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This work reports a simple method to form and visualize individual polyelectrolyte-nanoparticle necklace-like structures on paper, which is applicable to other porous surfaces. In this work, one-dimensional necklaces of negatively charged gold nanoparticles (AuNPs) have been electrostatically assembled along the backbone of a cationic polyacrylamide (CPAM) chain adsorbed on paper. The process involves rapidly passing a dilute CPAM solution through filter paper, adsorbing the polyelectrolyte on the surface, followed by the immediate filtration of an AuNP suspension through the same filter paper. The nanoparticles used were negatively charged, citrate ion capped AuNPs with an average diameter of 20 nm. Scanning electron microscopy images of the dried paper sample showed that the AuNP necklaces were adsorbed in a perpendicular direction to that of the cellulose fibers and along the length of the CPAM molecules which were draped over the fibers. The effects of CPAM polymer concentration, charge density, and molecular weight on such assembly of AuNPs were studied. This technique enables the visualization of polyelectrolyte molecules and the formation of very well organized and reproducible polyelectrolyte-nanoparticle necklaces on a porous, three-dimensional substrate., (Copyright © 2013 Elsevier Inc. All rights reserved.)

Anionic groups (AGs) on different cellulosic fiber surfaces were investigated by methylene blue (MB) and polyelectrolyte (PE) sorption, X-ray photoelectron spectroscopy (XPS), and total attenuated reflectance infrared spectrometry (FTIR-ATR). The MB sorption isotherms fitted well the Langmuir equation that gave consistent estimations of sorption capacities. FTIR-ATR showed that MB molecules had extensive accessibility to the fiber wall pores. Estimation of surface AGs by PE sorption gave much higher values than a new method combining MB sorption and XPS measurements (MB-XPS). The surface AGs in different cellulosic fibers accounted for 1-3% of the total AG content as revealed by MB-XPS. It was suggested that PE molecules can penetrate the fiber wall and form loops or unattached segments at external fiber surfaces that disrupt the PE sorption stoichiometry. The competition of MB and PE for the anionic sites in papermaking was assessed and it was shown that MB ions have a much stronger affinity to AGs than PE molecules.