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461.
The gadolinium nitrato complex with α-furancarboxylic acid (FA) and 2,2′-dipyridyl (Dipy) has been synthesized. According to X-ray diffraction results, the complex is composed of the [Gd(FA)2(NO3)(Dipy)]2 dimers. The crystals are triclinic: a = 9.942(2) Å, b = 10.231(2) Å, c = 11.037(2) Å, α = 85.50(3)°, β = 75.71(3)°, γ = 69.82(3)°, Z = 1. Two gadolinium atoms are linked by four carboxylate groups of furancarboxylic acid molecules. Each gadolinium atom is coordinated to seven oxygen atoms (five belonging to the FA carboxyl groups and two belonging to the bidentate nitrate group) and to two nitrogen atoms (from Dipy).  相似文献   
462.
Some bis-benzyltetrahydroisoquinolines [α,α′-di-N,N-(1-benzyl-1,2,3,4-tetrahydroisoquinoline)-p-xylene and various substituted analogues] give rise to very abundant doubly charged fragment ions under electron impact, corresponding to the loss of the two benzyl groups. Substituent effects, ionization and appearance energy measurements and metastable transitions show that these doubly charged ions are formed (at least in part) from singly charged precursors by a heterolytic cleavage (charge separation).  相似文献   
463.
[reaction: see text] N-Sulfinylimines derived from aromatic or aliphatic aldehydes and ketones react with nitromethane and NaOH in a highly diastereoselective manner under mild conditions. In the presence of TBAF, the reaction rates are strongly increased and the stereoselectivity is inverted. This method provides enantiomerically pure beta-nitroamines derived from enolizable aldimines and ketimines, which so far are hardly accessible by aza-Henry reactions.  相似文献   
464.
Cellulose - In recent times, the attention of scientific community has been focusing on the replacement of petroleum-based polymers by others more environmentally friendly. In this sense,...  相似文献   
465.
A three step efficient strategy for the synthesis of substituted 5-nitropiperidones in high de, employing Michael addition of N-p-tolylsulfinyl beta-nitroamines to alpha,beta-unsaturated esters, hydrolysis of the sulfinyl group, and cyclization of the resulting free amines, has been developed. A very simple experimental procedure involving mild conditions and only one chromatographic purification are the main features of the process.  相似文献   
466.
Debaryomyces hansenii NRRL Y-7426 metabolised ferulic acid into different phenolic compounds using a factorial design where glucose concentration (in the range of 1?C20?g/L), peptone concentration (2?C20?g/L) and yeast extract concentration (0.2?C10?g/L) were the independent variables. The interrelationship between dependent and operational variables was well fitted (R 2?>?0.95) to models including linear, interaction and quadratic terms. Depending on the glucose and nitrogen concentrations, which redirected the metabolism, the major degradation products were 1,226.2?mg 4-vinyl guaiacol/L after 72?h (molar yield of 86.0?%), 1,077.8?mg vanillic acid/L after 360?h (molar yield of 91.1?%) or 1,682.6?mg acetovanillone/L after 408?h (molar yield of 98.8?%) in fermentations carried out with 2,000?mg ferulic acid/L. Other metabolites such as vanillin, vanillyl alcohol or 4-ethylguaiacol were present in lower amounts.  相似文献   
467.
468.
    
Anionic species of aspartic acid, Asp, having a zwitterionic backbone and a deprotonated side chain, appears to be a good example for analyzing dipole-ion and ion pair interactions. Density functional theory calculations were herein performed to investigate the low energy conformers of Asp embedded in a dielectric continuum modeling an aqueous environment, through a scan of the potential energy as a function of the side chain (χ1, χ2) torsion angles. The most energetically favorable conformers having g+g and gg+ side chain orientations are found to be stabilized by charge-enhanced intramolecular H-bonding involving the positively charged () and the two negatively charged (COO) groups. These conformers were further used to analyze Asp + nW clusters (W: water, n = 1 or 3), and Asp/Asp pair formation. COO groups were found to be the most attractive sites for hosting a water molecule (binding energy: −6.0 ± 1.5 kcal/mol), compared to groups (binding energy: −4.7 ± 1.1 kcal/mol). Energy separation between g+g and gg+ conformers increases upon explicit hydration. Asp/Asp ion pairs, stabilized by the interaction between the group of a partner and the COO group of the other, shows a quite constant binding energy (−8.1 ± 0.2 kcal/mol), whatever the pair type, and the relative orientation of the two interacting partners. This study suggests a first step to achieve a more realistic image of intermolecular interactions in aqueous environment, especially upon increasing concentration. It can also be considered as a preliminary attempt to assess the interactions of the Lys+…Asp/Glu ion pairs stabilizing intra- and interchain interactions in proteins.  相似文献   
469.
One of the main limitations for achieving truly lab-on-a-chip (LOC) devices for point-of-care diagnosis is the incorporation of the "on-chip" detection. Indeed, most of the state-of-the-art LOC devices usually require complex read-out instrumentation, losing the main advantages of portability and simplicity. In this context, we present our last advances towards the achievement of a portable and label-free LOC platform with highly sensitive "on-chip" detection by using nanophotonic biosensors. Bimodal waveguide interferometers fabricated by standard silicon processes have been integrated with sub-micronic grating couplers for efficient light in-coupling, showing a phase resolution of 6.6 × 10(-4)× 2π rad and a limit of detection of 3.3 × 10(-7) refractive index unit (RIU) in bulk. A 3D network of SU-8 polymer microfluidics monolithically assembled at the wafer-level was included, ensuring perfect sealing and compact packaging. To overcome some of the drawbacks inherent to interferometric read-outs, a novel all-optical wavelength modulation system has been implemented, providing a linear response and a direct read-out of the phase variation. Sensitivity, specificity and reproducibility of the wavelength modulated BiMW sensor has been demonstrated through the label-free immunodetection of the human hormone hTSH at picomolar level using a reliable biofunctionalization process.  相似文献   
470.
4-Vinyl guaiacol (3-methoxy 4-hydroxystyrene) can be obtained by decarboxylation of ferulic acid by the strain Streptomyces setonii ATCC 39116. The formation of this metabolite was favoured by microaerobic conditions and the culture medium employed, increasing progressively the product concentration from 543.3 up to 885.1 mg/l when aeration level was diminished, reaching a highest volumetric productivity of 70.4 mg/l h and a product yield of 1.11 mol/mol. The identity of the metabolite was confirmed by gas chromatography–mass spectrometry. A metabolic study of ferulic acid and the main degradation products (ferulic acid, 4-vinyl guaiacol, protocatechuic acid, vanillyl alcohol, vanillic acid and vanillin) suggested that ferulic acid was the only substrate capable to be transformed into 4-vinyl guaiacol by this strain of S. setonii.  相似文献   
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