Three kinds of derivatives of the M1 factor of virginiamycin have been synthesised: esters with long chain fatty acids, oximes with modified polar amino acids and bis-derivatives with both the ester and oxime function. The study of the surface tension time dependence of M1 and its derivatives has shown that it is necessary to enhance simultaneously the hydrophobicity and the hydrophilicity of M1 to render M1 surface-active. A structure/function relationship study of the surface-active bis-derivatives has shown that enhancing the hydrophobicity of the molecule led to slower adsorption kinetics, higher stability of the monolayers formed and a better capacity to penetrate a membrane model. The repulsive electrostatic forces due to the presence of charges on the amino acids linked to M1 lead to higher surface tensions, a greater molecular area at the interface and lower penetration into a membrane model.This study has demonstrated that modifying systematically the hydrophobicity and hydrophilicity of a non surface-active molecule allows the production of surface-active derivatives. 相似文献
The novel amphipilic conjugate of a calix[4]arene with four Gd–1,4,7,10‐ tetra(carboxymethyl)‐1,4,7,10‐tetraazacyclododecane (DOTA) chelates has potential as a magnetic resonance imaging contrast agent, both in its monomeric and in its micellar form. The system, illustrated here with its nuclear magnetic relaxation profile, shows good relaxivities, thanks to its high rigidity.
The two most important concepts in metrology are certainly “traceability to standards” and “measurement uncertainty evaluation”.
So far the questions related to these concepts have been reasonably solved in the metrology of “classical quantities”, but
for the introduction of metrological concepts in new fields, such as chemistry and biology, a lot of problems remain and must
be solved in order to support international arrangements. In this presentation, the authors want to develop the strategy implemented
at Laboratoire national de métrologie et d’essais (LNE) in metrology in chemistry and biology. The strategy is based on: (1)
pure solutions for calibration of analytical instruments, (2) use of certified reference materials (matrix reference materials),
and (3) participation to proficiency testing schemes. Examples will be presented in organic and inorganic chemistry. For laboratory
medicine, proficiency testing providers play an important role in the organization of External Quality Assessment Schemes.
For the time being, the reference value or the assigned value of the comparison is calculated with the results obtained by
the participants. This assigned value is not often traceable to SI units. One of the methods suggested by LNE is to ensure
the metrological traceability to SI units of the assigned value for the more critical quantities carried on analytes by implementing
the Joint committee for traceability in laboratory medicine reference methods. 相似文献
Thirteen phases are now evidenced in the composition space diagram of the Al(OH)3–tren–HF–ethanol system at 190 °C. Solvothermal syntheses are performed under microwave heating. Six new organic–inorganic fluorides crystallise and their structures are determined: (H3O)·[H4tren]2·(AlF6)3·6H2O (P-1, Z = 2), [H3tren]2·(AlF5(H2O))3·8H2O (C2/c, Z = 8), [H3tren]4·(AlF6)2·(Al2F11)·(F)·10H2O (P21/n, Z = 2), [H3tren]2·(Al4F18)·3.5H2O (P63, Z = 2), [H3tren]2·(Al4F18) (P-1, Z = 1), and [H3tren]4·(Al8F35)·(OH)·H2O (P-1, Z = 1). The existence domains are approximately located for all phases. Tren amine is tetraprotonated at high HF concentration, otherwise it is triprotonated. A protonated water cluster, H3O+(H2O)6, appears in (H3O)·[H4tren]2·(AlF6)3·6H2O while a new Al4F18 unit, found in [H3tren]2·(Al4F18), is evidenced; it results from corner and edge sharing association of four AlF6 octahedra. Finally, the structure of [H3tren]4·(Al8F35)·(OH)·H2O revealed the largest known fluoroaluminate polyanion, built from eight vertex sharing AlF6 octahedra, (Al8F35)11−. 相似文献
Combined on-line transmission FTIR spectroscopy and band-target entropy minimization (BTEM) analysis were employed in order to monitor and analyze the kinetics of the alkaline hydrolysis reaction of diethyl phthalate (DEP) in aqueous-ethanol solvent mixture. This reaction is irreversible and involves two consecutive steps with the formation of the observable mono-ion intermediate species. The pure component mid-FTIR spectra of the reactive species involved in this reaction, namely DEP, mono-ion intermediate and di-ion product were successfully reconstructed using BTEM. Their corresponding concentrations were also calculated and subsequently employed to derive the kinetic rate parameters. The effect of temperature and the solvent mixture compositions on these two consecutive reaction steps were also discussed. The temperature variation study showed that both reaction rate coefficients increased with temperature. Both rate coefficients were also affected by the solvent mixture compositions and reached minimum values at certain water-ethanol solvent composition (circa 60% (v/v)). This study shows the utility of combined on-line transmission FTIR spectroscopy and chemometric techniques for the present, rather complex, consecutive organic reaction. Moreover, the present type of approach could facilitate better understanding of a wide variety of organic reactions that are performed in aqueous and mixed aqueous-organic solvents. 相似文献
The synthesis of a polypseudorotaxane, polyrotaxane, and polycatenane containing the electron-deficient cyclophane cyclobis(paraquat-p-phenylene) (CBPQT4+) subunit in the side chain is described. These interlocked supramolecular polymers have been prepared from an azide-functionalized polystyrene derivative and an acetylene-functionalized [2]rotaxane, [2]catenane and their parent tetracationic cyclophane via Cu(I)-catalyzed 1,3 dipolar cycloadditions (‘click chemistry’). The synthesis and characterization of the polymers and intermediates has been described using IR, 1H NMR, UV spectroscopies, and voltammetry. We have shown that the CBPQT4+ unit of the side chain polystyrene derivative has the ability to reversibly undergo complexation with a complementary dialkoxynaphthalene derivative. 相似文献
We evaluated the role of nitrate (NO3?) as a potential photosensitizer and the bacterial responses to dissolved organic matter (DOM) phototransformation from coastal waters in the northwestern Mediterranean Sea. In spring, without any addition of NO3?, the exposure of 0.2 μm filtered seawater (DOM-solution) to natural solar radiation (i.e. Full Sun [FS], including photosynthetically available [PAR: 400–700 nm], ultraviolet-A [UVAR: 315–400 nm] and ultraviolet-B [UVBR: 280–315 nm] radiations) stimulated bacterial production (BP) and abundance (BA) in natural assemblages (0.8 μm filtered seawater) by 80 and 20% as compared to unexposed (Dark) DOM-solutions, respectively. This stimulation resulted primarily from the exposure to PAR. When NO3? (30 μM) was added to DOM-solution before irradiation, BP and BA increased by 150 and 65% in FS compared to Dark, respectively, due to both PAR and UVBR. By contrast, in summer, the exposure of DOM-solution caused a decrease in BP by 30% but an increase in BA by 23% in FS compared to Dark, regardless of the NO3? addition before irradiation. The inhibition of BP resulted mainly from UVAR, whereas the stimulation of BA resulted from PAR. These results suggest contrasting effects along seasons of solar radiation and NO3? on DOM bioavailability, depending on its initial chemical composition. 相似文献