Rate constant for the deactivation of O2 (A3Σu+ by N2

A value of (9.3 ± 1.7) × 10^?15 cm³ molecule ^?1 has been determined as the rate constant for the quenching of O₂(A ³Σ_u⁺) by N₂ at 25°C.     

Reactive and non-reactive quenching of O(1D2) by COF2

Quenching of O(¹D₂) by COF₂ has been investigated by time-resolved resonance fluorescence monitoring of the product O(³P_J) following 248 nm pulsed laser photolysis of O₃. The rate constant for total removal of O(¹D₂) by COF₂ is (7.4 ± 1.2) × 10^?11 cm³ molecule^?1 s^?1. 71 ± 7% of the quenching interactions result in formation of O(³P^J).     

Vibration—vibration energy exchange between carbon monoxide and carbon dioxide

Measurements have been made on the vibration—vibration (V—V) energy exchange rate between carbon monoxide and carbon dioxide in the temperature range 180 to 345 K. A steady-state vibrational fluorecence quenching technique was used in conjunction with an open flow gas system. Vibrational excitation of the carbon monoxide was accomplished by absorption of infrared radiation from prospane—oxygen flames. The measured rate constant for the process CO* (υ = 1) + CO₂ → CO + CO^*₂(001) increased linearly with temperature, and after correction for the V—V exchange rate fo the back reaction, the rate constant has a value of (2.2 ± 0.3) × 10³ torr^?1 s^?1 at 296 K. The data are compared to results at highest temperatures and to available theoretical calculations.     

Photoinduced electron transfer of [ Ru (bpy)_2 (4, 4'-dcbpy)]~(2 ) with electron donors

Emission quenching of [Ru(bpy)2(4, 4'-dcbpy)] (PF6)2 (1) by benzenamine,4-[2-[5-[4-[4-dimethylamino]phenyl]-4,5-di-hydro-1-phenyl-1H-pyrazol-3-yl]-ethenyl]-N,N-dimetyl (2) or 1, 5-diphenyl-3-(2-phenothiazine)-2-pyrazoline (3) was observed. Measurements of the emission decay of 1 before and after addition of 2 or 3 by single photon counting technique con-finned the observations. The emission quenching of 1 by 2 or 3 was submitted to Stern-Volmer equation. It was calculated that the quenching rate constants (kq) are 5.5 × 109(mol/L)-1s-1 for 2 and 4.0 × 109(mol/L)-1s-1 for 3, respectively. These results indicated a character of dynamic quenching process. The singlet-state of 2 or 3 was also quenched by 1. The quenching behaviors did not conform to the Stern- Volmer equation and involved both static and dynamic quenching processes. The apparent quenching rate constant (kapp) was calculated to be 3 × 109 (mol/L)-1 for the interaction of excited 2 with 1, and 1.2 × 109 (mol/L)-1 for that of excited 3 wit     

Intermolecular interaction between squarylium cyanine and porphyrin

In this paper, the interaction between squarylium cyanine and porphyrin in chloroform is investigated by absorption and fluorescence spectroscopy. Emphasis has been put on the mechanism of intermolecular energy transfer. The overlap integral J between the absorption spectrum of squarylium cyanine and the fluorescence spectrum of porphyrin was calculated, which reveals that the singlet-singlet energy transfer may occur from porphyrin to squarylium cyanine in solution. In comparison of the observed rate constant [kqII=6.1 ×1013 (mol/L)-1·s-1] for fluorescence quenching of porphyrin by squarylium cyanine with the diffusion rate constant in chloroform [kdif=1.1×1010 (mol/L)-1·s-1] and the rate of energy transfer [ket≤6.7×104 (mol/L)-1·s-1 in the experimentally dilute solutions] estimated from Forster formula, the possibility of energy transfer by electron exchange or/and coulombic mechanism could be excluded. So it has been definitely convinced that the intermolecuiar energy transfer between them is     

Photoinitiated quenching reactions of excited triplet duroquinone by vitamin C in homogeneous and AOT (SDS) micelle solutions

Time-resolved EPR has been used to study the photoinitiated reactions of the excited triplet of duroquinone (³DQ^*) quenched by the antioxidant vitamin C (VC) in homogeneous solutions of ethylene glycol/water (EG/H₂O) and micelle solutions of aerosol OT (AOT) and sodium dodecyl sulphate (SDS). During the photolysis reactions of DQ and VC in homogeneous solutions of EG/H₂O, ³DQ^* abstracts hydrogen atoms from the solvent EG and the antioxidant VC. The rate constant for the quenching of ³DQ^* by VC is 4.90 × 10⁷ L mol^?1 s^?1, close to being diffusion-controlled. In AOT and SDS micelle solutions, rate constants for the quenching of ³DQ^* by VC are 3.28 × 10⁷ and 3.15 × 10⁷ L mol^?1 s^?1, respectively. Lipid-soluble ³DQ* and water-soluble VC need to diffuse to the w/o interface to react, which reduces the reaction rate between ³DQ* and VC. The charge repulsion interaction between the anionic shell of AOT (SDS) micelles and the VC monoanions AsH^? also slows the reaction.     

Quenching of triplet excitions by trapped holes in crystalline pyrene

The rate of quenching of triplet excitions by trapped holes in crystalline pyrene has been measured as a function of hole concentration. The rate constant is γ=4.5×10^?11 cm³ sec^?1 within 50%, not far below that of a diffusion limited process. The quenching by free holes is not observed in the experimental conditions used.     

Investigation on the Inclusion Behavior of ApoCopC with Vitamin B6

In neutral phosphate buffer solution of pH 7.0, the interaction between apoCopC and Vitamin B₆ has been investigated in detail by means of fluorescence spectroscopy. According to the change of Vitamin B₆ fluorescence spectra and fluorescence polarization, we can conclude that a novel supramolecular system is generated. ApoCopC can form a 1:5 host-guest inclusion supramolecular complex with Vitamin B₆, and the formation constant has been calculated to be (2.24 ± 0.08) × 10⁴ M^? 1. It suggests the strong inclusion ability of apoCopC to the guest molecules. In addition, the mechanism of the apoCopC protein fluorescence quenching by Vitamin B₆ was also discussed. And based on the Stern-Volmer equation, the apparent quenching constant was estimated to be (2.75 ± 0.05) × 10⁴ M^? 1.     

Comparison of singlet methylene removal rates by group IV hydrides

The technique of laser flash photolysis/laser absorption has been used to obtain an absolute removal rate constant of (3.85 ± 0.18) × 10^?10 cm³ molecule^?1 s^?1 for singlet methylene, ¹CH₂ (ã¹A₁), with germane (GeH₄) at ambient temperature. The removal rate constant is compared with the values for methane (CH₄) and silane (SiH₄) which have been determined previously. © 1995 John Wiley & Sons, Inc.     

Gas phase reaction of the hydroxyl radical with the unsaturated peroxyacyl nitrate CH2C(CH3)C(O)OONO2

The gas phase reaction of the hydroxyl radical with the unsaturated peroxyacyl nitrate CH₂ ? C(CH₃)C(O)OONO₂ (MPAN) has been studied at 298 ± 2 K and atmospheric pressure. The OH-MPAN reaction rate constant relative to that of OH + n-butyl nitrate is 2.08 ± 0.25. This ratio, together with a literature rate constant of 1.74 × 10^?12 cm³ molecule^?1 s^?1 for the OH + n-butyl nitrate reaction at 298 K, yields a rate constant of (3.6 ± 0.4)× 10^?12 cm³ molecule^?1 s^?1 for the OH-MPAN reaction at 298 ± 2 K. Hydroxyacetone and formaldehyde are the major carbonyl products. The yield of hydroxyacetone, 0.59 ± 0.12, is consistent with preferential addition of OH at the unsubstituted carbon atom. Atmospheric persistence and removal processes for MPAN are briefly discussed. © 1993 John Wiley & Sons, Inc.     

Synthesis,structural characterization and DNA-binding studies of a new cobalt (II) complex: (HAcr)<Subscript>4</Subscript>[Co(Sal)<Subscript>3</Subscript>]

A new cobalt (II) coordination compound was synthesized using proton transfer mechanism. The reaction between CoCl₂·2H₂O, Salicylic acid (H₂Sal) and acridine (Acr) gave a new coordination compound formulated as (HAcr)₄[Co(Sal)₃], which was characterized by elemental analysis, NMR, IR and UV/Vis spectroscopies. The interaction of this complex with DNA has been investigated in vitro using UV absorption, fluorescence spectroscopy, viscosity measurements and gel electrophoresis methods. The intrinsic binding constant has been estimated to be 5.8 × 10⁵ M^?1 using UV absorption. The interaction of DNA–Co (II) complex caused quenching in fluorescence. The binding constant, the number of binding site and Stern–Volmer quenching constant have been calculated to be 7.7 × 10⁴ M^?1, 1.143 and 1.5 × 10⁴ Lmol^?1, respectively. The increase in the viscosity of DNA with increasing the concentration of the Co (II) complex and the observations of other experiments suggest that the cobalt (II) complex binds to DNA by partial intercalation binding mode. Furthermore, the interaction of DNA–Co (II) complex was confirmed using gel electrophoresis studies. Moreover, molecular docking technique predicted partial intercalation binding mode for the complex.     

Photoinduced Degradation of the Herbicide Clomazone Model Reactions for Natural and Technical Systems

The photodegradation of the herbicide clomazone in the presence of S₂O₈^2? or of humic substances of different origin was investigated. A value of (9.4 ± 0.4) × 10⁸ m ^?1 s^?1 was measured for the bimolecular rate constant for the reaction of sulfate radicals with clomazone in flash‐photolysis experiments. Steady state photolysis of peroxydisulfate, leading to the formation of the sulfate radicals, in the presence of clomazone was shown to be an efficient photodegradation method of the herbicide. This is a relevant result regarding the in situ chemical oxidation procedures involving peroxydisulfate as the oxidant. The main reaction products are 2‐chlorobenzylalcohol and 2‐chlorobenzaldehyde. The degradation kinetics of clomazone was also studied under steady state conditions induced by photolysis of Aldrich humic acid or a vermicompost extract (VCE). The results indicate that singlet oxygen is the main species responsible for clomazone degradation. The quantum yield of O₂(a¹Δ_g) generation (λ = 400 nm) for the VCE in D₂O, Φ_Δ = (1.3 ± 0.1) × 10^?3, was determined by measuring the O₂(a¹Δ_g) phosphorescence at 1270 nm. The value of the overall quenching constant of O₂(a¹Δ_g) by clomazone was found to be (5.7 ± 0.3) × 10⁷ m ^?1 s^?1 in D₂O. The bimolecular rate constant for the reaction of clomazone with singlet oxygen was k_r = (5.4 ± 0.1) × 10⁷ m ^?1 s^?1, which means that the quenching process is mainly reactive.     

Rate coefficients for CS reactions with O2, O3 and NO2 AT 298 K

CS radicals have been produced by photodissociation of CS₂ at 193 nm and their disappearance monitored by LIF. The vibrationally excited CS radicals rapidly relax to CS(ν = 0). At 298 K, the rate coefficients for CS(ν = 0) reactions with O₂, O₃ and NO₂ are (2.9 ± 0.4) × 10_?19, (3.0 ± 0.4) × 10^?16 and (7.6 ± 1.1) × 10^?17 cm³ molecule^?1 s^?1 respectively. The quenching of CS(A ¹II)_ν=0 by He has a rate coefficient of (1.3 ± 0.2) × 10^?12 cm³ molecule^?1 s^?1.     

IONIC STRENGTH EFFECTS ON THE GROUND STATE COMPLEXATION and TRIPLET STATE ELECTRON TRANSFER REACTION BETWEEN ROSE BENGAL and METHYL VIOLOGEN

Abstract— The equilibrium constants, K_c, for complexation between methyl viologen dication (MV²+) and Rose Bengal, or Eosin Y, decrease with increasing ionic strength. At zero ionic strength K_c is 6500 (± 500) mol^?1 dm³ for Rose Bengal and 3200 (± 200) mol^?1 dm³ for Eosin Y, and these values decrease to 1500 (± 100) and 680 (± 40) mol^?1 dm³, respectively, at an ionic strength of 0.1 mol dm^?3. K_c is independent of pH between 4.5 and 10. ΔH is -25 (± 1) kJ mol^?1 for complexation with either dye, whereas ΔS is -15 (± 3) J K^?1 mol^?1 for Rose Bengal, and - 23 (± 3) J K^?1 mol^?1 for Eosin Y. The complexation constant for Rose Bengal and the neutral viologen, 4,4'-bipyridinium-N, N'-di(propylsulphonate), (4,4'-BPS), is 420 (± 35) mol^?1 dm³, and independent of ionic strength. No complexation could be observed for either Rose Bengal or Eosin with another neutral viologen, 2,2'-bipyridinium-N,N'-di(propylsulphonate), (2,2'-BPS). MV²+ quenches the triplet state of Rose Bengal with a rate constant of 7 × 10⁹ mol^?1 dm³ s^?1, and this rate constant decreases slightly as ionic strength increases. The cage escape yield following quenching, Φ_cc is very low (Φ_cc= 0.02 (± 0.005), and independent of ionic strength. 4,4'-BPS quenches the triplet state of Rose Bengal with a rate constant of 2.2 (± 0.1) × 10⁹ mol^?1 dm³ s^?1, and gives a cage escape yield of 0.033 (± 0.006). 2,2'-BPS quenches the Rose Bengal triplet with a rate constant of 6 (± 1) × 10⁸ mol^?1 dm³ s^?1 and gives a cage escape yield of 0.07 (± 0.01). Conductivity measurements indicate that MV²+(Cl^?)₂ is completely dissociated at concentrations below 2 × 10^?2 mol dm^?3.     

Micelle-Catalyzed Interaction Between [Ni(II)-Gly-Gly]+ and Ninhydrin

The effect of cationic micelles of cetyltrimethyl ammonium bromide (CTAB) on the observed pseudo-first-order rate constant for the interaction of nickel dipeptide complex [Ni(II)-Gly-Gly]⁺ with ninhydrin has been studied spectrophotometrically. At constant temperature and pH, increase in the [CTAB] from 0.0 to 60.0 × 10^?3 mol dm^?3 caused nearly three-fold increase of the rate constant. The micellar catalysis is explained in terms of the pseudophase model. From the observed kinetic data, binding constants of micelle–[Ni(II)-Gly-Gly]⁺ (K _S), and micelle–ninhydrin (K _N) are evaluated, respectively, to be 5.3 mol^?1 dm³ and 84.0 mol^?1 dm³. The role of added inorganic (NaCl, NaBr, Na₂SO₄) and organic salts (NaBenz, NaSal) on the reaction rate has also been examined.     

Quenching of C2(a 3Πu) produced in an intense infrared laser field

C₂(a ³Π_u) has been produced in the multiple-photon dissociation of acrylonitrile, C₂H₃CN, by a TEA CO₂ laser. Laser-induced fluorescence has been used to determine time-resolved relative C₂ concentrations in the presence of added Ar and O₂ and second-order rate constants of 2 × 10^?15 and 3.4 × 10^?12 cm³ molecule^?1 5^?1 have been obtained for these two quenchers, respectively. Vacuum-ultraviolet chemiluminescence is observed in the quenching by O₂.     

Mechanism and kinetics of the reaction between hydrogen iodide and ozone

The reaction between hydrogen iodide and ozone at 295 K has been investigated by the resonance fluorescence method applied to the detection of iodine atoms. A chain mechanism is suggested for this reaction. The chain initiation rate constant is k ₁ = (5.45 ± 1.80) × 10^?17 cm³/s, and the chain propagation rate constant is k ₃ = (1.1 ± 0.4) × 10^?12 cm³/s.     

Kinetics of the reaction of NH2 with NO2

The absolute rate constant of the reaction of NH₂ with NO₂ has been measured using a flash-photolysis laser resonance-fluorescence technique. The value obtained at room temperature is k₁ = 2.3 (± 0.2) × 10^?11 cm³ molecule ^?1 s^?1. A negative temperature coefficient has been found between 298 and 505 K for this reaction, k₁ = 3.8 × 10^?8 × T^?1.30 cm³ molecule^?1 s^?1. It is thought that this is the major reaction of NH₂ in the troposphere.     

Rate constant and a detailed error analysis for C2H3 + H reaction

The production and reactions of vinyl radicals and hydrogen atoms from the photolysis of vinyl iodide (C₂H₃I) at 193 nm have been examined employing laser photolysis coupled to kinetic-absorption spectroscopic and gas chromatographic product analysis techniques. The time history of vinyl radicals in the presence of hydrogen atoms was monitored using the 1,3-butadiene (the vinyl radical combination product) absorption at 210 nm. By employing kinetic modeling procedures a rate constant of 1.8 × 10^?10 cm² molecule^?1 s^?1 for the reaction C₂H₃ + H has been determined at 298 K and 27 KPa (200 torr) pressure. A detailed error analysis for determination of the C₂H₃ + H reaction rate constant, the initial C₂H₃ and H concentrations are performed. A combined uncertainty of ±0.43 × 10^?10 cm² molecule^?1 s^?1 for the above measured rate constant has been evaluated by combining the contribution of the random errors and the systematic errors (biases) due to uncertainties of each known parameter used in the modeling. © 1995 John Wiley & Sons, Inc.