Kinetics of Heterogeneous Isotopic Exchange Reaction in Finite Bath

A general method to find the rate constant and particle self-diffusion coefficient is suggested for a heterogeneous isotopic exchange reaction which is controlled by surface mass reaction or controlled by a combination of surface mass reaction and intraparticle diffusion. The values of the kinetic parameter, ξ₁ (ratio of the forward surface mass reaction rate to the intraparticle diffusion rate), particle self-diffusion coefficient D and rate constant k are obtained by the proposed method for the isotopic exchange reaction systems CaCO₃(s)/Ca²⁺(aq) and CaC₂O₄(s)/Ca²⁺(aq).     

Determination of alkyltrimethylammonium surfactants in hair conditioners and fabric softeners by gas chromatography-mass spectrometry with electron-impact and chemical ionization

The commercial hair conditioners and fabric softeners were analyzed for the content of alkyltrimethylammonium compounds (ATMACs) by gas chromatography-mass spectrometry (GC-MS) with electron impact (EI) and low-pressure positive-ion chemical ionization (PICI) modes. The method involves mixed diluted samples (adjust pH to 10.0) with potassium iodide to enhance the extraction of iodide-ATMA+ ion pairs by direct liquid-liquid extraction. The iodide-ATMA+ pairs were then demethylated to their corresponding nonionic alkyldimethylamines (ADMAs) by thermal decomposition in a GC injection-port. A high abundance of ADMAs was detected at the temperature above 300 degrees C in the GC injection-port. The enhanced selectivity of quasi-molecular ion chromatograms of C12-C18-ADMA, obtained using methanol PICI-MS enables ADMAs to be identified. The accuracy and precision of the method was validated and was successfully applied to determine contents of ATMAC in commercial hair conditioners and fabric softeners. The contents of total measured ATMAC ranged from 0.4 to 6.9% for hair conditioners, and from 3.3 to 4.6% for fabric softeners.     

Molecular structure and bonding properties of tris(N-methyl-formamide) formamide)(N,N, N', N'-tetramethylethylenediamine)-copper(II) perchlorate

Summary The x-ray crystal structure of tris(N-methylformamide) (N, N, N', N'-tetramethylethylenediamine)copper(II) perchlorate has been determined using three-dimensional x-ray diffraction data. The complex crystallizes in space group P2₁/c with Z=4. The cell dimensions are=8.255(3),b=17.951(6),c=16.541(4) Å, and =91.03(2)°. Least-squares refinement of the structure has yielded a final R value of 4.52% for 2108 independent reflect ions. The square pyramidal structure consists ofN, N, N', N'-tetramethylethylenediamine and twoN-methylformamide ligands forming a basal square plane with Cu–N bond lengths of 2.029(5) and 2.033(5) and Cu–O 1.981(4) and 1.985(4) Å, and a thirdN-methylformamide on the apex with a Cu–O distance of 2.181(4)Å. Each of the molecular plances of the three N-methylformamides lies nearly coplanar with thexy, yz andxz molecular coordination planes. The bonding properties of the title compound and its i.r. and uv-vis spectra are discussed with reference to the structure.     

Conformation of receptor-associated PGI2: An investigation by molecular modeling

Summary To elucidate the conformation of receptor-associated prostacyclin (PGI₂), we first performed structure-activity correlation analysis of over 200 PGI₂ analogues and derived from this analysis several crucial features pertaining to structural requirements for PGI₂ activity [Ah-lim Tsai and Kenneth K. Wu, Eicosanoids, 2 (1989) 131–143]. These structural features proved to be useful guidelines for selecting model molecules for further investigations by molecular mechanics. By properly selecting four analogues with either rigid or uniquely oriented -side chain structure for geometric fitting, we succeeded in maximally minimizing the degree of freedom of the carboxylate terminus of PGI₂. We were able to define the spatial relationship among the four critical functional groups, i.e., C1-COOH, C6a-O, C11-OH and C15-OH. More information is needed, however, to define the geometry of the -side chain, particularly for the moiety beyond C15. Nevertheless, results from structure-activity correlation analysis and molecular modeling provide useful information regarding the conformation of receptor-associated PGI₂, which assumes an elongated conformation instead of the traditional hairpin structure.     

Non-quadratic-intensity dependence of two-photon absorption induced fluorescence of organic chromophores in solution

We have provided a model to interpret the non-quadratic-intensity dependence behavior commonly observed in the two-photon fluorescence (TPF) experiment excited with high laser intensity. The model also provides one with a different technique to measure the two-photon absorption cross section of an organic chromophore in solution. In contrast to the commonly used low intensity technique that depends on the quadratic-intensity law, the present technique is based on the non-quadratic-intensity dependence of two-photon fluorescence. Auxiliary data such as two-photon quantum efficiency and fluorescence collection efficiency, essential in the low intensity method, are not required in the present technique. TPF measurements of Rhodamine B in methanol are carried out to demonstrate the validity of the present method. The method is used to determine the two-photon absorption cross section of a new chromophore attached with tricyano-derivatized furan as the electron acceptor. The two-photon absorption cross section measured using this method is also compared with that using a conventional transmission technique.     

Is there stereoselectivity in spin trapping superoxide by 5-tert-butoxycarbonyl-5-methyl-1-pyrroline N-oxide?

[reaction: see text] Ester-containing nitrones, including 5-tert-butoxycarbonyl-5-methyl-1-pyrroline N-oxide 5, have been reported to be robust spin traps for superoxide (O2*-). Using a chiral column, we have been able to isolate the two enantiomers of nitrone 5. With enantiomerically pure nitrone 5a and 5b we explored whether one of these isomers was solely responsible for the EPR spectrum of aminoxyl 6. Data obtained demonstrate that the spin trapping of O2*- by nitrone 5a and nitrone 5b affords the identical EPR spectra and lifetimes in homogeneous aqueous solution and exhibits the same ratio of cis and trans isomers. Quantum chemical modeling in vacuo also finds no difference, aside from the expected optical activity, arising from the difference in stereochemistry.     

Optimizing separation conditions for polycyclic aromatic hydrocarbons in micellar electrokinetic chromatography

We report the separation of polycyclic aromatic hydrocarbons (PAHs) using 0.1% poly(ethylene oxide) (PEO) in micellar electrokinetic chromatography (MEKC). In the presence of PEO, adsorption of PAHs on the capillary wall was reduced, leading to better resolution and reproducibility. Effects of tetrapentylammonium iodide (TPAI), dextran sulfate (DS), methanol, and sodium lauryl sulfate (SDS) on the separation of PAHs were elucidated. In terms of resolution and speed, DS, compared to TPAI, is a better additive for separation of PAHs. When using 0.1% PEO solution containing 45% methanol, 50 mM SDS, and 0.02% DS, separation of 10 PAHs containing 2 to 5 benzene rings was accomplished in less than 12 min at 15 kV in a commercial CE system. The method has also been tested for separating seven PAHs with high quantum yields when excited at 325 nm using a He-Cd laser. Unfortunately, separation of the seven PAHs was not achieved and sensitivity diminished under the same conditions. To optimize sensitivity, resolution and speed, a stepwise technique in MEKC has been proposed. The seven PAHs were resolved in 35 min at 15 kV when separation was performed in 0.1% PEO solution containing 35 mM SDS, 40% methanol and 0.02% DS for 2 min, and subsequently in 0.1% PEO solution containing 20 mM SDS, 50% methanol, and 0.02% DS.     

Photochemistry of bicyclo[2.2.2]oct-7-ene-2,5-diones and the corresponding 5-hydroxyimino and 5-methylene derivatives

Synthesis and photochemistry of several title compounds 1-3 containing multiple chromophoric systems are described. The Diels-Alder reactions of 2,6,6-trimethylcyclohexa-2,4-dienone (5) with acetylenes 6a-d provided the adducts 7a-d, which upon hydrolysis furnished the desired bicyclo[2.2.2]octenediones 1a-d. Oximes 2a-d were prepared from diones 1a-d by treatment with hydroxylamine hydrochloride in pyridine. 5-Methylenebicyclo[2.2.2]oct-7-en-2-ones 3a-d were obtained via chemoselective Wittig reaction of the corresponding diones 1a-d. Bicyclo[2.2.2]octenediones 1a-c underwent chemoselective oxa-di-pi-methane rearrangement under sensitized conditions and suffered formal ketene extrusion upon direct irradiation. Direct irradiation of 1d afforded 11d via formal ketene extrusion but under sensitization it remained unchanged. Oximes 2a-d suffered ketene extrusion upon direct irradiation and E/Z isomerization under sensitized conditions. On the other hand, 5-methylenebicyclo[2.2.2]oct-7-en-2-ones 3a-d generally underwent 1,3-acyl shift. The plausible courses of all these photochemical processes are discussed.