Atmospheric chemistry of CH3CHF2 (HFC-152a): kinetics, mechanisms, and products of Cl atom- and OH radical-initiated oxidation in the presence and absence of NO(x)

Smog chamber/Fourier transform infrared (FTIR) and laser-induced fluorescence (LIF) spectroscopic techniques were used to study the atmospheric degradation of CH3CHF2. The kinetics and products of the Cl(2P(3/2)) (denoted Cl) atom- and the OH radical-initiated oxidation of CH3CHF2 in 700 Torr of air or N2; diluents at 295 +/- 2 K were studied using smog chamber/FTIR techniques. Relative rate methods were used to measure k(Cl + CH3CHF2) = (2.37 +/- 0.31) x 10(-13) and k(OH + CH3CHF2) = (3.08 +/- 0.62) x 10(-14) cm3 molecule(-1) s(-1). Reaction with Cl atoms gives CH3CF2 radicals in a yield of 99.2 +/- 0.1% and CH2CHF2 radicals in a yield of 0.8 +/- 0.1%. Reaction with OH radicals gives CH3CF2 radicals in a yield >75% and CH2CHF2 radicals in a yield <25%. Absolute rate data for the Cl reaction were measured using quantum-state selective LIF detection of Cl(2P(j)) atoms under pseudo-first-order conditions. The rate constant k(Cl + CH3CHF2) was determined to be (2.54 +/- 0.25) x 10(-13) cm3 molecule(-1) s(-1) by the LIF technique, in good agreement with the relative rate results. The removal rate of spin-orbit excited-state Cl(2P(1/2)) (denoted Cl) in collisions with CH3CHF2 was determined to be k(Cl + CH3CHF2) = (2.21 +/- 0.22) x 10(-10) cm3 molecule(-1) s(-1). The atmospheric photooxidation products were examined in the presence and absence of NO(x). In the absence of NO(x)(), the Cl atom-initiated oxidation of CH3CHF2 in air leads to formation of COF2 in a molar yield of 97 +/- 5%. In the presence of NO(x), the observed oxidation products include COF2 and CH3COF. As [NO] increases, the yield of COF2 decreases while the yield of CH3COF increases, reflecting a competition for CH3CF2O radicals. The simplest explanation for the observed dependence of the CH3COF yield on [NO(x)] is that the atmospheric degradation of CH3CF2H proceeds via OH radical attack to give CH3CF2 radicals which add O2 to give CH3CF2O2 radicals. Reaction of CH3CF2O2 radicals with NO gives a substantial fraction of chemically activated alkoxy radicals, [CH3CF2O]. In 1 atm of air, approximately 30% of the alkoxy radicals produced in the CH3CF2O2 + NO reaction possess sufficient internal excitation to undergo "prompt" (rate >10(10) s(-1)) decomposition to give CH3 radicals and COF2. The remaining approximately 70% become thermalized, CH3CF2O, and undergo decomposition more slowly at a rate of approximately 2 x 10(3) s(-1). At high concentrations (>50 mTorr), NO(x) is an efficient scavenger for CH3CF2O radicals leading to the formation of CH3COF and FNO.     

Role of edge-to-face interaction between aromatic rings in clathrate formation of 1-benzoyl-2-hydroxyindoline derivatives with benzene. X-ray crystal and PM6 analyses of the interaction

(4-Nitrophenyl- and 4-chlorophenyl)(2-hydroxy-3,3-dimethylindolin-1-yl)methanone (4a,b) serve as clathrate hosts for benzene guests. X-ray crystal analyses of the inclusion compounds of 4a and 4b with benzene indicate that the ‘edge-to-face interaction’ plays an important role in the formation of the inclusion complexes with benzene as well as in the host-host interactions. PM6 molecular orbital calculations were found to reproduce the characteristic structural features of both intra- and intermolecular edge-to-face interactions.     

Photobiological information obtained from XPA gene-deficient mice

The XPA gene-deficient mouse, an animal model of xeroderma pigmentosum (XP), develops enhanced photobiologic reactions including acute inflammation, immunosuppression and skin carcinogenesis, because of the defect in the excision repair of ultraviolet-induced DNA lesions. The results strongly suggest that nuclear DNA is an important chromophore to initiate acute and chronic skin damages. The model mouse is a useful experimental animal not only to investigate the mechanisms of photosensitivity in XP, but also to study physiological photobiology in humans, because photobiologic reactions are greatly intensified in this mouse.     

cis-to-trans isomerization promoted by pyridine as a crucial step for the selective preparation of trans-Pt(SAr)(Cl)(PAr'3)2

The general strategy for the syntheses of trans-Pt(SAr)(Cl)(PAr'3)2 (1) (Ar = Ph, C6H4-2-Me, C6H4-3-OMe C6H4-2-F, etc.; Ar' = Ph, C6H4-4-OMe, C6H4-4-Me, and C6H4-4-CF3) by the reaction of cis-PtCl2(PAr'3)2 with ArSH has been developed. The mechanistic investigation suggested that isomerization of cis-1 into trans-1 promoted by the combined use of C6H6 as a solvent and pyridine as a base was the key to the successful preparation of 1.     

Evaluation of electrodeposited gold nanostructures for applications in QCM sensing

The electrodeposition of gold nanostructures increases the surface area of a biosensor, which brings an enhancement of the sensitivity by increasing the amount of analyte binding to the surface. To evaluate the relationship among the surface structure, the area and the analyte binding, we quantitatively analyzed them for quartz crystal microbalance (QCM) sensing by scanning electron microscopy and cyclic voltammetry measurements. The results indicate a several-times increase of analyte bindings, and also the limitation of the sensing performance.     

Kinetics of the reactions of Cl*(2P(1/2)) and Cl(2P(3/2)) atoms with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH at 295 K

The title reactions were studied using laser flash photolysis/laser-induced-fluorescence (FP-LIF) techniques. The two spin-orbit states, Cl*(2P(1/2)) and Cl(2P(3/2)), were detected using LIF at 135.2 and 134.7 nm, respectively. Measured reaction rate constants were as follows (units of cm3 molecule(-1) s(-1)): k(Cl(2P(3/2))+CH3OH) = (5.35 +/- 0.24) x 10(-11), k(Cl(2P(3/2))+C2H5OH) = (9.50 +/- 0.85) x 10(-11), k(Cl(2P(3/2))+n-C3H7OH) = (1.71 +/- 0.11) x 10(-10), and k(Cl(2P(3/2))+i-C3H7OH) = (9.11 +/- 0.60) x 10(-11). Measured rate constants for total removal of Cl*(2P(1/2)) in collisions with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH were (1.95 +/- 0.13) x 10(-10), (2.48 +/- 0.18) x 10(-10), (3.13 +/- 0.18) x 10(-10), and (2.84 +/- 0.16) x 10(-10), respectively; quoted errors are two-standard deviations. Although spin-orbit excited Cl*(2P(1/2)) atoms have 2.52 kcal/mol more energy than Cl(2P(3/2)), the rates of chemical reaction of Cl*(2P(1/2)) with CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH are only 60-90% of the corresponding Cl(2P(3/2)) atom reactions. Under ambient conditions spin-orbit excited Cl* atoms are responsible for 0.5%, 0.5%, 0.4%, and 0.7% of the observed reactivity of thermalized Cl atoms toward CH3OH, C2H5OH, n-C3H7OH, and i-C3H7OH, respectively.     

Regioselective synthesis of substituted 1-indanols, 2,3-dihydrobenzofurans and 2,3-dihydroindoles by electrochemical radical cyclization using an arene mediator

Electrochemical reduction of haloarenes carrying 2-(1-hydroxybut-3-enyl), 2-allyloxy or N-allyl-N-methylamino group in the presence of phenanthrene as a mediator generated the corresponding aryl radicals and gave the corresponding 5-exo cyclization products in good yields. Higher regio- and stereoselectivities than those of usual radical cyclization using AIBN-Bu₃SnH were achieved.     

The effect of mixing particles of different size on the electrorheological response under steady shear flow

 The effect of mixing particles of different sizes on the electrorheological response of suspensions under steady shear flow was investigated. Two sizes, 15 μm and 50 μm, of monodisperse spherical sulfonated poly(styrene-co-divinylbenzene) particles were used. Several electrorheological fluids were made containing different proportions of small and large particles dispersed in silicone oil, but with constant overall particulate concentration. It was found that the mixed size system produced the highest electrorheological response under the shear rates used (10 s⁻¹ to 500 s⁻¹), which is the opposite trend to previous studies of bimodal systems with larger size ratios. Received: 21 December 2000 Accepted: 29 March 2001     

Direct Differentiation of the Types of Polarization Responsible for the Electrorheological Effect By a Dielectric Method

Debye polarization, ionic displacement polarization, and Maxwell-Wagner (interfacial) polarization are discussed in this paper, because they would most likely take place in an electrorheological (ER) suspension. The temperature dependences of the dielectric loss tangent maximums governed by these three types of polarization are theoretically found to be quite different. Given this fact, a method that can directly distinguish the polarization type and clarify which polarization would be mainly responsible for the ER effect is proposed. Two kinds of typical ER suspensions, heterogeneous particle type and homogeneous liquid crystalline polymer type, are studied using our method. It is found that Maxwell-Wagner polarization would be responsible for the ER effect both in a heterogeneous and in a homogeneous ER system. These findings present direct experimental evidence for the previous assumption that the Maxwell-Wagner polarization would dominate in the heterogeneous ER system and also shed light on the ER mechanism in a liquid crystalline polymer-type ER system. Copyright 2001 Academic Press.