could be arranged as follows:τpF>τmF>τ0F and k0F>kmF>kpF

Mechanistic studies of aromatic ketone-sensitized photoreduction of bis(acetylacetonato)copper(II)

1983 ◽  
Vol 61 (5) ◽  
pp. 801-808 ◽  
Author(s):  
Yuan L. Chow ◽  
Gonzalo E. Buono-Core ◽  
Bronislaw Marciniak ◽  
Carol Beddard
Keyword(s):  
Rate Constant ◽  
Rate Constants ◽  
Flash Photolysis ◽  
Decay Rates ◽  
Polynuclear Aromatic Hydrocarbons ◽  
Aromatic Ketone ◽  
Quantum Yields ◽  
Triplet States ◽  
Quenching Rate ◽  
Triplet Energy

Bis(acetylacetonato)copper(II), Cu(acac)2, quenches triplet excited states of ketones and polynuclear aromatic hydrocarbons efficiently, but only aromatic ketones with high triplet energy successfully sensitize photoreduction of Cu(acac)2 in alcohols under nitrogen to give derivatives of aeetylacetonatocopper(I), Cu(acac). For the triplet state benzophenone-sensitized photoreduction of Cu(acac)2, the quantum yields of photoreduction (ΦC) and those of benzophenone disappearance (ΦB) were determined in methanol with various concentrations of Cu(acac)2. The values of the quenching rate constant, kq, determined from these two types of monitors on the basis of the proposed mechanism were in good agreement (6.89 ~ 7.35 × 109 M−1 s−1). This value was higher, by a factor of about two, than that obtained from the monitor of the benzophenone triplet decay rates generated by flash photolysis in the presence of Cu(acac)2. The quenching rate constants of various aromatic ketone and hydrocarbon triplet states by Cu(acac)2 were determined by flash photolysis to be in the order of the diffusion rate constant and the quantum yields of these photoreductions were found to be far from unity. Paramagnetic quenching, with contributions of electron exchange and charge transfer, was proposed as a possible quenching mechanism. For a series of aromatic ketone sensitizers with higher triplet energy, this mechanism was used to rationalize the observed high quenching rate constants in contrast to the low quantum yields of photoreduction.

Wavelength controlled production of SO4- radicals in the ultraviolet photolysis of ceric sulfate solutions

1984 ◽  
Vol 37 (3) ◽  
pp. 475 ◽  
Author(s):  
RW Matthews
Keyword(s):  
Rate Constants ◽  
Photochemical Reaction ◽  
Transfer Reaction ◽  
Quantum Yields ◽  
Oh Radical ◽  
Transfer Energy ◽  
Fluorescence Measurements ◽  
Sulfate Solutions ◽  
Ultraviolet Photolysis ◽  
Primary Photochemical Reaction

Solutions of cerium(III)/(IV) and formic acid in 0.4 M sulfuric acid have been photolysed under 254 nm and 365 nm light. Marked differences in the reaction kinetics and quantum yields are observed at the two different wavelengths. At 365 nm, the reactions leading to cerium(IV) reduction are caused almost exclusively by the SO4- radical. The ratio of rate constants, k(SO4- + CeIII)/ k(SO4- + HCOOH), is 116 � 11 and the quantum yield of sulfate radicals, ф(SO4-), is 0.023 � 0.002. At 254 nm, the reactions leading to cerium(IV) reduction are caused mainly by the OH radical, but approximately 35% of the oxidizing radicals formed in the primary photochemical reaction are SO4-. Cerium(III) species, excited at 254 nm, transfer energy to cerium(IV) and this results in an additional yield of OH and SO4- radicals. Fluorescence measurements confirmed the efficiency of the energy transfer reaction. The ratio of rate constants, k(OH+CeIII)/k(OH+HCOOH), is 2.22 � 0.18 and ф(CeIV*) and ф(CelIII*) giving oxidizing radicals are 0.116 � 0.010 and 0.0083 � 0.0008 respectively. Thus about 5 times more total oxidizing radicals are produced from excited cerium(IV) species at 254 nm than at 365 nm.

scholarly journals Probing Protein Shelf Lives from Inverse Mean First Passage Times

2019 ◽  
Author(s):  
Vishal Singh ◽  
Parbati Biswas
Keyword(s):  
Protein Aggregation ◽  
Rate Constants ◽  
Survival Probability ◽  
First Passage Time ◽  
Passage Time ◽  
First Passage ◽  
First Order Kinetics ◽  
The Mean ◽  
Passage Times ◽  
Good Agreement

Protein aggregation is investigated theoretically via protein turnover, misfolding, aggregation and degradation. The Mean First Passage Time (MFPT) of aggregation is evaluated within the framework of Chemical Master Equation (CME) and pseudo first order kinetics with appropriate boundary conditions. The rate constants of aggregation of different proteins are calculated from the inverse MFPT, which show an excellent match with the experimentally reported rate constants and those extracted from the ThT/ThS fluorescence data. Protein aggregation is found to be practically independent of the number of contacts and the critical number of misfolded contacts. The age of appearance of aggregation-related diseases is obtained from the survival probability and the MFPT results, which matches with those reported in the literature. The calculated survival probability is in good agreement with the only available clinical data for Parkinson’s disease.<br>

Vitrimer enhanced carbazole-based organic room-temperature phosphorescent materials

2021 ◽  
Author(s):  
Tianqi Xu ◽  
Peng Wu ◽  
Lingyun Lou ◽  
Yuzhan Li ◽  
Dong Wang ◽  
...  
Keyword(s):  
Room Temperature ◽  
Radiative Transition ◽  
Quantum Yields

Organic room-temperature phosphorescent(RTP) materials have promising applications, but due to the lack of inter-system scaling and susceptibility to non-radiative transition, they typically have low quantum yields (<2%) and short lifetimes...

The Mean Lifetimes of Carbon, Nitrogen, and Oxygen Nuclei in the CNO Bicycle.

1962 ◽  
Vol 136 ◽  
pp. 453 ◽  
Author(s):  
Georgeanne R. Caughlan ◽  
William A. Fowler
Keyword(s):  
The Mean ◽  
Mean Lifetimes

Luminescence of 5-Phenyltetrazole and its Derivatives. Part II. Phosphorescence

1984 ◽  
Vol 39 (6) ◽  
pp. 556-559 ◽  
Author(s):  
I. Gryczyński ◽  
A. Kawski ◽  
Z. Grzonka ◽  
A. Rażyńska
Keyword(s):  
Triplet State ◽  
Quantum Yields ◽  
Intersystem Crossing ◽  
Thermal Deactivation ◽  
Fluorescence Quantum Yields ◽  
Radiative Transitions ◽  
Polyvinyl Alcohol Film ◽  
Methyl Derivatives ◽  
Temperature Responses ◽  
Phosphorescence Spectra

The phosphorescence spectra, mean lifetimes of phosphorescence and ratios of phosphorescence/ fluorescence quantum yields have been measured for 5-phenyltetrazole and its three methyl derivatives in a polyvinyl alcohol film over the temperature range of (77-250) K. Temperature responses of the non-radiative intersystem crossing constant. KST, and the non-radiative triplet state deactivation constant, km, have been investigated on the basis of these measurements. The energy of activation for the non-radiative transitions has been determined. With the methyl 5-phenyltetrazoles, the thermal deactivation of the triplet state, contrary to the intersystem crossing, has been found to be influenced by the position of the methyl substituent in the phenyl ring.

scholarly journals GC×GC measurements of C<sub>7</sub>-C<sub>11</sub> aromatic and n-alkane hydrocarbons on Crete, in air from Eastern Europe during the MINOS campaign

2003 ◽  
Vol 3 (5) ◽  
pp. 1461-1475 ◽  
Author(s):  
X. Xu ◽  
C. Williams ◽  
H. Plass-Dülmer ◽  
H. Berresheim ◽  
G. Salisbury ◽  
...  
Keyword(s):  
Rate Constants ◽  
Field Measurements ◽  
Early Morning ◽  
Reaction Model ◽  
Sequential Reaction ◽  
Related Data ◽  
Mixing Ratios ◽  
Ground Station ◽  
The Mean ◽  
The Relationship

Abstract. During the Mediterranean Intensive Oxidant Study (MINOS) campaign in August 2001 gas-phase organic compounds were measured using comprehensive two-dimensional gas chromatography (GCxGC) at the Finokalia ground station, Crete. In this paper, C7-C11 aromatic and n-alkane measurements are presented and interpreted. The mean mixing ratios of the hydrocarbons varied from 1±1 pptv (i-propylbenzene) to 43±36 pptv (toluene). The observed mixing ratios showed strong day-to-day variations and generally higher levels during the first half of the campaign. Mean diel profiles showed maxima at local midnight and late morning, and minima in the early morning and evening. Results from analysis using a simplified box model suggest that both the chemical sink (i.e. reaction with OH) and the variability of source strengths were the causes of the observed variations in hydrocarbon mixing ratios. The logarithms of hydrocarbon concentrations were negatively correlated with the OH concentrations integral over a day prior to the hydrocarbon measurements. Slopes of the regression lines derived from these correlations for different compounds are compared with literature rate constants for their reactions with OH. The slopes for most compounds agree reasonably well with the literature rate constants. A sequential reaction model has been applied to the interpretation of the relationship between ethylbenzene and two of its potential products, i.e. acetophenone and benzeneacetaldehyde. The model can explain the good correlation observed between [acetophenone]/[ethylbenzene] and [benzeneacetaldehyde]/[ethylbenzene]. The model results and field measurements suggest that the reactivity of benzeneacetaldehyde may lie between those of acetophenone and ethylbenzene and that the ratio between yields of acetophenone and benzeneacetaldehyde may be up to 28:1. Photochemical ages of trace gases sampled at Finokalia during the campaign are estimated using the sequential reaction model and related data. They lie in the range of about 0.5-2.5 days.

Laser flash photolysis studies of the formation and reactivities of phenyl(naphthyl)methyl carbocations generated from phosphonium salt precursors

1992 ◽  
Vol 70 (6) ◽  
pp. 1784-1794 ◽  
Author(s):  
E. O. Alonso ◽  
L. J. Johnston ◽  
J. C. Scaiano ◽  
V. G. Toscano
Keyword(s):  
Rate Constants ◽  
Phosphonium Salt ◽  
Flash Photolysis ◽  
Laser Flash Photolysis ◽  
Ion Pairs ◽  
Laser Flash ◽  
Product Formation ◽  
Quantum Yields ◽  
Back Reaction ◽  
Transient Experiments

The photolysis of several substituted phenyl(naphthyl)methyl triphenylphosphonium chlorides has been examined using a combination of laser flash photolysis experiments and product studies. Both carbocation and radical intermediates have been characterized in the transient experiments, with the relative yields depending strongly on the solvent. For example, in alcohols, acetonitrile, or aqueous solvents cation formation predominates while acetonitrile/dioxane mixtures (5–10%) are required for the observation of radicals. Quantum yields for cation formation vary from 0.79 in methanol to 0.093 in 1:4 acetonitrile/dioxane, as measured by product studies and transient experiments, respectively. The addition of perchlorate salts leads to dramatic enhancements in the cation lifetimes; the effects are particularly pronounced for acetonitrile/dioxane mixtures where the cation yields also increase by factors of 3–4. In this case the effects are attributed primarily to replacement of chloride by perchlorate in the initial ion pairs. The combined data from both solvent and perchlorate salt effects on the cation lifetimes and yields suggest that the excited state of the phosphonium salt cleaves homolytically, followed by electron transfer within the initial radical/triphenylphosphine radical cation pair to generate carbocation, as opposed to direct heterolytic cleavage. The cation yields also indicate that back reaction to regenerate starting material, as well as product formation within the initial geminate cage, occur in some solvents. The effects of solvent and added perchlorate salts on the rate constants for reaction with nucleophiles have been examined. For example, rate constants that vary by an order of magnitude have been measured for quenching by azide ion in various aqueous acetonitrile and trifluoroethanol mixtures.

Statistical Modeling of Pharmacokinetic Systems

1976 ◽  
Vol 98 (1) ◽  
pp. 37-43 ◽  
Author(s):  
J. O. Tsokos ◽  
C. P. Tsokos
Keyword(s):  
Oral Administration ◽  
Drug Concentration ◽  
Rate Constants ◽  
Pharmacokinetic Model ◽  
Compartmental Model ◽  
Statistical Treatment ◽  
Numerical Comparison ◽  
The Mean ◽  
Intravenous And Oral Administration ◽  
Initial Drug

A statistical treatment of a pharmacokinetic compartmental model is described, wherein the initial drug concentration and/or the rate constants governing the distribution of the drug between the appropriate compartments are considered to be random variables. A specific pharmacokinetic model which describes the profile of the antibiotic coumermycin A, following intravenous and oral administration in man, is stochastized and a numerical comparison between the deterministic and the mean of the random solutions as a function of time is presented.

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