The photolysis of SO2 at 3130 Å in the presence of cis- and trans-2-pentene

The photolysis of SO₂ at 3130 Å, FWHM = 165 Å, and 22°C has been investigated in the presence of cis- and trans-2-pentene. Quantum yields for the SO₂ photosensitized isomerization of one isomer to the other have been made for a variation in the [SO₂]/[C₅H₁₀] ratio of 3.41–366 for cis-2-C₅H₁₀ and of 1.28–367 for trans-2-C₅H₁₀. A kinetic analysis of each of these systems permitted new estimates to be made for the SO₂ collisionally induced intersystem crossing ratio at 3130 Å from SO₂(¹B₁) to SO₂(³B₁). The estimates of k_1a/(k_1a + k_1b) obtained are 0.12 ± 0.01 and 0.12 ± 0.02 (two different kinetic analyses in the cis-2-C₅H₁₀ study) and 0.20 ± 0.05 and 0.20 ± 0.04 (two different kinetic analyses in the trans-2-C₅H₁₀ study). Collisionally induced intersystem crossing ratios of k_2a/(k_2a + k_2b) = 0.51 ± 0.10 and k_3a/(k_3a + k_3b) = 0.62 ± 0.12 were obtained for cis- and trans-2-pentene, respectively. Quenching rate constants at 22°C for removal of SO₂(³B₁) molecules by cis- and trans-2-C₅H₁₀ were estimated as (1.00 ± 0.29) × 10¹¹ l./mole·sec and (0.857 ± 0.160) × 10¹¹ l./mole/sec, respectively. Prolonged irradiations, extrapolated to infinite irradiation times, for mixtures initially containing SO₂ and pure isomer, either the cis or trans, yielded a photostationary composition of [trans-2-pentene]/[cis-2-pentene] = 2.1 ± 0.1.     

Photochemistry of 5-phenyl-1-pentene in the gas phase

The photochemistry of the title compound has been studied in the gas phase using 254-nm irradiation. In addition to meta cycloadducts analogous to those observed in solution, population of S1(vib) in the gas phase gives several products, the relative amounts of which depend on quencher gas pressure but not on excitation wavelength. For example, in the absence of butane, the major photoproduct is compound 5. This product is formed by a [1,5] hydrogen shift in the primary photoproduct, compound 4. Compound 4 is an intramolecular meta cycloadduct that is generated in the gas phase with sufficient excess vibrational energy to undergo rearrangement unless quencher gas is present. Likewise, there is evidence that two other meta cycloadducts (2 and 3) are also formed with appreciable vibrational energy in the absence of a quencher gas. A unique intramolecular ortho cycloadduct is also formed from 1 but only within a narrow range of quencher gas pressures. This is a two-photon product, with the initial cycloadduct (11) ring opening to a cyclooctatriene (12) that photochemically closes to 6. The pressure dependence of this ortho cycloaddition may be due to a requirement for vibrational deactivation of 11 (Scheme 5) or a precursor species (Scheme 6). The overall chemistry is outlined in Scheme 7.     

The mechanism of the photochemical reactions of SO2 with isobutane excited at 3130 Å

The mechanism of the reactions of electronically excited SO₂ with isobutane has been studied through the measurement of the initial quantum yields of product formation in 3130 Å irradiated gaseous binary mixtures of SO₂ and isobutane and ternary mixtures of SO₂, isobutane, C₆H₆ or CO₂. Under low-pressure conditions (P < 10 torr) the kinetic treatment of the present data shows that only one singlet and one triplet state, presumably the ¹B₁ and ³B₁ states, are involved in the photoreaction mechanism. The data give k_2a = 8.4 × 10⁹; SO₂(¹B₁) + isobutane → products (2a); k_5a ? k₅ = 8.7 × 10⁸ l./mol·sec; SO₂(³B₁) + isobutane → products (5a) SO₂(³B₁) + isobutane → (SO₂) + isobutane (5b) k_1a/k₁ = 0.145 ± 0.037; SO₂(¹B₁) + SO₂ → SO₂(³B₁) + SO₂ (1a) SO₂(¹B₁) + SO₂ → (2SO₂) (1b) k_2b/k₂ = 0.273 ± 0.018; SO₂(¹B₁) + isobutane → SO₂(³B₁) + isobutane (2b); SO₂(¹B₁) + isobutane → (SO₂) + isobutane (2c) error limits are ± 2 σ. The contribution from the excited SO₂(¹B₁) molecules to the quantum yields of the photolyses of SO₂–isobutane mixtures is not negligible. Under high-pressure conditions (P > 10 torr) the low-pressure mechanism coupled with the saturation effect on the phosphorescence lifetimes of SO₂(³B₁) molecules cannot alone rationalize the quantum yields. The evaluation suggests that some nonradiative intermediate state (X) is involved in the formation of “extra” triplet molecules. This ill-defined state decays largely nonradiatively to SO₂ in experiments at low pressures, X → SO₂ (12). In the presence of C₆H₆ the low-pressure data give k₇ = (8.5 ± 1.8) × 10¹⁰, and the high-pressure data give k₇ = (8.3 ± 0.6) × 10¹⁰ and (9.9 ± 0.9) × 10¹⁰l./mol·sec; SO₂(³B₁) + C₆H₆ → nonradiative products (7). These estimates are in good agreement with values directly measured from low-pressure lifetime studies, (8.1 ± 0.7) × 10¹⁰ and (8.8 ± 0.8) × 10¹⁰l./mol·sec.     

The photolysis of N2O at 2139 Å and 1849 Å

The method of chemical difference was utilized to accurately determine the relative importance of all the reaction steps in the direct photolysis of N₂O at 2139 Å (25° and 250°C) and 1849 Å (25° C), as well as in the Hg6(¹P₁)-sensitized photolysis of N₂O at 1849 Å (25°C). In all cases, the primary process is predominantly, if not exclusively, Experiments with trace amounts of C₃H₆ added showed a slight, but not significant, difference in product ratios (N₂ and O₂). From these experiments the quantum yield of O(³P) from all possible sources was estimated as 0.02 ± 0.02. Experiments with excess N₂ at 1849 Å indicated that O(¹S) was not produced in the direct photolysis. The O(¹S) yield is probably zero, and certainly <0.05. The O(¹D) atom can react with N₂O via The ratio k₂/k₃ was found to be 0.69 ± 0.05 in all cases. When combined with other data from our laboratory, the average value is 0.65 ± 0.07. This represents the value for translationally energetic O(¹D) atoms. When excess He was added to remove the excess translational energy, k₂/k₃ rose to 0.83 ± 0.06, which is in reasonable agreement with the value of 1.01 ± 0.06 found in another laboratory. We conclude that for O(¹D) atoms with no excess thermal energy, k₂/k₃ = 0.90 ± 0.10.     

The photolysis of SO2 at 3080 Å in the presence of cis- and trans-1,2-difluoroethylene

The photolysis of SO₂ at 3080 Å, FWHM = 150 Å, and 22°C has been investigated in the presence of cis- and trans-C₂F₂H₂. Quantum yield measurements for the photosensitized isomerization of cis-C₂F₂H₂ to trans-C₂F₂H₂ have been made for a variation in the [SO₂]/[cis-C₂F₂H₂] ratio from 0.992 to 253. The results fit a mechanism which is consistent with the SO₂(³B₁) state being the reactive excited state of sulfur dioxide. A mechanism employing only the SO₂(¹B₁) and SO₂(³B₁) excited states is quite satisfactory to rationalize the data. A value for the SO₂ collisionally induced intersystem crossing efficiency from SO₂(¹B₁) to SO₂(³B₁) of 0.35 ± 0.14 was estimated while the cis-C₂F₂H₂ efficiency was found to be 0.030 ± 0.012. The rate constant at 22°C for the removal of SO₂(³B₁) molecules by cis-C₂F₂H₂ was found to be (1.43 ± 0.13) × 10¹⁰1./mole · sec. A photostationary composition, [cis]/[trans] = 1.0 ± 0.1, was found from prolonged irradiations of SO₂ in the presence of the cis and trans isomers.     

The photolysis of N2O at 1470 Å

The photolysis of pure N₂O, N₂O and N₂, and N₂O and C₃H₆ mixtures at 1470 Å and room temperature has been studied to determine the relative importance of the primary processes. The results are where ?{O(¹D)} = 0.515 represents both the O(¹D) produced in the primary act and that produced by collisional quenching of O(¹S); ?{N₂(³Σ)} = 0.084 represents only that portion of N₂(³?) which dissociates N₂O on deactivation; and ?{O(¹S)} = 0.38 – ±{N(²D)} represents only that portion of O(¹S) which enters into chemical reaction with N₂O. If the reaction of O(¹S) with N₂O yields only N₂ and O₂ as products, which seems likely from potential-energy curve considerations then ±{O(¹S)} = 0.135 ± 0.06 and ?{N(²D)} = 0.245 ± 0.06. Young and coworkers [4] have found from spectroscopic observations that the total quantum yield of O(¹S) is about 0.5. Thus it can be concluded that collisional removal of O(¹S) by N₂O yields mainly O(¹D) with chemical reaction being less important. Furthermore, most of the O(¹D) is produced this way, and the true primary yield of O(¹D) is about 0.15. The metastable N(²D) is not deactivated by N₂O, but is removed by chemical reaction to produce N₂ and NO. The results further indicate that N₂(³Σ) dissociates N₂O at least 80% of the time during quenching. The relative efficiency of N₂O compared to N₂ is about 2 for the removal of O(¹D). O(¹S) is removed about 90 times as efficiently by C₃H₆ as by N₂O.     

Kinetics of fluorescence decay of SO2 excited in the 2662–3273 Å region

The kinetics of fluorescence decay of SO₂ excited in the 2975–3273 Å region was studied using a powerful, frequency doubled, tunable dye laser system. The existence of two emitting species, first observed by Brus and McDonald, was confirmed. The collision-free lifetimes of the long-lived (L) species ranged from 100 to 300 μsec and the short-lived (S) species from 17 to 43 μsec over the wavelength range employed. The magnitude of the bimolecular quenching rate constant for the L state was a function of the excitation energy; the data show that about 1 kcal/mol of internal energy is lost per collision of the SO₂(L) species excited in the range of 2998–3107 Å. Studies of the relative initial fluorescence intensity of the S to that of the L state (I_S°/I_L°) were made in experiments which extended to 0.11 mtorr. The pressure dependence of the I_S°/I_L° ratio for experiments at 3107, 3211, and 3225 Åproved that the S and L states do not decay independently. Either efficient bimolecular S → L conversion occurs or bimolecular S ? L interconversion of both states is important. These data coupled with spectroscopic studies of Hamada and Merer and Shaw and coworkers favor the designation of the S and L states as SO₂(¹A₂) and SO₂(¹B₁), respectively. However, if the assignment is correct, then the band origin of the ¹B₁ state must be at a somewhat longer wavelength, λ> 3273 Å than tentative spectroscopic assignments suggest. Bimolecular quenching rate constants for the L and S components with various atmospheric gases were determined in 3130- and 2662-Å studies.     

Dynamic Coupling at the Ångström Scale

While momentum transfer from active particles to their immediate surroundings has been studied for both synthetic and biological micron‐scale systems, a similar phenomenon was presumed unlikely to exist at smaller length scales due to the dominance of viscosity in the ultralow Reynolds number regime. Using diffusion NMR spectroscopy, we studied the motion of two passive tracers—tetramethylsilane and benzene—dissolved in an organic solution of active Grubbs catalyst. Significant enhancements in diffusion were observed for both the tracers and the catalyst as a function of reaction rate. A similar behavior was also observed for the enzyme urease in aqueous solution. Surprisingly, momentum transfer at the molecular scale closely resembles that reported for microscale systems and appears to be independent of swimming mechanism. Our work provides new insight into the role of active particles on advection and mixing at the Ångström scale.     

X-Ray Structure of Bacteriorhodopsin at 2.5 Å Resolution

Microfocussed X-rays produced by an electron synchrotron were essential for the first structure elucidation of protein crystals having extremely small dimensions (5×20–40 μm). A further prerequisite for the successful crystal structure analysis of bacteriorhodopsin was a novel crystallization method using a lipid matrix. These methodological breakthroughs pave the way for further advances in structure determinations of membrane proteins.     

DFT, FT-Raman and FT-IR investigations of 5-o-tolyl-2-pentene

FT-IR and Raman spectra of 5-o-tolyl-2-pentene (OTP) have been experimentally reported in the region of 4000-10 cm(-1) and 4000-100 cm(-1), respectively. The optimized geometric parameters, normal mode frequencies and corresponding vibrational assignments of cis and trans isomers of OTP (C12H16) have been theoretically examined by means of B3LYP hybrid density functional theory (DFT) method together with 6-31G(d) and 6-31++G(d,p) basis sets. Furthermore, reliable vibrational assignments have made on the basis of potential energy distribution (PED) calculated. Comparison between the experimental and theoretical results indicates that density functional B3LYP method is able to provide satisfactory results for predicting vibrational wavenumbers and trans isomer is supposed to be the most stable form of OTP molecule.     

The SO2-sensitized phosphorescence of biacetyl vapor in photolyses at 2650 and 2875 Å. The intersystem crossing ratio in sulfur dioxide

Quantum yields of the triplet sulfur dioxide (³SO₂)-sensitized phosphoresence (Φ_sens) in biacetyl (Ac₂) have been determined in experiments over a wide range of pressures of SO₂ and Ac₂. Excited singlet sulfur dioxide (¹SO₂) was generated using 2650-Å and 28757hyphen;Å light. The values of Φ_sens were dependent on the [SO₂]/[Ac₂] ratio, as anticpated theoretically. However, in runs at a fixed [SO₂]/[Ac₂] ratio, the measured Φ_sens values were dependent on the total pressure. This theoretically unexpected effect is probably largely the result of biacetyl triplet diffusion with deactivation at the cell wall. Treatment of the quantum yield data in terms of the complete mechanism gave new estimates of the following rate functions: ¹SO₂ + SO₂ → (2SO₂) (1), ¹SO₂ + SO₂ → ³SO₂ + SO₂ (2), k₂/(k₁ + k₂) = 0.082 ± 0.003 (2650 Å), 0.095 ± 0.005 (2875 Å) ³SO₂ + Ac₂ → SO₂ + ³Ac₂ (9a), ³SO₂ + Ac₂ → SO₂ + Ac₂ (9b), k_9a + k_9b = (8.4 ± 2.1) × 10¹⁰ (2650 Å), (8.1 ± 3.0) × 10¹⁰ l./mole-sec (2875 Å) ³SO₂ → SO₂ + hv_p (6), k₆ = (7.3 ± 1.3) × 10¹ sec^?1.     

Temperature dependence of the rate constants of the reactions of oxygen atoms with 1-pentene, 1-hexene,cis-2-pentene,and trans-2-pentene

The kinetics of the reactions of ground state oxygen atoms with 1-pentene, 1-hexene, cis-2-pentene, and trans-2-pentene was investigated in the temperature range 200 to 370 K. In this range the temperature dependences of the rate constants can be represented by k = A′ Tⁿ exp(− E′_a/RT) with A′ = (1.0 ± 0.6) · 10⁻¹⁴ cm³ s⁻¹, n = 1.13 ± 0.02, E′_a = 0.54 ± 0.05 kJ mol⁻¹ for 1-pentene: A′ = (1.3 ± 1.2) · 10⁻¹⁴ cm³ s⁻¹, n = 1.04 ± 0.08, E′_a = 0.2 ± 0.4 kJ mol⁻¹ for 1-hexene; A′ = (0.6 ± 0.6) · 10⁻¹⁴ cm³ s⁻¹, n = 1.12 ± 0.05, E′_a = − 3.8 ± 0.8 kJ mol⁻¹ for cis-2-pentene; and A′ = (0.6 ± 0.8) · 10⁻¹⁴ cm³ s⁻¹, n = 1.14 ± 0.06, E′_a = − 4.3 ± 0.5 kJ mol⁻¹ for trans-2-pentene. The atoms were generated by the H₂-laser photolysis of NO and detected by time resolved chemiluminescence in the presence of NO. The concentrations of the O(³P) atoms were kept so low that secondary reactions with products are unimportant. © 1997 John Wiley & Sons, Inc.     

The three-dimensional structure of trichosanthin refined at 2.7resolution

The three-dimensional structure of trichosanthin crystallizing in space group C2 has beenrefined at 2.7 resolution from a previously reported starting model at 3 resolution based on asolvent flattened map and the revised primary structure consisting of 247 amlno-acids.The finalR-factor is 19.2% with the root mean-square deviations of 0.018 from ideal bond lengths andof 2.2° from ideal bond angles.Trichosanthin molecule is composed of two domains,the largedomain consisting of 181 amino-acld residues starting from N-terminus and the small domain con-sisting of the rest of the amino-acid residues.The molecule contains eight α-helices,five β-sheetsmade of sixteen β-strands,and some reverse turns.It is noteworthy that some of the α-helicesand β-sheets show irregular hydrogen bonding patterns.Six of the thirteen residues absolutelyconserved in eleven ribosome-inactivating proteins are located in a cleft near the interface ofthe two domains and they are likely to be active sites.Three additional conservative residueslocated in the cleft region might make some functional contribution as well.     

H2S-promoted thermal isomerization of cis-2-pentene to 1-pentene and trans-2-pentene around 800 K

H₂S accelerates the thermal isomerization of cis-2-pentene (P2c) to 1-pentene (P1) and trans-2-pentene (P2t) to around 800 K. This effect is interpreted on the basis of a free radical mechanism in which 2-pentenyl and thiyl radicals are the main chain carriers. P1 formation is essentially explained by the competing processes: P2t formation is due to addition-elimination processes: the importance of which has been evaluated against process (?4μ): The following ratios of rate constants have been measured and are discussed: (RT in cal mol^?1).     

Photochemistry of Thiophen-2(5H)-ones

Mechanistic evidence for the light-induced ring opening of thiophen-2(5H)-ones 1 in alcohols affording α, β-unsaturated mercapto esters 2 is presented. Regio-and stereochemical aspects of the ring closure of alkenylthio (type 3 ) radicals 15 and 17 to S-heterocycles 16 and 18 , of 3-thiahex-5-enyl radicals 4 to (tetrahydrothien-3-yl)methyl radicals 6 and of (2,3-dihydrothien-3-yl)methyl radicals 30 (type 7, but-3-enyl radicals) to cyclopropane-methyl radicals 29 are discussed. Irradiation (λ 350 nm) of 1 in cyclohexane in the presence of 2,3-dimethylbut-2-ene affords [2 + 2] cycloadducts 14 albeit in very low yields.     

Photochemistry of 2-alkoxymethyl-5-methylphenacyl chloride and benzoate

Irradiation of 2-(alkoxymethyl)-5-methyl-alpha-chloroacetophenones (1a-c) and 2-(methoxymethyl)-5-methylphenacyl benzoate (1d) in dry, nonnucleophilic solvents afforded 3-alkoxy-6-methylindan-1-ones (3a-c) in very high chemical yields. 3-Methylisobenzofuran-1(3H)-one (2) was, however, isolated as a major photoproduct in the presence of trace amounts of water. Quenching experiments and laser flash spectroscopy revealed that the indanone derivatives 3 are formed by 1,5-hydrogen migration from the lowest triplet excited state of the acetophenones 1 and cyclization of the resulting photoenols. In contrast, production of the lactone 2 in wet solvents was found to result from two consecutive photochemical transformations. The photoenols produced by photolysis of 1a-c add water as a nucleophile to form 2-acetyl-4-methylbenzaldehyde (4), which is further converted to 2 via a second, singlet state photoenolization process. Exhaustive photolysis of 1a in methanol produced the acetal 2-(dimethoxymethyl)-5-methylacetophenone (7a) as the exclusive product. The remarkable selectivity of these photoreactions may well be useful in synthetic organic chemistry.