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691.
692.
Biomedical research has been empowered by tools that enable spatial and temporal control of biological systems. These have predominantly come from photocaged bioactive molecules (optochemical control; N. Ankenbruck, T. Courtney, Y. Naro, A. Deiters, Angew. Chem. Int. Ed. 2018 , 57, 2768–2798) and light-dependent proteins (optogenetic control; L. Fenno, O. Yizhar, K. Deisseroth, Annu. Rev. Neurosci. 2011 , 34, 389–412). Recent advances in photocatalysis offer the opportunity to amplify these strategies by providing new dimension of biorthogonality. Photocatalysis also empowers bioconjugation with unprecedented reactivities enabling new crosslinking chemistry or biomolecule functionalization, while merging photocatalysis with biocatalysis extends the scope of both of these powerful classes of transformation. 相似文献
693.
We describe the diastereoselective α-allylation of various amines using an anodic oxidation-amidoalkylation sequence. Especially, we found that an acyclic amine, diethylamine, can be allylated with an excellent diastereoselectivity, as high as 94/6. Following our simple protocol, functionalized piperidine, pyrrolidine, morpholine, and tetrahydroisoquinoline were also obtained with moderate to good diastereomeric excesses and in good to excellent yields. 相似文献
694.
695.
Brunilde Castano Tommaso Pedrazzini Massimo Sisti Emma Gallo Fabio Ragaini Nicola Casati Alessandro Caselli 《应用有机金属化学》2011,25(11):824-829
The synthesis and characterization of copper(I) complexes of the novel pyridine‐containing macrocyclic ligand (PC‐L) and their use as catalysts in the Henry reaction are reported. The pyridine‐based 12‐membered tetraaza macrocyclic (PC‐L) ligand 1 can be obtained in good overall yield (85%) from commercially available starting materials. The Cu(I) complexes showed good catalytic activities in the Henry reaction of different aldehydes and nitroalkanes. Remarkable diastereoselectivity was observed when isatine was reacted with nitroethane under catalytic conditions. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
696.
697.
Louise Malm Emma Palm Amina Souihi Merle Plassmann Jaanus Liigand Anneli Kruve 《Molecules (Basel, Switzerland)》2021,26(12)
Non-targeted screening (NTS) with reversed phase liquid chromatography electrospray ionization high resolution mass spectrometry (LC/ESI/HRMS) is increasingly employed as an alternative to targeted analysis; however, it is not possible to quantify all compounds found in a sample with analytical standards. As an alternative, semi-quantification strategies are, or at least should be, used to estimate the concentrations of the unknown compounds before final decision making. All steps in the analytical chain, from sample preparation to ionization conditions and data processing can influence the signals obtained, and thus the estimated concentrations. Therefore, each step needs to be considered carefully. Generally, less is more when it comes to choosing sample preparation as well as chromatographic and ionization conditions in NTS. By combining the positive and negative ionization mode, the performance of NTS can be improved, since different compounds ionize better in one or the other mode. Furthermore, NTS gives opportunities for retrospective analysis. In this tutorial, strategies for semi-quantification are described, sources potentially decreasing the signals are identified and possibilities to improve NTS are discussed. Additionally, examples of retrospective analysis are presented. Finally, we present a checklist for carrying out semi-quantitative NTS. 相似文献
698.
Eduardo Beltrán Emma Cavero Dr. Joaquín Barberá Dr. José Luis Serrano Prof. Anabel Elduque Dr. Raquel Giménez Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(36):9017-9023
Chiral polycatenar 1H‐pyrazoles self‐assemble to form columnar mesophases that are stable at room temperature. X‐ray diffraction and CD studies in the mesophase indicate a supramolecular helical organization consisting of stacked H‐bonded dimers. The liquid‐crystalline compounds reported are 3,5‐bis(dialkoxyphenyl)‐1H‐pyrazoles that incorporate two or four dihydrocitronellyl chiral tails. It can be observed that the grafting of these branched chiral substituents onto the 3,5‐diphenyl‐1H‐pyrazole core has a beneficial role in inducing mesomorphism, because isomeric linear‐chain compounds are not liquid crystalline; this is not the usual scheme of behavior. Furthermore, the molecular chirality is transferred to the columnar mesophase, because preferential helical arrangements are observed. Films of the compounds are luminescent at room temperature and constitute an example of the self‐organization of nondiscoid units into columnar liquid‐crystalline assemblies in which the functional molecular unit transfers its properties to a hierarchically built superstructure. 相似文献
699.
The interaction of acetonitrile with superoxide radicals over a polycrystalline TiO2 (Degussa P25) surface was investigated using continuous-wave electron paramagnetic resonance (cw-EPR) spectroscopy. For the
first time, a thermally unstable radical intermediate has been observed following the low-temperature exposure of acetonitrile
to surface-adsorbed O2− radicals. The radical intermediate has been identified as an [O2−···CH3CN] type surface complex characterised by the g values of g
1 = 2.031, g
2 = 2.010 and g
3 = 2.003. This surface complex is thermally unstable and decomposes at temperatures of T > 240 K. A second oxygen-centred species was also observed following acetonitrile adsorption, characterised by the spin Hamiltonian
parameters of g
1 = 2.028, g
2 = 2.010, g
3 = 2.004, A
1 = 1.2 mT, A
2 = 1.0 mT and A
3 = 1.0 mT, and was assigned to a hydroperoxy radical (HO2•). 相似文献
700.
Pierluigi Quagliotto Nadia Barbero Claudia Barolo Emma Artuso Carlotta Compari Emilia Fisicaro Guido Viscardi 《Journal of colloid and interface science》2009,340(2):269-275
A series of pyridinium-based cationic surfactants has been synthesised and their amphiphilic properties have been studied by conductivity and surface tension measurements. The modification of the substitution pattern on the pyridinium ring by hydrophobic moieties (methyl vs. hydrogen and presence or not of condensed benzene ring) gave the opportunity to investigate structure–activity relationships. Characterization by conductivity and surface tension measurements shed light on the behaviour at the air/water interface and in the micellar environment. In particular, the tendency to form ion pairs at very low concentration was evidenced for all the surfactants substituted on the ring, but not for the simple pyridinium ones. The formation of ion pairs affects both the conductivity and the surface tension plots, showing that a series of steps is involved during the adsorption to the air/water surface. An attempt was made to qualify the single steps in the adsorption at the surface layer. Those steps were attributed to different chemical species (free surfactant ions or ion pairs) and to different arrangements of the surfactant. This work also represents a contribution of investigation at very low surfactant concentrations and high surface tension values. 相似文献