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81.
Bermejo JF Ortega P Chonco L Eritja R Samaniego R Müllner M de Jesus E de la Mata FJ Flores JC Gomez R Muñoz-Fernandez A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(2):483-495
Novel amine- or ammonium-terminated carbosilane dendrimers of type nG-[Si{OCH2(C6H3)-3,5-(OCH2CH2NMe2)2}]x, nG-[Si{O(CH2)2N(Me)(CH2)2NMe2}]x and nG-[Si{(CH2)3NH2}]x or nG-[Si{OCH2(C6H3)-3,5-(OCH2CH2NMe3 +I-)2}]x, nG-[Si{O(CH2)2N(Me)(CH2)2NMe3 +I-}]x, and nG-[Si{(CH2)3NH3 +Cl-}]x have been synthesized and characterized up to the third generation by two strategies: 1) alcoholysis of Si--Cl bonds with amino alcohols and subsequent quaternization with MeI, and 2) hydrosilylation of allylamine with Si--H bonds of the dendritic systems and subsequent quaternization with HCl. Quaternized carbosilane dendrimers are soluble in water, although degradation is apparent due to hydrolysis of Si--O bonds. However, dendrimers containing Si--C bonds are water-stable. The biocompatibility of the second-generation dendrimers in primary cell cultures of peripheral blood mononuclear cells (PBMCs) and erythrocytes have been analyzed, and they show good toxicity profiles over extended periods. In addition, we describe a study on the interactions between the different carbosilane dendrimers and DNA oligodeoxynucleotides (ODNs) and plasmids along with a comparative analysis of their toxicity. They can form complexes with DNA ODNs and plasmids at biocompatible doses via electrostatic interaction. Also a preliminary transfection assay has been accomplished. These results demonstrate that the new ammonium-terminated carbosilane dendrimers are good base molecules to be considered for biomedical applications. 相似文献
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Díez-Pascual AM Monroy F Ortega F Rubio RG Miller R Noskov BA 《Langmuir : the ACS journal of surfaces and colloids》2007,23(7):3802-3808
A brief summary of dilational surface viscoelatic properties of spread and adsorbed surfactant polymer films at the air-water interface is reported. The viscoelastic moduli have been measured as a function of frequency and surface pressure. The combination of several techniques, oscillating drop and barrier experiments and electrocapillary waves (ECW), has allowed us to investigate a broad frequency range. The dynamic elasticity epsilon shows a slight change with frequency and a noticeable pressure dependence for both kinds of monolayers. In the spread films, elasticity increases steeply with surface pressure, and reaches a constant value before the polymer begins to dissolve into the bulk. On the other hand, the adsorbed films exhibit a pronounced elasticity maximum, followed by a considerable decay when a loose surface structure is formed. The position of the maximum depends on the polymer chemical composition and molecular weight. The results on the overlapping surface pressure range confirm the dynamic equivalence of spread and adsorbed monolayers. At low surface concentration, the agreement between static and dynamic elasticity is quite satisfactory, but the values diverge considerably at higher surface pressures. The loss modulus omegakappa decreases monotonically with increasing omega, becoming zero (it can even take apparent negative values) for the highest frequencies. The frequency dependence of the elasticity has been well described by the diffusive control model of Lucassen-van den Tempel (LVT). However, its predictions for omegakappa do not coincide with the experimental data. The differences between experimental and theoretical values increase at low frequencies. 相似文献
84.
New Insights into the Reactivity of Cisplatin with Free and Restrained Nucleophiles: Microsolvation Effects and Base Selectivity in Cisplatin–DNA Interactions 下载免费PDF全文
Dr. Abel de Cózar Dr. Olatz Larrañaga Prof. Dr. F. Matthias Bickelhaupt Dr. Eider San Sebastián Elisabeth Ortega‐Carrasco Dr. Jean‐Didier Maréchal Prof. Agustí Lledós Prof. Dr. Fernando P. Cossío 《Chemphyschem》2016,17(23):3932-3947
The reactivity of cisplatin towards different nucleophiles has been studied by using density functional theory (DFT). Water was considered first to analyze the factors that govern the transformation of cisplatin into more electrophilic aquated species by using an activation‐strain model. It was found that the selectivity and reactivity of cisplatin is a delicate trade‐off between strain and interaction energies and that the second chloride is a worse leaving group than the first. When similar studies were carried out with imidazole, guanine (G), and adenine (A), it was found that in general the second nucleophilic substitution reactions have lower activation barriers than the first ones. Finally, simulations of the structural restrictions imposed by the DNA scaffold in intra‐ and interstrand processes showed that the geometries of the reaction products are nonoptimal with respect to the unrestrained A and G nucleophiles, although the energetic cost is not considerable under physiological conditions, which thus permits nucleophilic substitution reactions that lead to highly distorted DNA. 相似文献
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86.
[reaction: see text] (1S,2S,3S,4R,5R)-4-amino-5-(hydroxymethyl)cyclopentane-1,2,3-triol 1 is prepared stereoselectively from D-lyxose and displays anomer-selective inhibition for beta-galactosidase (Ki = 3.0 x 10(-6) M) and beta-glucosidase (Ki = 1.5 x 10(-7) M), over alpha-galactosidase (Ki = 2.3 x 10(-5) M) and alpha-glucosidase (IC50 = 1.0 x 10(-4) M). There is no observable cross-reactivity with alpha-mannosidase, beta-mannosidase, or alpha-L-fucosidase. 相似文献
87.
Velázquez MM Ortega F Monroy F Rubio RG Pegiadou S Pérez L Infante MR 《Journal of colloid and interface science》2005,283(1):144-152
We report the formation of Langmuir monolayers of pure zwitterionic hexadecyl 1-N-L-tryptophan glycerol ether (C(16)-TGE) surfactant and mixed monolayers of cationic-zwitterionic surfactant obtained modifying the pH of the subphase. The pressure-area and surface potential-area isotherms and fluorescence microscopy measurements have been used to characterize the surface phase transitions in the monolayers. These transitions appeared at larger areas as the pH decreased from 6.0 to 2.0 and almost disappeared as the pH decreased further. The analysis of the surface potential and the infrared reflection-absorption spectroscopy data suggests that the phase transition is associated with a change of orientation of both the hydrocarbon chain and the aromatic group of the surfactant with respect to the air-water surface. The surface rheology of the monolayers was studied by quasielastic light scattering and by the oscillatory barrier technique. The results indicate that there is at least one relaxation process in the monolayer. 相似文献
88.
P Cardon J P Parente Y Leroy J Montreuil B Fournet 《Journal of chromatography. A》1986,356(1):135-146
High-performance liquid chromatography has been applied to the separation of isomers of mono-, di-, tri- and tetrasialylated oligosaccharides derived from alpha 1-acid glycoprotein by hydrazinolysis. The separation of the sialyl-oligosaccharides on the basis of their negative charges was carried out with quaternary amine-bonded silica. Within each class, the anionic oligosaccharides were fractionated on the basis of their net carbohydrate content on alkylamine-modified silica using a mobile phase consisting of a mixture of acetonitrile and potassium dihydrogen phosphate with 0.01% of 1,4-diaminobutane or 0.01% of tetraethylpentamine. 相似文献
89.
Marie-Ange Lespinasse Dr. Kaiyao Wei Justine Perrin Dr. Matthias Winkler Sieme Hamaidia Alexis Leroy Dr. Zuzana Macek Jilkova Dr. Christian Philouze Dr. Patrice N. Marche Dr. Carlo Petosa Dr. Jérôme Govin Dr. Anouk Emadali Dr. Yung-Sing Wong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(64):e202202293
The pharmaceutical industry has a pervasive need for chiral specific molecules with optimal affinity for their biological targets. However, the mass production of such compounds is currently limited by conventional chemical routes, that are costly and have an environmental impact. Here, we propose an easy access to obtain new tetrahydroquinolines, a motif found in many bioactive compounds, that is rapid and cost effective. Starting from simple raw materials, the procedure uses a proline-catalyzed Mannich reaction followed by the addition of BF3 ⋅ OEt2, which generates a highly electrophilic aza-ortho-quinone methide intermediate capable of reacting with different nucleophiles to form the diversely functionalized tetrahydroquinoline. Moreover, this enantioselective one-pot process provides access for the first time to tetrahydroquinolines with a cis-2,3 and trans-3,4 configuration. As proof of concept, we demonstrate that a three-step reaction sequence, from simple and inexpensive starting compounds and catalysts, can generate a BD2-selective BET bromodomain inhibitor with anti-inflammatory effect. 相似文献
90.