Nanometer-Thick Ion-Selective Polyelectrolyte Multilayer Coatings to Inhibit the Disintegration of Inorganic Upconverting Nanoparticles

Protective and ion selective polyelectrolyte multilayer coatings from poly(sodium 4-styrenesulfonate) and poly(diallyldimethylammonium chloride) were manufactured on the NaYF4:Yb3+,Er-3+ upconverting nanoparticle surface. The ion selective coatings would be effective in hindering the disintegration of inorganic nanoparticle in an aqueous environment used in various applications such as in vitro assays and biomedical imaging. The disintegration is prominent especially in detrimental phosphate-based buffers. The effect of the used counteranion on the multilayer formation and the luminescent properties of the coated materials is discussed. The multilayer coating was confirmed with Fourier transform infrared spectroscopy, thermal analysis, and transmission electron microscopy. The behavior of the coated nanoparticles in aqueous environment was monitored by using fluoride ion selective electrode. We observed that the ion selective coatings prepared using fluoride or chloride as a counteranion were the most effective in slowing the disintegration of the nanoparticles. The deceleration in the disintegration process was observed also in phosphate-based buffer which emphasizes the ion selective properties of the multilayer coating. The upconversion luminescence measurements of the coated nanoparticles showed that coatings manufactured with bromide counteranion were most efficient in shielding the upconversion luminescence in solid state

Oxidative Layer-By-Layer Multilayers Based on Metal Coordination: Influence of Intervening Graphene Oxide Layers

Layer-by-layer (LbL) fabricated oxidative multilayers consisting of successive layers of inorganic polyphosphate (PP) and Ce(IV) can electrolessly form thin conducting polymer films on their surface. We describe the effect of substituting every second PP layer in the (PP/Ce) multilayers for graphene oxide (GO) as a means of modifying the structure and mechanical properties of these (GO/Ce/PP/Ce) films and enhancing their growth. Both types of LbL films are based on reversible coordinative bonding between the metal ions and the oxygen-bearing groups in PP and GO, instead of purely electrostatic interactions. The GO incorporation leads to the doubling of the areal mass density and to a dry film thickness close to 300 nm after 4 (GO/Ce/PP/Ce) tetralayers. The film roughness increases significantly with thickness. The (PP/Ce) films are soft materials with approximately equal shear storage and loss moduli, but the incorporation of GO doubles the storage modulus. PP displays a marked terminating layer effect and practically eliminates mechanical losses, making the (GO/Ce/PP/Ce) films almost pure soft elastomers. The smoothness of the (PP/Ce) films and the PP-termination effects are attributed to the reversible coordinative bonding. The (GO/Ce/PP/Ce) films oxidize pyrrole and 3,4-ethylenedioxythiophene (EDOT) and form polypyrrole and PEDOT films on their surfaces. These polymer films are considerably thicker than those formed using the (PP/Ce) multilayers with the same nominal amount of cerium layers. The GO sheets interfere with the polymerization reaction and make its kinetics biphasic. The (GO/Ce) multilayers without PP are brittle and thin.</p

Oxidative Spin-Spray-Assembled Coordinative Multilayers as Platforms for Capacitive Films

The spin-spray-assisted layer-by-layer (LbL) assembly technique was used to prepare coordinative oxidative multilayers from Ce(IV), inorganic polyphosphate (PP), and graphene oxide (GO). The films consist of successive tetralayers and have a general structure (PP/Ce/GO/Ce)(n). Such oxidative multilayers have been shown to be a general platform for the electrodeless generation of conducting polymer and melanin-type films. Although the incorporation of GO enhances the film growth, the conventional dip LbL method is very time consuming. We show that the spin-spray method reduces the time required to grow thick multilayers by the order of magnitude and the film growth is linear from the beginning, which implies a stratified structure. We have deposited poly(3,4-ethylenedioxothiophene), PEDOT, on the oxidative multilayers and studied these redox-active films as models for melanin-type capacitive layers for supercapacitors to be used in biodegradable electronics, both before and after the electrochemical reduction of GO to rGO. The amount of oxidant and PEDOT scales linearly with the film thickness, and the charge transfer kinetics is not mass transfer-limited, especially after the reduction of GO. The areal capacitance of the films grows linearly with the film thickness, reaching a value of ca. 1.6 mF cm(-2) with 20 tetralayers, and the specific volumetric (per film volume) and mass (per mass of PEDOT) capacitances are ca. 130 F cm(-3) and 65 F g(-1), respectively. 5,6-Dihydroxyindole can also be polymerized to a redox-active melanin-type film on these oxidative multilayers, with even higher areal capacitance values

Effective Shielding of NaYF4:Yb3+,Er3+ Upconverting Nanoparticles in Aqueous Environments Using Layer-by-Layer Assembly

Aqueous solutions are the basis for most, biomedical assays, but they quench the upconversion luminescence significantly. Surface modifications of upconverting nanoparticles are vital for shielding the obtained luminescence. Modifications also provide new possibilities for further use by introducing attaching sites for biomolecule conjugation. We demonstrate the use of a layer-by-layer surface modification method combining varying lengths of negatively charged polyelectrolytes with positive neodymium ions in coating the upconverting NaYF4:Yb3+,Er3+ nanoparticles. We confirmed the formation of the bilayers and investigated the surface properties with Fourier transform infrared and reflectance spectroscopy, thermal analysis, and (zeta-potential measurements. The effect of the coating on the upconversion luminescence properties was characterized, and the bilayers with the highest improvement in emission intensity were identified. In addition, studies for the nanoparticle and surface stability were carried out in aqueous environments. It was observed that the bilayers were able to shield the materials' luminescence from quenching also in the presence of phosphate buffer that is currently considered the most disruptive environment for the nanoparticles

Polydopamine Nanoparticles Prepared Using Redox-Active Transition Metals

Autoxidation of dopamine to polydopamine by dissolved oxygen is a slow process that requires highly alkaline conditions. Polydopamine can be formed rapidly also in mildly acidic and neutral solutions by using redox-active transition-metal ions. We present a comparative study of polydopamine nanoparticles formed by autoxidation and aerobic or anaerobic oxidation in the presence of Ce(IV), Fe(III), Cu(II), and Mn(VII). The UV-vis spectra of the purified nanoparticles are similar, and dopaminechrome is an early intermediate species. At low pH, Cu(II) requires the presence of oxygen and chloride ions to produce polydopamine at a reasonable rate. The changes in dispersibility and surface charge take place at around pH 4, which indicates the presence of ionizable groups, especially carboxylic acids, on their surface. X-ray photoelectron spectroscopy shows the presence of three different classes of carbons, and the carbonyl/carboxylate carbons amount to 5-15 atom %. The N 1s spectra show the presence of protonated free amino groups, suggesting that these groups may interact with the pi-electrons of the intact aromatic dihydroxyindole moieties, especially in the metal-induced samples. The autoxidized and Mn(VII)-induced samples do not contain metals, but the metal content is 1-2 atom % in samples prepared with Ce(IV) or Cu(II), and ca. 20 atom % in polydopamine prepared in the presence of Fe(III). These differences in the metal content can be explained by the oxidation and complexation properties of the metals using the general model developed. In addition, the nitrogen content is lower in the metal-induced samples. All of the metal oxidants studied can be used to rapidly prepare polydopamine at room temperature, but the possible influence of the metal content and nitrogen loss should be taken into account

Is there a generalized timing impairment in Autism Spectrum Disorders across time scales and paradigms?

Individuals with ASD have abnormal motor and perceptual functions that do not currently form diagnostic criteria of ASD, but nevertheless may affect everyday behaviour. Temporal processing seems to be one of such non-diagnostic yet impaired domains, although the lack of systematic studies testing different aspects of timing in the same sample of participants prevents a conclusive assessment of whether there is a generalized temporal deficit in ASD associated with diagnostic symptoms. 17 children diagnosed with ASD and 18 typically developing age- and IQ-matched controls carried out a set of motor and perceptual timing tasks: free tapping, simultaneity judgment, auditory duration discrimination, and verbal duration estimation. Parents of participants filled in a questionnaire assessing the sense and management of time. Children with ASD showed faster and more variable free tapping than controls. Auditory duration discrimination thresholds were higher in the ASD group than controls in a sub-second version of the task, while there were no group differences in a supra-second discrimination of intervals. Children with ASD showed more variable thresholds of simultaneity judgment, and they received lower parental scores for their sense and management of time. No group differences were observed in the verbal duration estimation task in the minute-range. Different timing functions were correlated in the ASD group but not among controls, whilst several timing measures correlated with ASD symptoms. We conclude that children with ASD show a broad range of abnormalities in temporal processing tasks including motor timing, perceptual timing, and temporal perspective

Is there a generalized timing impairment in Autism Spectrum Disorders across time scales and paradigms?

Individuals with ASD have abnormal motor and perceptual functions that do not currently form diagnostic criteria of ASD, but nevertheless may affect everyday behaviour. Temporal processing seems to be one of such non-diagnostic yet impaired domains, although the lack of systematic studies testing different aspects of timing in the same sample of participants prevents a conclusive assessment of whether there is a generalized temporal deficit in ASD associated with diagnostic symptoms. 17 children diagnosed with ASD and 18 typically developing age- and IQ-matched controls carried out a set of motor and perceptual timing tasks: free tapping, simultaneity judgment, auditory duration discrimination, and verbal duration estimation. Parents of participants filled in a questionnaire assessing the sense and management of time. Children with ASD showed faster and more variable free tapping than controls. Auditory duration discrimination thresholds were higher in the ASD group than controls in a sub-second version of the task, while there were no group differences in a supra-second discrimination of intervals. Children with ASD showed more variable thresholds of simultaneity judgment, and they received lower parental scores for their sense and management of time. No group differences were observed in the verbal duration estimation task in the minute-range. Different timing functions were correlated in the ASD group but not among controls, whilst several timing measures correlated with ASD symptoms. We conclude that children with ASD show a broad range of abnormalities in temporal processing tasks including motor timing, perceptual timing, and temporal perspective.</p