PubMed · 10503505
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K Miyanaka, K Tomita. 1999. [Dimethylamine].. https://pubmed.ncbi.nlm.nih.gov/10503505/
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The initial phase of ozone decomposition in natural water (t < 20 s) is poorly understood. It has recently been shown to result in very high transient HO* concentrations and, thereby, plays an essential role during processes such as bromate formation or contaminants oxidation. Phenols and amines are ubiquitous moieties of natural organic matter. Naturally occurring concentrations of primary, secondary, and tertiary amines, amino acids, and phenol were added to surface water, and ozone decomposition as well as HO* generation were measured starting 350 milliseconds after ozone addition. Six seconds into the process, 5 microM of dimethylamine and phenol had generated integral of HO* dt = 1 x 10(-10) M*s and 1.8 x 10(-10) M*s, respectively. With 10 microM dimethylamine and 1.5 mg O3/L, R(ct), (integral of HO*dt/ integral of O3dt) reached 10(-6), which is larger than in advanced oxidation processes (AOP) such as O3/H2O2. Experiments in the presence of HO*-scavengers indicated that a significant fraction of phenol-induced ozone decomposition and HO* generation results from a direct electron transfer to ozone. For dimethylamine, the main mechanism of HO* generation is direct formation of O2*- which reacts selectively with O3 to form O3*-. Pretreatment of phenol-containing water with HOCl or HOBr did not decrease HO* generation, while the same treatment of dimethylamine-containing water considerably reduced HO* generation.
Genetic analysis of the three methanol-specific methyltransferase 1 operons (mtaCB1, mtaCB2, and mtaCB3) in Methanosarcina acetivorans led to the suggestion that each of them has a discrete function during growth on methanol, which might be reflected in differential gene regulation (Pritchett and Metcalf, Mol. Microbiol. 56:1183-1194, 2005). To test this suggestion, reporter gene fusions were constructed for each of the three operons, and their expression was examined under various growth conditions. Expression of the mtaCB1 and mtaCB2 fusions was 100-fold and 575-fold higher, respectively, in methanol-grown cells than in trimethylamine (TMA)-grown cells. The mtaCB3 fusion was expressed at low levels on methanol, TMA, and dimethylamine but was significantly upregulated on monomethylamine and acetate. When TMA- or acetate-grown cultures were shifted to methanol, the mtaCB1 fusion was expressed most highly during exponential phase, whereas the mtaCB2 fusion, although strongly induced prior to mtaCB1 expression, did not reach full expression levels until stationary phase. The mtaCB3 fusion was transiently expressed prior to entry into exponential phase during a TMA-to-methanol substrate shift experiment. When acetate-grown cells were shifted to medium containing both TMA and methanol, TMA utilization commenced prior to utilization of methanol; however, these two substrates were consumed simultaneously later in growth. Under these conditions expression of the mtaCB2 and mtaCB3 fusions was delayed, suggesting that methylamines may repress their expression.
The cation of 2-phenylethyl-N,N-dimethylamine (PENNA) offers two local sites for the charge: the amine group and 0.7 eV higher in energy the phenyl chromophore. In this paper, we investigate the dynamics of the charge transfer (CT) from the phenyl to the amine site. We present a femtosecond resonant two-color photoionization spectrum which shows that the femtosecond pump laser pulse is resonant in the phenyl chromophore. As shown previously with resonant wavelengths the aromatic phenyl chromophore can be then selectively ionized. Because the state "charge in the phenyl chromophore" is the first excited state in the PENNA cation, it can relax to the lower-energetic state "charge in the amine site". To follow this CT dynamics, femtosecond probe photoabsorption of green light (vis) is used. The vis light is absorbed by the charged phenyl chromophore, but not by the neutral phenyl and the neutral or cationic amine group. Thus, the absorption of vis photons of the probe laser pulse is switched off by the CT process. For detection of the resonant absorption of two or more vis photons in the cation the intensity of a fragmentation channel is monitored which opens only at high internal energy. The CT dynamics in PENNA cations has a time constant of 80 +/- 28 fs and is therefore not a purely electronic process. Because of its structural similarity to phenylalanine, PENNA is a model system for a downhill charge transfer in peptide cations.