Optimizing the Heavy Metal Ion Sensing Properties of Functionalized Silver Nanoparticles: The Role of Surface Coating Density

We present a colorimetric sensor based on functionalized silver nanoparticles for the detection of metal ions in aqueous solutions. The interaction between the target metal ion and the functionalizing agent triggers the aggregation of these nanoparticles, and the consequent change in optical properties allows the detection/quantification of the analyte. In detail, this work describes the synthesis of AgNPs by a chemical reduction method, and the production of mercaptoundecanoic acid functionalized NPs with different surface densities (multi-, full-, and two partial layers). UV-Vis spectroscopy was used to monitor the functionalization processes, and to investigate the aggregation behavior of each AgNPs@11MUA sensor upon titration with the metal ions of interest, namely Ni2+, Zn2+, Co2+, Cd2+, Mn2+, and Cu2+. The resulting UV-Vis raw data obtained for each layer density were submitted to principal component analysis to dissect the role of the metal ions in NP aggregation and in establishing the sensitivity and selectivity of the AgNPs@11MUA sensor. Interestingly, we observed an increase in sensor sensitivity and selectivity at a lower density of the functionalizing agent on the AgNPs’ surface, which results in characteristic colors of the NP suspension upon titration with each metal ion

Study of solvent extraction of mercury(II) with dibenzo-18-crown-6 from hydrochloric acid solution into benzene

The effect of Li+, K+, NH+4, Ca2+ or Sr2+ in the extraction of mercury(II) as chloro-complexes from solutions in hydrochloric acid with dibenzo-18-crown-6 (DB18C6) into benzene and the stoichiometries of the reactions have been studied. The crystalline extracted species were characterized by morphological and microanalysis measurements by scanning electron microscopy and energy dispersive X-ray spectrometry respectively

Aggregation behavior of a tetracarboxylic porphyrin in aqueous solution.

The aggregation of 3,8,13,18-tetramethyl-21H,23H-porphine-2,7,2,17-tetrapropionic acid (Coproporphyrin-I) has been investigated by UV–vis spectroscopy in aqueous solutions. The aggregation occurred by total neutralization of propionic groups and can be induced by alkaline salts, hydrogen peroxide or acidification. The hydrogen peroxide effect is investigated in the presence of different concentrations and it has been observed that only high concentrations favour the formation of H-aggregates. The dimerization constants in the several experimental conditions are reported. The H-dimers of Coproporphyrin-I in particular experimental conditions formed highly aggregate species depending on the pH. The kinetic of aggregation has been studied at different pHs and the results have showed that the log of kinetic constants kP were linearly dependent on the pH. The morphology of these aggregates, investigated by SEM spectroscopy, showed that the solvent polarity influenced their structures

Interaction of Porphyrins with Carbon Nanotube

Porphyrins are the light-absorbing chromophores that play a central role in photosynthesis. They show absorption in the 400–450 nm region of Soret band and in the 500–700 nm region of Q-bands and are particularly interesting for their long-lived intermediate electronic state that is accessed upon their irradiation by visible light. A variety of spectroscopic studies performed in solution indicate1,2 that a photoinduced electron transfer (PET) occurs from the porphyrin to the carbon-based species. Cu(II) and Zn(II) complexes of Coproporphyrin-I (2,7,12,17-tetrapropionic acid of 3,8,13,18- tetramethyl-21H,23H porphyrin or CPI), has been synthesized in our laboratory and tested as sensitizers in DSSC 3. In this study the reactions of CPI, CPIZn and CPICu with CNT have been monitored, with Uv-Vis Spectroscopy, and kinetics and thermodynamic data of CNT-(CPI-dyes) it has been obtained. The obtained “compounds” has been characterized after absorption on conventional nanostructured semiconducting TiO2 layer with scanning electron microscopy (SEM). The CNT-(CPI-dyes) concentrations and adsorption times affected the adsorption on TiO2 surfaces and the equilibrium and kinetic data obtained have permit to establish the best experimental conditions for the adsorption of these CNT-(CPI-dyes) and have demonstrated that these, according to the Langmuir model and with pseudo first-order kinetics, are adsorbed effectively in the support of TiO2 monolayer. The obtained CNT-(CPI-dyes) will be used as sensitizers in order to explore their potentiality in the DSSC applications

HPLC-DAD-ESI/MS Identification of Light Harvesting and Light Screening Pigments in the Lake Sediments at Edmonson Point

The composition of sedimentary pigments in the Antarctic lake at Edmonson Point has been investigated and compared with the aim to provide a useful analytical method for pigments separation and identification, providing reference data for future assessment of possible changes in environmental conditions. Reversed phase high performance liquid chromatography (HPLC) with electrospray-mass spectrometry (ESI-MS) detection and diode array detection (DAD) has been used to identify light screening and light harvesting pigments.The results are discussed in terms of local environmental conditions

Water Decontamination from Cr(VI) by Transparent Silica Xerogel Monolith

Cr(VI) is highly soluble and mobile in water solution and extremely toxic. In order to obtain a specific material with adsorption properties towards Cr(VI), and that can be used in environmental remediation of water contaminated with Cr(VI), one-step sol-gel technique, at low temperature (50 °C), has been optimized to prepare transparent silica-based xerogel monolith by using tetraethyl orthosilicate as precursor. The obtained xerogel, with disk shape, was fully characterized by Raman, BET, FE-SEM and XRD analysis. The results indicated that the material showed silica amorphous phase and high porosity. The study of the adsorption properties towards different concentrations of Cr(VI), in the form of HCrO4− in acidic condition, showed prominent results. The absorption kinetics were evaluated by studying different models, the final result showing that the absorption of Cr(VI) occurred through intra-particle diffusion process, following two steps, and that the absorption equilibrium is regulated by Freundlich isotherm model. The material can be restored by reducing the hazardous Cr(VI) to Cr(III), a less toxic form of chromium, by 1,5-diphenylcarbazide, and with successive treatment in acidic water

Silver Nanoparticle-Based Sensor for the Selective Detection of Nickel Ions

Silver nanoparticles (AgNPs) can be used as a surface plasmon resonance (SPR) colorimetric sensor; the correlation between the SPR phenomenon and the aggregation state of nanoparticle allows the real-time detection of a target molecule. Surface functionalization of NPs with proper molecular baits is often performed to establish the selectivity of the sensor. This work reports on the synthesis of AgNPs under reducing conditions and on the functionalization thereof with mercaptoundecanoic acid (11-MUA). UV-VIS Spectroscopy confirmed the formation of AgNPs, eliciting a surface plasmon absorption band (SPAB) at 393 nm that shifted to 417 nm upon surface coating. Dynamic light scattering was used to investigate the surface coatings; moreover, pelleted AgNPs@11MUA nanoparticles were characterized by scanning electron microscopy (SEM), energy dispersive X-ray analyzers (EDX), and infrared spectroscopy to corroborate the presence of 11MUA on the surface. Most interestingly, the resulting AgNPs@11MUA selectively detected micromolar levels of Ni2+, also in the presence of other cations such as Mn2+, Co2+, Cd2+, Cu2+, Zn2+, Fe2+, Hg2+, Pb2+, and Cr3+