The formation of a N−N bond is a unique biochemical transformation, and nature employs diverse biosynthetic strategies to activate nitrogen for bond formation. Among molecules that contain a N−N bond, biosynthetic routes to diazeniumdiolates remain enigmatic. We here report the biosynthetic pathway for the diazeniumdiolate-containing amino acid l -alanosine. Our work reveals that the two nitrogen atoms in the diazeniumdiolate of l -alanosine arise from glutamic acid and aspartic acid, and we clarify the early steps of the biosynthetic pathway by using both in vitro and in vivo approaches. Our work demonstrates a peptidyl-carrier-protein-based mechanism for activation of the precursor l -diaminopropionate, and we also show that nitric oxide can participate in non-enzymatic diazeniumdiolate formation. Furthermore, we demonstrate that the gene alnA, which encodes a fusion protein with an N-terminal cupin domain and a C-terminal AraC-like DNA-binding domain, is required for alanosine biosynthesis. 相似文献
Complexation of three kinds of tris(imidazolyl)calix[6]arenes containing alternate p-substituents (Calix-tBu, R(1) = R(2) = tert-butyl; Calix-NH(2), R(1) = tert-butyl, R(2) = NH(2); Calix-NO(2), R(1) = tert-butyl, R(2) = NO(2)) with Zn(ClO(4))(2)(H(2)O)(6) in acetonitrile, methanol, and THF was investigated via isothermal titration calorimetry (ITC). For the coordination of these calixarene ligands to Zn(II) in acetonitrile, typical one-phase exothermic titration curves were obtained, indicating the formation of 1:1 ligand-Zn(II) complexes accompanied by large conformational changes of the ligands. In contrast, the complexation in methanol was endothermic and dominated by favorable entropy changes. The entropy gains were achieved by extensive desolvation from both Zn(II) and the ligands. ITC measurements suggest a 2:1 ligand-Zn(II) complex formation in THF in the presence of excess ligands (Calix-NH(2) and Calix-NO(2)). The 2:1 complexes were converted to 1:1 complexes upon further addition of Zn(ClO(4))(2)(H(2)O)(6). The results indicate the important role of a coordinating solvent (acetonitrile) for direct formation of the 1:1 complexes under the conditions of excess ligand. Complexation of a ditopic ligand (Calix-Tri) with three triazole moieties on the wider rim was also studied via ITC. The first coordination of the imidazole moieties to Zn(II) was an exothermic process. This was followed by the entropically favorable coordination of the triazole moieties to the divalent cation. We have also investigated exchange of the fourth ligand (H(2)O) of the Zn(II) complex of Calix-NH(2) with butylamine, heptylamine, acetonitrile, and acetamide in a noncompetitive solvent, THF. The ΔH(0) tended to decrease upon increasing the electron-pair-donating ability of the guest ligand, whereas it was also affected by an entropic term due to restricted rotation of the guest ligand inside the calixarene cavity. 相似文献
Micellization behavior was investigated for polyoxyethylene-type nonionic surfactants with varying chain length (C(n)E(m)) in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF(4)). Critical micelle concentration (cmc) was determined from the variation of (1)H NMR chemical shift with the surfactant concentration. The logarithmic value of cmc decreased linearly with the number of carbon atoms in the surfactant hydrocarbon chain, similarly to the case observed in aqueous surfactant solutions. However, the slope of the straight line is much smaller in bmimBF(4) than in aqueous solution. Thermodynamic parameters for micelle formation estimated from the temperature dependence of cmc showed that the micellization in bmimBF(4) is an entropy-driven process around room temperature. This behavior is also similar to the case in aqueous solution. However, the magnitude of the entropic contribution to the overall micellization free energy in bmimBF(4) is much smaller compared with that in aqueous solution. These results suggest that the micellization in bmimBF(4) proceeds through a mechanism similar to the hydrophobic interaction in aqueous surfactant solutions, although the solvophobic effect in bmimBF(4) is much weaker than the hydrophobic effect. 相似文献
Treatment of alkylbenzenes with (diacetoxyiodo)benzene in the presence of catalytic amounts of p-toluenesulfonamide or p-nitrobenzenesulfonamide, and molecular iodine in 1,2-dichloroethane at 60 °C gave the corresponding (α-acetoxy)alkylbenzenes in good to moderate yields. The present reaction is a simple method for the introduction of an acetoxy group to the benzylic position of alkylbenzenes. 相似文献
A palladium-catalyzed asymmetric synthesis of 2-pyrrolidinones with a quaternary stereocenter at the 3-position has been achieved by the reaction of γ-methylidene-δ-valerolactones with alkyl isocyanates. High enantioselectivity has been realized by employing a newly synthesized chiral phosphoramidite ligand. 相似文献
Chloroform is available as not only an organic solvent but also photochemical molecular storage for synthetically important chemicals such as Cl(2), HCl, and COCl(2). We have succeeded in synthesizing organochlorine compounds, hydrochloric salt of amines, ureas, organic carbonates, and polycarbonate in practical high yields with photodecomposed chloroform. 相似文献
Anthraquinone–lectin hybrids were effectively synthesized using water‐soluble anthraquinone derivative 11 with concanavalin A (ConA) and hygrophorus russula lectin (HRL) to give anthraquinone–ConA ( 16 ) and anthraquinone–HRL ( 17 ) hybrids, respectively. These anthraquinone–lectin hybrids effectively and selectively degraded oligosaccharides containing a mannose residue as a non‐reducing terminal sugar, which has affinity for ConA and HRL, under photo‐irradiation with long‐wavelength UV light without additives and under neutral conditions. In addition, anthraquinone–HRL ( 17 ) selectively photo‐degraded only Man(α1,6)Man, which has a high affinity for HRL, among several mannosides by recognition of both the type and glycosidic linkage profile of the sugar in an oligosaccharide. 相似文献
Novel conjugated carbazole polymers based on the alkyne‐linked 1,8‐carbazole structure are synthesized in high yield by the Sonogashira cross‐coupling reaction and acetylenic oxidative coupling reaction. The polymers are thermally stable and highly soluble in common organic solvents such as CHCl3, CH2Cl2, and THF. As compared to ethynylene‐linked polymer, the butadiynylene‐linked polymer display a bathochromic shift in the absorption maximum and end absorption position. In addition, the fluorescence behaviors in CH2Cl2 are almost identical for both polymers. Electrochemical measurements indicate that the ethynylene‐linked polymer possesses a lower first oxidation potential than the butadiynylene‐linked one.
Application of high hydrostatic pressure (HHP) treatment to food processing is expected as a non-thermal fermentation regulation technology that supresses over fermentation. However, the yeast Saccharomyces cerevisiae used for Japanese rice wine (sake) brewing shows high tolerance to HHP. Therefore, we aimed to generate pressure-sensitive (piezosensitive) sake yeast strains by mating sake with piezosensitive yeast strains to establish an HHP fermentation regulation technology and extend the shelf life of fermented foods. The results of phenotypic analyses showed that the generated yeast strains were piezosensitive and exhibited similar fermentation ability compared with the original sake yeast strain. In addition, primary properties of sake brewed using these strains, such as ethanol concentration, sake meter value and sake flavor compounds, were almost equivalent to those obtained using the sake yeast strain. These results suggest that the piezosensitive strains exhibit brewing characteristics essentially equivalent to those of the sake yeast strain. 相似文献