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41.
Selenium nanoparticles (SeNPs) have attracted great attention in recent years due to their unique properties and potential bioactivities. While the production of SeNPs has been long reported, there is little news about the influence of reaction conditions and clean-up procedure on their physical properties (e.g., shape, size) as well as their antioxidant activity. This study takes up this issue. SeNPs were synthesized by two methods using cysteine and ascorbic acid as selenium reductants. The reactions were performed with and without the use of polyvinyl alcohol as a stabilizer. After the synthesis, SeNPs were cleaned using various procedures. The antioxidant properties of the obtained SeNPs were investigated using DPPH and hydroxyl radical scavenging assays. It was found that their antioxidant activity does not always depend only on the nanoparticles size but also on their homogeneity. Moreover, the size and morphology of selenium nanoparticles are controlled by the clean-up step.  相似文献   
42.
A method to prepare amino-substituted 5,6,7,8-tetrahydroquinolines and 5,6,7,8-tetrahydroisoquinolines via catalytic hydrogenation of the corresponding acetamido-substituted quinolines and isoquinolines followed by acetamide hydrolysis is described. The yields of the products are good when the acetamido substituent is present on the pyridine ring and moderate with the acetamido substituent on the benzene ring. This method has also been applied to the regioselective reduction of quinoline substrates bearing other substituents (R = OMe, CO(2)Me, Ph).  相似文献   
43.
Chiral oligomeric diimides prepared from pyromellitic dianhydride, (R,R)-1,2-diaminocyclohexane and phthalic anhydride fold into M or P helical conformers; trimer 1 folds into the P conformer in the crystal but the M conformer dominates in solution; longer chain oligomers 2 and 3 form preferentially P conformers in solution, as a result of intermolecular interactions.  相似文献   
44.
An excellent linear correlation is found between a large body of experimental spin–spin carbon–carbon couplings, J(CC), across one, two and three bonds in pyridine and diazine ring systems and the corresponding B3PW91/6‐311++G(d,p)//B3PW91/6‐311++G(d,p) computations. The correlation does not differ significantly from the simplest relationship possible, J(CC)exp. = J(CC)calcd., within a small and random spread of about 1 Hz. There are 276 experimental values considered, and 124 out of these are new and come from the present work. The aromatic carbon–carbon couplings vary from ?7.6 through +78.5 Hz. It is shown that the correlation provides a reliable tool for predictions of the signs of aromatic J(CC)'s even if the magnitudes of the latter are of the order of 1 Hz. It is demonstrated, for the first time, that the relatively weak 2 J(CC) couplings, in the heteroaromatic systems studied, can bear either sign and span a considerable range of about 11 Hz. The character of the correlation indicates that rovibronic effects on aromatic J(CC)'s and those of nuclear motions on aromatic J(CC)'s are practically negligible. All of this is in a perfect agreement with our recent extensive studies on aromatic J(CC)'s in analogous benzene ring system. Substituent effects on the aromatic J(CC)'s turn out to be significant not only for 1J(CC)'s but also for most of 3J(CC)'s and 2 J(CC)'s, and the computation neatly reciprocates these trends. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   
45.
A series of hydrophopic ( 2 and 3) and new hydrophilic ( 4– 7) molecular receptors of the PNP-lariat ether with tetra-substituted cyclotriphosphazene subunits have been prepared by the complete nucleophilic substitution of chlorine atoms in the reactive PNP-crown precursor 1 with the respective sodium cation-paired oxyanions (phenoxy 2, -naphthoxy 3, and methoxytrioxyethylenoxy 4) and aliphatic amines (n-propylamine 5 aziridine 6, and pyrrolidine 7). Their structures were established by MS and 31P NMR spectroscopy and their metal ion complexing properties tested by a TLC method. Comparison of the complexation behaviour for ligands 1– 7 shows that the affinity for particular cations is strongly substituent-dependent and, in general, is significantly enhanced by cooperation of the side arm donor atoms (O or N) with the parent PNP-crown structure in the binding process. The remarkable affinity of some ligands for selected cations, in particular lithium, cesium, and silver ions, is interpreted in terms of structure-property relationships.  相似文献   
46.
Photodehydrocyclization of 1-phenyl-2-/2-arylethenyl/-3,3-dialkyl-3H-indolium cations leads in very good yield to 7H-indolo[1,2-a]quinolinium cations.  相似文献   
47.
48.
We have synthesized and characterized a family of self-assembled monolayers containing pyrene derivatives on gold and indium-doped tin oxide (ITO) substrates. The covalently bound pyrene functionalities serve as either spectroscopic or electrochemical probes of their immediate environment, and we explore their electrochemical response in this paper. When these compounds are the only constituents bound to the interfaces, the molecules enjoy significant structural freedom. The addition of aliphatic adsorbates to the interfaces serves to place the pyrene derivatives in a more restricted environment. Cyclic voltammetry shows that the organization of a monolayer with pyrene derivatives, and the position of the terminal pyrene within such monolayer, depend sensitively on the length of the pyrene tether and the presence or absence of aliphatic interfacial species, as well as the identity of the substrate.  相似文献   
49.
Iron and copper complexes of tetraphenyl-m-benziporphyrin (TPmBPH)H have been prepared and structurally characterized. The iron system, (TPmBPH)Fe(II)Br, contains a high-spin Fe(II) center. In the solid state the complex forms dimeric units linked by weak CH.Br hydrogen bonds. The Cu complex contains a tetrameric copper cluster with a Cu(2)Cl(4)(2)(-) unit bridging two [(TPmBPCl)Cu(II)](+) fragments. The formation of (TPmBPCl)H represents an example of copper-catalyzed chlorination on the internal carbon atom of (TPmBPH)H.  相似文献   
50.
Candida antarctica lipase B has been used to kinetically resolve a structurally diverse series of bicyclic 1-heteroaryl primary amines by enantioselective acetylation. High yields of either enantiomer could be obtained with excellent enantioselectivity (90-99% ee), while the undesired enantiomer could, in some cases, be recycled by thermal racemization. The absolute stereochemistry of the products was confirmed by an X-ray crystal structure.  相似文献   
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