This work describes the syntheses of a new poly(amidoamine) (PAMAM) dendrimer family possessing a disulfide function (cystamine) in its core. Traditional redox-chemistry associated with the disulfide core in these dendrimer structures, provides a versatile strategy for designing unique sizes, shapes and controlling the regio-disposition of chemical groups on the surface of these dendrimers. Various single site, sulfhydryl functionalized dendron reactants may be generated in situ, under standard reducing conditions (i.e. dithiothreitol (DTT)). Facile control of size, shape and chemical functionality placement involves covalent hybridization of these single point, sulfhydryl reactive dendron components. This is accomplished by re-oxidation in the presence of air, to yield generation/surface chemistry differentiated cross-over products which may be isolated by preparative thin layer or column chromatography. Differentiated cystamine core dendrimers derived from combination and permutation of lower generation (i.e. Gen.=0-3) sulfhydryl functionalized dendrons possessing amino, hydroxyl, acetamido or dansyl surface groups, were synthesized and isolated. They were characterized by a variety of methods including; 13C NMR, capillary electrophoresis (CE), gel electrophoresis (PAGE), thin layer chromatography (TLC) and electrospray (ES) or matrix assisted laser desorption ionization (MALDI-TOF) mass spectrometry. This general strategy has broad implications for the systematic size, shape and regio-chemical control of a wide range of dendritic nanostructures, many of which may be designed to mimic the sizes, shapes and regio specific chemo-domains observed for globular proteins. 相似文献
A homologous series of first-to third-generation dendritic polyamides 2a, 3, and 5 with tris(aminoethyl) amine (TREA) as the core and the protected amino functional groups at the periphery were synthesized
via active ester route from “Schlüter” type dendron 1a. Their structures were characterized by 1H-NMR and mass spectra. Based on the efficient synthesis of the first generation dendrimer 2a (yield 75%), the synthesis of second-generation dendrimer 3 was found to be more efficient via the convergent method (yield 69%), while the mixed strategy was applied efficiently for the synthesis of the higher generation
dendrimer 5 (yield 37%). The overall yield for the third generation dendrimer 5 from Schlüter dendron is 12%.
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Translated from Huaxue Tongbao (Chemistry), 2005, 68(12) (in Chinese) 相似文献
This work demonstrated for the first time that myoglobin cross‐linked in polylysine films is electrochemically active at 6 °C. At 6 °C, these protein films exhibited reversible reduction/oxidation peaks which are characteristic of FeIII/FeII redox couple. The estimated current function densities (J=1.6×10?4 C/V cm2), surface concentrations (ΓT=0.10 nmol/cm2) and standard electron transfer constant (ks=13.86 s?1) at 6 °C for the data taken at a scan rate of 0.1 V/s were similar to those which were obtained at 10, 15 and 23 °C. Basically, this study shows a possible electrocatalytic application of these myoglobin/polylysine films, for example in low temperature sensing applications. 相似文献
A compact 0-dimensional space has a -separating rank 1 family of clopen sets iff it is the continuous image of a compact 0-dimensional linearly ordered space.
We report the analytical performance of glassy carbon electrodes (GCE) modified with a dispersion of multiwall carbon nanotubes (MWCNT) in polylysine (Plys) (GCE/MWCNT‐Plys). The resulting electrodes show an excellent electrocatalytic activity towards different bioanalytes like ascorbic acid, uric acid and hydrogen peroxide, with important decrease in their oxidation overvoltages. The dispersion of 1.0 mg/mL MWCNT in 1.0 mg/mL polylysine is highly stable, since after 2 weeks the sensitivity for hydrogen peroxide at GCE modified with this dispersion remained in a 90% of the original value. The MWCNT‐Plys layer immobilized on glassy carbon electrodes has been also used as a platform to build supramolecular architectures by self‐assembling of polyelectrolytes based on the polycationic nature of the polylysine used to disperse the nanotubes. The self‐assembling of glucose oxidase has allowed us to obtain a supramolecular multistructure for glucose biosensing. The influence of glucose oxidase concentration and adsorption time as well as the effect of using polylysine or MWCNT‐Plys as polycationic layers for further adsorption of GOx is also evaluated. 相似文献
Summary: A series of regioselectively dendronized cellulose derivatives has been prepared by the treatment of cellulose in a N,N‐dimethylacetamide/LiCl solvent system with dendrons possessing isocyanate focal substituents. These new materials were characterized using FT‐IR and 13C NMR spectroscopies, and thermogravimetric analysis; the products were highly soluble in a wide range of organic solvents.
Substitution pattern of the dendronized cellulose. 相似文献
We compare herein the interfacial reactivity of self-assembled monolayers (SAMs) of 11-mercaptoundecanoic acid (MUA), 1-undecanethiol (UDT) and 11-mercaptoundecanol (MUD) on gold surfaces towards aqueous solutions of poly-(
-lysine) (PL). Liquid-phase labelling of PL with the alkyne dicobalt hexacarbonyl cluster 1 combined with analysis of the substrates by Fourier transform infrared reflection–absorption spectroscopy (FT-IRRAS) and X-ray photoelectron spectroscopy (XPS) revealed that irreversible binding of PL occurred in all cases. However, the mechanism of binding involved differed markedly from one monolayer to the other. The main mode of interaction of PL to MUA SAM was of electrostatic nature between the terminal carboxylate of MUA and the ammonium groups of PL. For a similar number of bound thiolate molecules, the UDT adsorbed layer was found less continuous than the MUA one, allowing a higher fraction of PL to directly bind to the gold surface. As for MUD, very little thiolate molecules were adsorbed, leaving bare gold surface areas for non specific adsorption of PL. 相似文献