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1.
CAS SCF and CCI calculations have been performed in order to establish the existence or non-existence of the HO3 radical. The potential surface for the dissociation reaction, HO3 → O2(3Σ) + OH, along one chosen coordinate has been calculated. The calculations show that although the wavefunctions describing the short-distance and long-distance states are of different character, the energies are the same and the curve connecting the states is very flat. There is probably no barrier towards dissociation of the radical. However, the existence of HO3 can still not be excluded. 相似文献
2.
Genson KL Hoffman J Teng J Zubarev ER Vaknin D Tsukruk VV 《Langmuir : the ACS journal of surfaces and colloids》2004,20(21):9044-9052
An amphiphilic heteroarm star polymer containing 12 alternating hydrophobic/hydrophilic arms of polystyrene (PS) and poly(acrylic acid) (PAA) connected to a well-defined rigid aromatic core was studied at the air-water and the air-solid interfaces. At the air-water interface, the molecules spontaneously form pancakelike micellar aggregates which measure up to several microns in diameter and 5 nm in thickness. Upon reduction of the surface area per molecule to 7 nm2, the two-dimensional micelles merged into a dense monolayer. We suggest that confined phase separation of dissimilar polymer arms occurred upon their segregation on the opposite sides of the rigid disklike aromatic core, forcing the rigid cores to adopt a face-on orientation with respect to the interface. Upon transfer onto solid supports the PS chains face the air-film interface making it completely hydrophobic, and the PAA chains were found to collapse and form a thin flattened underlayer. This study points toward new strategies to create large 2D microstructures with facial amphiphilicity and suggests a profound influence of star molecular architecture on the self-assembly of amphiphiles at the air-water interface. 相似文献
3.
From analysis by gas chromatography/mass spectrometry (GC/MS), the presence of either 2,4,5-tribromo-1H-imidazole (1) or 3,4,5-tribromo-1H-pyrazole (2) was tentatively identified in lipophilic extracts from the egg masses of three muricid molluscs. Synthesis of these compounds, followed by comparison of the GC retention times and fragmentation patterns from electron impact MS, with those of the natural products, indicated that it was 2,4,5-tribromo-1H-imidazole rather than the pyrazole. This imidazole is likely to be responsible for some of the antimicrobial activity observed in the egg extracts. This is the first report of this compound from a natural source. 相似文献
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Hau Sun Sam Chan Amber L. Thompson Kirsten E. Christensen Jonathan W. Burton 《Chemical science》2020,11(42):11592
Laurefurenynes C–F are four natural products isolated from Laurencia species whose structures were originally determined on the basis of extensive nuclear magnetic resonance experiments. On the basis of a proposed biogenesis, involving a tricyclic oxonium ion as a key intermediate, we have reassigned the structures of these four natural products and synthesized the four reassigned structures using a biomimetic approach demonstrating that they are the actual structures of the natural products. In addition, we have developed a synthesis of the enantiomers of the natural products laurencin and deacetyllaurencin from the enantiomer of (E)-laurefucin using an unusual retrobiomimetic strategy. All of these syntheses have been enabled by the use of tricyclic oxonium ions as pivotal synthetic intermediates.The synthesis and structural reassignment of laurefurenynes C–F has been achieved, with the new structures fitting with a proposed biosynthesis. Also reported is the synthesis of ent-laurencin and ent-deacetyllaurencin via a retrobiomimetic approach. 相似文献
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A high performance liquid chromatography (HPLC) method with fluorescence detection including an on-line purification was established for determination of catecholamines in human urine. The method was evaluated using samples of pooled urine spiked with catecholamines and validated for measurements of catecholamines in urine of healthy individuals in a field study. The laboratory method evaluation study showed that the recovery of the method was 0.82 (confidence interval (CI): 0.79-0.86) and 0.92 (CI: 0.89-0.95) for noradrenaline and adrenaline, respectively. Thus, correction factors of 0.82(-1) and 0.92(-1) were applied to correct the measurement results for this systematic effect. Furthermore, an uncertainty budget was generated for the analytical method using the BIPM-approach recommended by the International Organization for Standardization. The relative uncertainty of the method was estimated to be 10-12%, which was consistent with the observed relative variability found in the method evaluation. The method was evaluated in accordance with EURACHEM Guidance Document No 1 concerning accreditation for chemical laboratories with respect to accuracy and precision. The field study showed that the standard deviation of the method was sufficiently low to distinguish between persons working with two different processes of garbage collection, i.e. collection using four wheeled containers versus collection using bins. 相似文献
9.
Holzmueller J Genson KL Park Y Yoo YS Park MH Lee M Tsukruk V 《Langmuir : the ACS journal of surfaces and colloids》2005,21(14):6392-6398
Amphiphilic dendron-rod molecules with three hydrophilic poly(ethylene oxide) (PEO) branches attached to a hydrophobic octa-p-phenylene rod stem were investigated for their ability to form two-dimensional micellar structures on a solid surface. A treelike shape of the molecules was reported to be a major factor in the formation of nonplanar micellar structures in solution and in the bulk state (cylindrical and spherical). We observed that in these treelike amphiphilic molecules the hydrophilic terminated dendron branches assemble themselves in surface monolayers with the formation of two-dimensional layered or circular micellar structures. We suggested the formation of the planar ribbon-like structures with interdigitated layering within the loosely packed monolayers and circular, ringlike structures (2D circular aggregates) in the precollapsed state. 相似文献
10.
Kirsten Gesenberg Prashant P. Deshpande Annie Pullockaran Feng Xu Dedong Wu Qi Gao Charles Pathirana John Castoro Nachimuthu Soundararajan Andrew Staab 《Tetrahedron letters》2007,48(15):2675-2677
Transformation of 4,7-dimethoxy-6-azaindole into 4-hydroxy-7-methoxy-6-azaindole or 7-hydroxy-4-methoxy-6-azaindole can be readily controlled by careful selection of a reagent. Treatment with concentrated HCl results in hydrolysis at the 4-position exclusively, while TMS-I provides demethylation at the 7-position only. Products were unambiguously identified by single crystal X-ray crystallography. 相似文献