Self-assembly of a hydrophobic groove

Heptakis(2,6-di-O-methyl)-β-cyclodextrin interacts with 5,15-diphenylporphine to produce a 2:1 complex in dimethyl sulfoxide. This complex possesses a hydrophobic groove that circumscribes the metal binding site of the porphyrin moiety.     

Partial molal heat capacities of aqueous tetraalkylammonium bromides as functions of temperature

Enthalpies of solution have been measured from 5 to 85°C for aqueous tetraethyl- and tetrapropylammonium bromides, and the integral heat method is employed to evaluate for these electrolytes over a wide temperature range. Data taken from the literature have been used to evaluate for aqueous Bu₄NBr over a similar temperature range. These data, along with similar data for Me₄NBr, previously reported, have been used to evaluate absolute ionic heat capacities. While the absolute values agree only qualitatively with two other methods of division, the temperature dependences of the three methods essentially agree up to 65°C. Heat capacities due to structural effects on the solvent, obtained by subtracting the inherent heat capacities of the ions, are extraordinarily positive for all four tetraalkylammonium ions and have negative temperature coefficients, indicating that all four ions, including the tetramethylammonium ion, are structure-making ions.     

A definitive investigation of the reaction of cyclopentadiene with cis-3,4-dichlorocyclobutene: A literature correction

Structural assignments are made to the three adducts derived from the title reaction. ¹H-n.m.r., ¹³C-n.m.r. and euroshift data are used to support the new structures.     

Coal solubilization by enhanced enzyme activity in organic solvents

Applied Biochemistry and Biotechnology - Both oxidative and reductive enzymes can be utilized to enhance coal solubilization in aqueous and organic media. Aerobic solubilization was carried out...     

Deuterium exchange of 4-pyrimidones and 4-pyrimidthiones

The hydrogen-deuterium exchange of H-2 in 4-pyrimidone, a number of 1- and 3-alkyl-4-pyrimidones and several of their thione analogs in deuterium oxide at moderate temperatures is reported. This reaction is apparently not susceptible to acid or base catalysis. Cations of the 4-pyrimidones were found not to exchange H-2 at all in acid media. Catalytic amounts of bases do not alter the exchange rates whereas more concentrated alkali decompose the pyrimidone. However, 1,4(3,4)-dihydro-1,3-dimethyl-4-oxopyrimidinium iodide (and its 6-methyl analog) exchange H-2 quite rapidly in neutral deuterium oxide, almost instantly when triethylamine is added as a catalyst, and very slowly in dilute solutions of deuterium chloride in deuterium oxide. Mechanisms are proposed to account for these phenomena.     

Enzymatic polymerizations using surfactant microstructures and the preparation of polymer-ferrite composites

Applied Biochemistry and Biotechnology - Horseradish peroxidase has been used as a biocatalyst to synthesize a polymeric material from alkyl-substituted phenols. The synthesis is carried out in a...     

Optimization of a portable microanalytical system to reduce electrode fouling from proteins associated with biomonitoring of lead (Pb) in saliva

There is a need to develop reliable portable analytical systems for on-site and real-time biomonitoring of lead (Pb) from both occupational and environmental exposures. Saliva is an appealing matrix since it is easily obtainable, and therefore a potential substitute for blood due to existing reasonably good correlation between Pb levels in blood and saliva. The microanalytical system is based on flow-injection/stripping voltammetry with a wall-jet (flow-onto) microelectrochemical cell. Samples that contain as little as 1% saliva can cause electrode fouling, resulting in significantly reduced responsiveness and irreproducible quantitations. In addition, incomplete Pb release from salivary protein can also yield a lower Pb response than expected. This paper evaluates the extent of in vitro Pb-protein binding and the optimal pretreatment for releasing Pb from the saliva samples. Even in 50% by volume of rat saliva, the electrode fouling was not observed, due to the appropriate sample pretreatment and the constant flow of the sample and acidic carrier that prevented passivation by the protein. The system offered a linear response over a low Pb range of 1-10 ppb, low detection limit of 1 ppb, excellent reproducibility, and reliability. It also yielded the same Pb concentrations in unknown samples as did the ICP-MS. These encouraging results suggest that the microanalytical system represents an important analytical advancement for real-time non-invasive biomonitoring of Pb.     

The isolation and structure determination of cryptomisrine,a novel indolo[3,2-b]quinoline dimeric alkaloid from cryptolepis sanguinolenta

The isolation and structure determination of cryptomisrine, a novel indolo[3,2-b]quinoline dimeric alkaloid obtained from extracts of the roots of the Ghanaian medicinal plant Cryptolepis sanguinolenta is reported. The structure determination was made via a consideration of the spectral data, including uv, ir, nmr, and mass spectra. In particular, one-dimensional proton/carbon nmr, one-dimensional nOe difference nmr, and a series of homonuclear (COSY) and inverse-detected heteronuclear two-dimensional (HMQC, HMBC) experiments were utilized, as well as high resolution FABMS. Cryptomisrine is most unusual in that its two monomeric parts apparently exist in such a C₂ symmetric environment that only one set of proton and carbon nmr resonances are observed. Cryptomisrine is the first example of a dimeric indolo-[3,2-b]quinoline alkaloid to have been isolated from nature.