No abstract

The naturally occurring peptidyl protease inhibitor leupeptin (N-acetyl-L-leucyl-L-leucyl-L-argininal) has been prepared labeled with 13C at the argininal carbonyl. 13C chemical shift data for the trypsin-leupeptin inhibitor complex in the pH range 3.0-7.6 reveal the presence of two pH-dependent covalent complexes, suggestive of two interconverting diastereomers at the new asymmetric tetrahedral center created by covalent addition of Ser195 to either side of the 13C-enriched aldehyde of the inhibitor. At pH 7 two signals are observable at delta 98.8 and delta 97.2 (84:16 ratio), while at pH 3.0 the latter signal predominates. In the selective proton 13C-edited NOE spectrum of the major diastereomer at pH 7.4, a strong NOE is observed between the hemiacetal proton of the inhibitor and the C2 proton of His57 of the enzyme, thus defining the stereochemistry of the high pH complex to the S configuration in which the hemiacetal oxygen resides in the oxyanion hole. pH titration studies further indicate that the 13C chemical shift of the S diastereomer follows a titration curve with a pKa of 4.69, the magnitude of which is consistent with direct titration of the hemiacetal oxygen. Similar pH-dependent chemical shifts were obtained by using CPMAS 13C NMR, providing evidence for the existence of the same diastereomeric equilibrium in the solid state.

A moisture-triggered release system was developed using porous metal-organic materials as encapsulating agents. Release of both hydrophilic (ethyl butyrate) and hydrophobic (D-limonene) fragrance compounds was investigated by gas adsorption measurement, thermogravimetric analysis and gas chromatography-mass spectroscopy. These materials exhibit exceptional fragrance compatibility and controlled release compared to the current leading encapsulation technology.

Two new methoxychalcones, kukulkanins A (2',4'-dihydroxy-3',4-dimethoxychalcone) and B (2',4',4-trihydroxy-3'-methoxychalcone), were isolated by flash chromatography of extracts of small branches of Mimosa tenuefolia. The compounds were identified using ir, nmr, uv, and mass spectroscopy, and their structures were confirmed by X-ray crystallography.

No abstract