This critical review summarizes existing knowledge on the use of diazonium salts as a new generation of surface modifiers and coupling agents for binding synthetic polymers, biomacromolecules, and nanoparticles to surfaces. Polymer grafts can be directly grown at surfaces through the so-called grafting from approaches based on several polymerization methods but can also be pre-formed in solution and then grafted to surfaces through grafting onto strategies including "click" reactions. Several routes are also described for binding biomacromolecules through aryl layers in view of developing biosensors and protein arrays, while the use of aryl diazonium coupling agents is extended to the attachment of nanoparticles. Patents and industrial applications of the surface chemistry of diazonium compounds are covered. This review stresses the paramount role of aryl diazonium coupling agents in adhesion, surface and materials sciences (114 references).
An essential issue in the development of materials presenting an accurately functionalized surface is to achieve control of layer structuring. Whereas the very popular method based on the spontaneous adsorption of alkanethiols on metal faces stability problems, the reductive electrografting of aryldiazonium salts yielding stable interface, struggles with the control of the formation and organization of monolayers. Here we report a general strategy for patterning surfaces using aryldiazonium surface chemistry. Calix[4]tetra-diazonium cations generated in situ from the corresponding tetra-anilines were electrografted on gold and carbon substrates. The well-preorganized macrocyclic structure of the calix[4]arene molecules allows the formation of densely packed monolayers. Through adequate decoration of the small rim of the calixarenes, functional molecules can then be introduced on the immobilized calixarene subunits, paving the way for an accurate spatial control of the chemical composition of a surface at molecular level.
Monodisperse ruthenium nanoparticles were prepared by reduction of RuCl3 in 1,2-propanediol. The mean particle size was controlled by appropriate choice of the reduction temperature and the acetate ion concentration. Colloidal solutions in toluene were obtained by coating the metal particles with dodecanethiol. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XANES and EXAFS for the Ru K-absorption edge) were performed on particles of two different diameters, 2 and 4 nm, and in different environments, polyol/acetate or thiol. For particles stored in polyol/acetate XPS studies revealed superficial oxidation limited to one monolayer and a surface coating containing mostly acetate ions. Analysis of the EXAFS spectra showed both oxygen and ruthenium atoms around the ruthenium atoms with a Ru-Ru coordination number N smaller than the bulk value, as expected for fine particles. In the case of 2 nm acetate-capped particles N is consistent with particles made up of a metallic core and an oxidized monolayer. For 2 nm thiol-coated particles, a Ru-S bond was evidenced by XPS and XAS. For the 4 nm particles XANES and XPS studies showed that most of the ruthenium atoms are in the zerovalent state. Nevertheless, in both cases, when capped with thiol, the Ru-Ru coordination number inferred from EXAFS is much smaller than for particles of the same size stored in polyol. This is attributed to a structural disorganization of the particles by thiol chemisorption. HRTEM studies confirm the marked dependence of the structural properties of the ruthenium particles on their chemical environment; they show the acetate-coated particles to be single crystals, whereas the thiol-coated particles appear to be polycrystalline.
Platinum nanoparticles with a mean size of 1.7 nm were synthesized by reduction in sodium acetate solution in 1,2-ethanediol. The particles were then functionalized with dodecylamine, dodecanethiol, and omega-mercapto-undecanoic acid (MUDA). Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) showed important variations of the particle surface state with functionalization whereas their structure differs only slightly. Platinum-to-sulfur charge transfer inferred from XPS of thiol-coated particles enabled the identification of the formation of Pt (delta+)-S (delta-) bonds. The native carbon monoxide (CO) at the surface of the particles was a very efficient probe for following the functionalization of the particles by FTIR. The red shift of nu(CO) accounts for the nature of the ligands at the surface of the particles and also for their degree of functionalization. Immobilization on alumina substrates of particles functionalized with MUDA was realized by immersion in colloidal solutions. Free molecules, isolated particles, and aggregates of particles interconnected by hydrogen bonds at the surface of alumina were evidenced by FTIR. With successive washings, the energy variation of the CO stretch of carbon monoxide and of carboxylic acid groups and the relative intensity nu(CH2)/nu(CO) showed that the free molecules are eliminated first, followed by aggregates and less-functionalized particles. Particles presenting a high degree of functionalization by MUDA remain and interact strongly with alumina.
Citrate-capped gold nanoparticles as well as planar gold surfaces can be efficiently grafted with a covalently attached polymer monolayer a few nanometers thick, by simple contact of the metal surface with dilute aqueous solutions of hydrophilic polymers that are end-capped with disulfide moieties, as shown by UV/vis absorption, dynamic light scattering, and surface plasmon resonance studies. The hydrophilic polymer-coated gold colloids can be freeze-dried and stored as powders that can be subsequently dissolved to yield stable aqueous dispersions, even at very large concentrations. They allow for applying filtrations, gel permeation chromatography, or centrifugation. They do not suffer from undesirable nonspecific adsorption of proteins while allowing the diffusion of small species within the hydrogel surface coating. In addition, specific properties of the original hydrophilic polymers are retained such as a lower critical solution temperature. The latter feature could be useful to enhance optical responses of functionalized gold surfaces toward interaction with various substrates.
This paper describes a general stepwise strategy combining diazonium salt, surface-initiated atom transfer radical polymerization (SI-ATRP), and click chemistry for an efficient gold surface functionalization by poly(N-isopropylacrylamide) (PNIPAM) brushes and gold nanoparticle assemblies. We designed by this way a new plasmonic device made of gold nanoparticles separated from a gold film through a thermoresponsive polymer layer. This organic layer responds to temperature variations by conformational changes (with a characteristic temperature called the lower critical solution temperature, LCST) and is therefore able to vary the distance between the gold nanoparticles and the gold film. The optical properties of these stimulable substrates were probed by surface-enhanced raman scattering (SERS) using methylene blue (MB) as a molecular probe. We show that an increase of the external temperature reversibly induces a significant enhancement of the MB SERS signal. This was attributed to a stronger interaction between the gold nanoparticles and the gold substrate. The temperature-responsive plasmonic devices developed in this paper thus provide a dynamic SERS platform, with thermally switchable electromagnetic coupling between the gold nanoparticles and the gold surface.
Vapor-deposited H2O ice films grown between 38 and 150 K under ultrahigh vacuum conditions have been investigated using near-edge x-ray absorption fine structure (NEXAFS) spectroscopy at the oxygen K-edge, in conventional mode—which is bulk sensitive-, and using the photon-stimulated desorption mode (PSD-NEXAFS), which is surface sensitive. By recording simultaneously those two signals, we have evidenced the differences between the surface and bulk electronic and atomic structures, for both amorphous porous ice condensed at 40 K and crystalline ice condensed at 150 K. We have also followed the bulk and surface evolutions of an amorphous ice film annealed from 38 to 147 K. A steep change in the local atomic structure of the bulk is observed, likely related to the high-density amorphous ice→low-density amorphous ice phase transition between 38 and 55 K. We have shown that the surface of crystalline ice is well ordered, but this order is different from that of the bulk. We have evidenced that the H2O–H2O intermolecular distance at the surface of ice is always longer than in the bulk, and that this difference increases with temperature, as the thermally induced reordering of the surface proceeds. SCF-Xα multiple scattering calculations allow us to figure out those structural differences, both in the bulk and at the surface of amorphous ice, but further calculations are necessary for crystalline ice. We have shown that the PSD-NEXAFS signal is sensitive to the surface morphology that changes with temperature because of the micropores collapse. We have used a model [E. Vichnevetski, A. D. Bass, and L. Sanche, J. Chem. Phys. 113, 3874 (2000)] that quantitatively describes the effect of the surface porosity on the ion yield. The surface of ice at 38 K is well described by a network of vertical cylindrical pores of 20 Å of diameter, separated by 6 Å, collapsing when annealing the film. This model also properly accounts of the peculiar temperature evolution of the PSD signal at the O1s−14a1+1 excitation, and therefore, allows to establish the relation between the PSD-NEXAFS signal and the surface porosity.
The grafting of stimuli-responsive polymer brushes on plasmonic structures provides a perfectly controlled two-dimensional active device with optical properties that can be modified through external stimuli. Herein, we demonstrate thermally induced modifications of the plasmonic response of lithographic gold nanoparticles functionalized by thermosensitive polymer brushes of (poly(N-isopropylacrylamide), PNIPAM). Optical modifications result from refractive local index changes due to a phase transition from a hydrophilic state (swollen regime) to a hydrophobic state (collapsed regime) of the polymer chains occurring in a very small range of temperatures. The refractive index of the polymer in aqueous solution is estimated in both states, deduced from the discrete dipole approximation (DDA) method. The combination of lithographic gold NPs and thermoresponsive polymer chains leads to a new generation of perfectly calibrated and dynamically controlled hybrid gold/polymer system for real-time nanosensors.
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