Evidence for photolytic and microbial degradation processes in the dissipation of leptospermone, a natural ß-triketone herbicide.

Bioherbicides appear as an ecofriendly alternative to synthetic herbicides, generally used for weed management, because they are supposed to have low side on human health and ecosystems. In this context, our work aims to study abiotic (i.e., photolysis) and biotic (i.e,. biodegradation) processes involved in the fate of leptospermone, a natural ß-triketone herbicide, by combining chemical and microbiological approaches. Under controlled conditions, the photolysis of leptospermone was sensitive to pH. Leptospermone has a half-life of 72 h under simulated solar light irradiations. Several transformation products, including hydroxy-leptospermone, were identified. For the first time, a bacterial strain able to degrade leptospermone was isolated from an arable soil. Based on its 16S ribosomal RNA (rRNA) gene sequence, it was affiliated to the Methylophilus group and was accordingly named as Methylophilus sp. LS1. Interestingly, we report that the abundance of OTUs, similar to the 16S rRNA gene sequence of Methylophilus sp. LS1, was strongly increased in soil treated with leptospermone. The leptospermone was completely dissipated by this bacteria, with a half-life time of 6 days, allowing concomitantly its growth. Hydroxy-leptospermone was identified in the bacterial culture as a major transformation product, allowing us to propose a pathway of transformation of leptospermone including both abiotic and biotic processes.

Simultaneous determination of total hypericin and hyperforin in St. John's wort extracts by HPLC with electrochemical detection.

An analytical procedure was developed for the simultaneous determination of total hypericin (protopseudohypericin, pseudohypericin, protohypericin and hypericin) and hyperforin in Hypericum perforatum (St. John's wort) extracts and its preparations. The determination of total hypericin and hyperforin in one step was achieved by exposing the samples to artificial daylight in amber glass vials. This procedure allows both the photoconversion of the protoforms into the appropriate hypericins and the protection of the photosensitive hyperforin. For quantification, an HPLC method with electrochemical detection was applied. As an example of the application of the principle, two preparations containing St. John's wort were assayed.

Bimolecular hole transfer from the trimethoxybenzene radical cation in the excited state.

Bimolecular hole transfer quenching of the 1,3,5-trimethoxybenzene radical cation (TMB*+) in the excited state (TMB*+*) by hole quenchers (Q) such as biphenyl (Bp), naphthalene (Np), anisole (An), and benzene (Bz) with higher oxidation potentials than that of TMB was directly observed during the two-color two-laser flash photolysis at room temperature. From the linear relationships between the inverse of the transient absorption changes of TMB*+ during the second 532-nm laser excitation versus the inverse of the concentration of Q, the rate constant of the hole transfer from TMB*+* to Q was estimated to be (8.5 +/- 0.4) x 10(10), (1.4 +/- 0.7) x 10(11), (1.3 +/- 0.6) x 10(11), and (6.4 +/- 0.3) x 10(10) M(-1)s(-1) for Bp, An, Np, and Bz, respectively, in acetonitrile based on the lifetime of TMB*+*. The estimated rate constants are larger than the diffusion-controlled rate constant in acetonitrile. Short lifetime, high energy, and high oxidation potential of TMB*+* cause the lifetime-dependent quenching process or static quenching process as the major process during the quenching of TMB*+* by Q as indicated by the Ware's theoretical model. The subsequent hole transfer from Q*+ to TMB, giving TMB*+, was found to occur at the diffusion-controlled rate for Bp and An as Q. For Q such as Np and Bz, the dimerization of Q*+ with Q to give dimer radical cation (Q2*+) occurred competitively with the hole transfer from Q*+ to TMB.