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61.
A range of tricyclic nitrogen heterocycles were synthesized in a straightforward and efficient manner via a sequence involving palladium-catalyzed N-arylation and C(sp(3))-H arylation as the key steps. Whereas the C(sp(3))-H arylation furnished fused 6,5,6-membered ring systems efficiently, the formation of the more strained 6,5,5-membered systems proved to be more challenging and required a subtle adjustment of the reaction conditions. 相似文献
62.
In this paper we first introduce a novel fabrication process, which allows for easy integration of thin track-etched nanoporous membranes, within 2D or 3D microchannel networks. In these networks, soluble chemical compounds can diffuse out of the channels through well-defined and spatially organized microfabricated porous openings. Interestingly, multiple micron-scale porous areas can be integrated in the same device and each of these areas can be connected to a different microfluidic channel and reservoir. We then present and characterize several membrane-based microdevices and their use for the generation of stable diffusible concentration gradients and complex dynamic chemical landscapes under shear free conditions. We also demonstrate how a simple flow-focusing geometry can be used to generate "on-demand" concentration profiles. In turn, these devices should provide an ideal experimental framework for high throughput cell-based assays: long term high-resolution video microscopy experiments can be performed, under multiple spatially and temporally controlled chemical conditions, with simple protocols and in a cell-friendly environment. 相似文献
63.
Dubois M Becher F Herbet A Ezan E 《Rapid communications in mass spectrometry : RCM》2007,21(3):352-358
In order to increase the sensitivity of liquid chromatography/mass spectrometry (LC/MS) assays of recombinant proteins for pharmacokinetics studies, we have developed an immuno-mass spectrometry assay for EPI-hNE4, a 6237 Da protein currently developed for respiratory distress syndromes. After immunocapture of the analyte in human plasma with magnetic beads coated with anti-EPI-hNE4 antibodies, the intact protein was eluted and separated in reversed-phase LC and then analysed by tandem mass spectrometry (MS/MS) in selected reaction monitoring (SRM) mode. The problem of analytical interference due to endogenous binding antibodies was addressed by successive steps of acidification and neutralisation before immunocapture. Furthermore, potential variations in the recovery of analyte during sample extraction were compensated for by addition of an internal standard recognised by the antibodies. The precision of the assay remained therefore below 15%. A significant increase in assay sensitivity was achieved since the extraction step allowed sample concentration and removal of matrix components interfering with the electrospray ionisation process. Using 0.4 mL of plasma, a limit of quantification at 0.5 ng/mL (80 pM) was reached, which represents a 10-fold improvement in sensitivity over our previous work using sample precipitation. This technique was able to monitor EPI-hNE4 kinetics in the plasma of human subjects for 36 h after an intravenous administration of 0.125 mg/kg. 相似文献
64.
A molecular dyad was synthesized in which a Ru(bpy)(3)(2+) (bpy = 2,2'-bipyridine) photosensitizer and a phenothiazine redox partner are bridged by a sequence of tetramethoxybenzene, p-dimethoxybenzene, and p-xylene units. Hole transfer from the oxidized metal complex to the phenothiazine was triggered using a flash-quench technique and investigated by transient absorption spectroscopy. Optical spectroscopic and electrochemical experiments performed on a suitable reference molecule in addition to the above-mentioned dyad lead to the conclusion that hole transfer from Ru(bpy)(3)(3+) to phenothiazine proceeds through a sequence of hopping and tunneling steps: Initial hole hopping from Ru(bpy)(3)(3+) to the easily oxidizable tetramethoxybenzene unit is followed by tunneling through the barrier imposed by the p-dimethoxybenzene and p-xylene spacers. The overall charge transfer proceeds with a time constant of 41 ns, which compares favorably to a time constant of 1835 ns associated with equidistant hole tunneling between the same donor-acceptor couple bridged by three identical p-xylene units. The combined hopping/tunneling sequence thus leads to an acceleration of hole transfer by roughly a factor of 50 when compared to a pure tunneling mechanism. 相似文献
65.
Stefano Agnello Michael Brand Mathieu F. Chellat Silvia Gazzola Rainer Riedl 《Angewandte Chemie (International ed. in English)》2019,58(11):3300-3345
The natural phenomenon of drug resistance is a widespread issue that hampers the performance of drugs in many major clinical indications. Antibacterial and antifungal drugs are affected, as well as compounds for the treatment of cancer, viral infections, or parasitic diseases. Despite the very diverse set of biological targets and organisms involved in the development of drug resistance, the underlying molecular mechanisms have been identified to understand the emergence of resistance and to overcome this detrimental process. Detailed structural information on the root causes for drug resistance is nowadays frequently available, so next‐generation drugs can be designed that are anticipated to suffer less from resistance. This knowledge‐based approach is essential for fighting the inevitable occurrence of drug resistance. 相似文献
66.
67.
The synthesis of a new series of stable and soluble EDOT oligomers end-capped with n-hexyl groups is described. Optical and electrochemical results indicate that the synergy between the direct electron-releasing effects of the ethylenedioxy groups and the self-rigidification resulting from intramolecular interactions controls to a large extent the HOMO-LUMO gap. 相似文献
68.
Mélanie Turgis Mathieu Millette Stéphane Salmieri Monique Lacroix 《Radiation Physics and Chemistry》2012,81(8):1170-1172
A combined treatment of an edible coating composed of trans-cinnamaldehyde (TCN; 0.5% p/p) with γ-irradiation was investigated against Listeria inoculated in peeled mini-carrots. First, the D10 value (γ-irradiation dose required to eliminate 90% of the bacterial population) of TCN was evaluated under air. This treatment resulted in a 3.66-fold increase in relative bacterial radiosensitivity (RBR) as compared to the control without antimicrobial coating. Secondly, the shelf life of mini-carrots during 21 day of storage at 4 °C was studied. Antimicrobial coating containing TCN was assayed in combination with two irradiation doses (0.25 and 0.5 kGy). Results suggested that the inactive coating did not have any antimicrobial effect against Listeria while the coating containing TCN resulted in a 1.29 log reduction in carrots packed under air after 21 days of storage. Hence, these observations indicated that the combination of irradiation with antimicrobial coating played an important role in enhancing the radiosensitization of Listeria to γ-irradiation. 相似文献
69.
Dr. William Erb Akila Hellal Mathieu Albini Prof. Jacques Rouden Dr. Jérôme Blanchet 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(22):6608-6612
An unprecedented spontaneous reactivity between diazonium salts and diboronic acid has been unveiled, leading to a versatile arylboronic acid synthesis directly from (hetero)arylamines. This fast reaction (35 min overall) tolerates a wide range of functional groups and is carried out under very mild conditions. The radical nature of the reaction mechanism has been investigated. 相似文献
70.