Optical Chemical Sensors: Design and Applications.

More than ever, optical chemical sensing is a thriving research field with a strong outlook in terms of future development and penetration into growing industrial markets [...].

Colorimetric and Fluorescent Sensing of Copper Ions in Water through o-Phenylenediamine-Derived Carbon Dots.

Fluorescent nitrogen and sulfur co-doped carbon dots (NSCDs) were synthesized using a simple one-step hydrothermal method starting from o-phenylenediamine (OPD) and ammonium sulfide. The prepared NSCDs presented a selective dual optical response to Cu(II) in water through the arising of an absorption band at 660 nm and simultaneous fluorescence enhancement at 564 nm. The first effect was attributed to formation of cuprammonium complexes through coordination with amino functional groups of NSCDs. Alternatively, fluorescence enhancement can be explained by the oxidation of residual OPD bound to NSCDs. Both absorbance and fluorescence showed a linear increase with an increase of Cu(II) concentration in the range 1-100 µM, with the lowest detection limit of 100 nM and 1 µM, respectively. NSCDs were successfully incorporated in a hydrogel agarose matrix for easier handling and application to sensing. The formation of cuprammonium complexes was strongly hampered in an agarose matrix while oxidation of OPD was still effective. As a result, color variations could be perceived both under white light and UV light for concentrations as low as 10 µM. Since these color changes were similarly perceived in tap and lake water samples, the present method could be a promising candidate for simple, cost-effective visual monitoring of copper onsite.

Tuning the Sensing Properties of N and S Co-Doped Carbon Dots for Colorimetric Detection of Copper and Cobalt in Water.

In this study, nitrogen and sulfur co-doped carbon dots (NS-CDs) were investigated for the detection of heavy metals in water through absorption-based colorimetric response. NS-CDs were synthesized by a simple one-pot hydrothermal method and characterized by TEM, STEM-coupled with energy dispersive X-ray analysis, NMR, and IR spectroscopy. Addition of Cu(II) ions to NS-CD aqueous solutions gave origin to a distinct absorption band at 660 nm which was attributed to the formation of cuprammonium complexes through coordination with amino functional groups of NS-CDs. Absorbance increased linearly with Cu(II) concentration in the range 1-100 µM and enabled a limit of detection of 200 nM. No response was observed with the other tested metals, including Fe(III) which, however, appreciably decreased sensitivity to copper. Increase of pH of the NS-CD solution up to 9.5 greatly reduced this interference effect and enhanced the response to Cu(II), thus confirming the different nature of the two interactions. In addition, a concurrent response to Co(II) appeared in a different spectral region, thus suggesting the possibility of dual-species multiple sensitivity. The present method neither requires any other reagents nor any previous assay treatment and thus can be a promising candidate for low-cost monitoring of copper onsite and by unskilled personnel.

Colorimetric Detection of Chromium(VI) Ions in Water Using Unfolded-Fullerene Carbon Nanoparticles.

Water pollution caused by hexavalent chromium (Cr(VI)) ions represents a serious hazard for human health due to the high systemic toxicity and carcinogenic nature of this metal species. The optical sensing of Cr(VI) through specifically engineered nanomaterials has recently emerged as a versatile strategy for the application to easy-to-use and cheap monitoring devices. In this study, a one-pot oxidative method was developed for the cage opening of C60 fullerene and the synthesis of stable suspensions of N-doped carbon dots in water-THF solutions (N-CDs-W-THF). The N-CDs-W-THF selectively showed variations of optical absorbance in the presence of Cr(VI) ions in water through the arising of a distinct absorption band peaking at 550 nm, i.e., in the transparency region of pristine material. Absorbance increased linearly, with the ion concentration in the range 1-100 µM, thus enabling visual and ratiometric determination with a limit of detection (LOD) of 300 nM. Selectivity and possible interference effects were tested over the 11 other most common heavy metal ions. The sensing process occurred without the need for any other reactant or treatment at neutral pH and within 1 min after the addition of chromium ions, both in deionized and in real water samples.

Detection of Heavy Metals in Water Using Graphene Oxide Quantum Dots: An Experimental and Theoretical Study.

In this work, we investigate by ab initio calculations and optical experiments the sensitivity of graphene quantum dots in their use as devices to measure the presence, and concentration, of heavy metals in water. We demonstrate that the quenching or enhancement in the optical response (absorption, emission) depends on the metallic ion considered. In particular, two cases of opposite behaviour are considered in detail: Cd2+, where we observe an increase in the emission optical response for increasing concentration, and Pb2+ whose emission spectra, vice versa, are quenched along the concentration rise. The experimental trends reported comply nicely with the different hydration patterns suggested by the models that are also capable of reproducing the minor quenching/enhancing effects observed in other ions. We envisage that quantum dots of graphene may be routinely used as cheap detectors to measure the degree of poisoning ions in water.

Top-Down N-Doped Carbon Quantum Dots for Multiple Purposes: Heavy Metal Detection and Intracellular Fluorescence.

In the present study, we successfully synthesized N-doped carbon quantum dots (N-CQDs) using a top-down approach, i.e., hydroxyl radical opening of fullerene with hydrogen peroxide, in basic ambient using ammonia for two different reaction times. The ensuing characterization via dynamic light scattering, SEM, and IR spectroscopy revealed a size control that was dependent on the reaction time, as well as a more pronounced -NH2 functionalization. The N-CQDs were probed for metal ion detection in aqueous solutions and during bioimaging and displayed a Cr3+ and Cu2+ selectivity shift at a higher degree of -NH2 functionalization, as well as HEK-293 cell nuclei marking.

Designing Cascades of Electron Transfer Processes in Multicomponent Graphene Conjugates.

A novel family of nanocarbon-based materials was designed, synthesized, and probed within the context of charge-transfer cascades. We integrated electron-donating ferrocenes with light-harvesting/electron-donating (metallo)porphyrins and electron-accepting graphene nanoplates (GNP) into multicomponent conjugates. To control the rate of charge flow between the individual building blocks, we bridged them via oligo-p-phenyleneethynylenes of variable lengths by ß-linkages and the Prato-Maggini reaction. With steady-state absorption, fluorescence, Raman, and XPS measurements we realized the basic physico-chemical characterization of the photo- and redox-active components and the multicomponent conjugates. Going beyond this, we performed transient absorption measurements and corroborated by single wavelength and target analyses that the selective (metallo)porphyrin photoexcitation triggers a cascade of charge transfer events, that is, charge separation, charge shift, and charge recombination, to enable the directed charge flow. The net result is a few nanosecond-lived charge-separated state featuring a GNP-delocalized electron and a one-electron oxidized ferrocenium.

Polystyrene Opals Responsive to Methanol Vapors.

Photonic crystals (PCs) show reflectance spectra depending on the geometrical structure of the crystal, the refractive index (neff), and the light incident angle, according to the Bragg-Snell law. Three-dimensional photonic crystals (3D-PCs) composed of polymeric sub-micrometer spheres, are arranged in an ordered face cubic centered (fcc) lattice and are good candidates for vapor sensing by exploiting changes of the reflectance spectra. We synthesized high quality polystyrene (PS) 3D-PCs, commonly called opals, with a filling factor f near to the ideal value of 0.74 and tested their optical response in the presence of different concentrations of methanol (MeOH) vapor. When methanol was present in the voids of the photonic crystals, the reflectance spectra experienced energy shifts. The concentration of methyl alcohol vapor can be inferred, due to a linear dependence of the reflectance band maximum wavelength as a function of the vapor concentration. We tested the reversibility of the process and the time stability of the system. A limit of detection (LOD) equal to 5% (v/v0), where v was the volume of methanol and v0 was the total volume of the solution (methanol and water), was estimated. A model related to capillary condensation for intermediate and high methanol concentrations was discussed. Moreover, a swelling process of the PS spheres was invoked to fully understand the unexpected energy shift found for very high methanol content.

Discriminating between Different Heavy Metal Ions with Fullerene-Derived Nanoparticles.

A novel type of graphene-like nanoparticle, synthesized by oxidation and unfolding of C60 buckminsterfullerene fullerene, showed multiple and reproducible sensitivity to Cu2+, Pb2+, Cd2+, and As(III) through different degrees of fluorescence quenching or, in the case of Cd2+, through a remarkable fluorescence enhancement. Most importantly, only for Cu2+ and Pb2+, the fluorescence intensity variations came with distinct modifications of the optical absorption spectrum. Time-resolved fluorescence study confirmed that the common origin of these diverse behaviors lies in complexation of the metal ions by fullerene-derived carbon layers, even though further studies are required for a complete explanation of the involved processes. Nonetheless, the different response of fluorescence and optical absorbance towards distinct cationic species makes it possible to discriminate between the presence of Cu2+, Pb2+, Cd2+, and As(III), through two simple optical measurements. To this end, the use of a three-dimensional calibration plot is discussed. This property makes fullerene-derived nanoparticles a promising material in view of the implementation of a selective, colorimetric/fluorescent detection system.

Functionalization of Carbon Spheres with a Porphyrin-Ferrocene Dyad.

Meso-tetraphenylporphyrin connected with a ferrocene molecule in the beta-position of the macrocycle through a triple carbon-carbon bond has been bound to carbon spheres using the Prato-Maggini reaction. The ethynyl or/and phenylene ethynylene subunits were chosen as a linking bridge to give a high conjugation degree between the donor (i. e., ferrocene), the photoactive compound (i. e., porphyrin), and the acceptor (i. e., carbon spheres). The molecular bridges have been directly linked to the beta-pyrrole positions of the porphyrin ring, generating a new example of a long-range donor-acceptor system. Steady-state fluorescence studies together with Raman and XPS measurements helped understanding the chemical and physical properties of the porphyrin ring in the new adduct. The spectroscopic characteristics were also compared with those obtained from a similar compound bearing fullerene instead of carbon spheres.

Sensitivity to Heavy-Metal Ions of Unfolded Fullerene Quantum Dots.

A novel type of graphene-like quantum dots, synthesized by oxidation and cage-opening of C60 buckminsterfullerene, has been studied as a fluorescent and absorptive probe for heavy-metal ions. The lattice structure of such unfolded fullerene quantum dots (UFQDs) is distinct from that of graphene since it includes both carbon hexagons and pentagons. The basic optical properties, however, are similar to those of regular graphene oxide quantum dots. On the other hand, UFQDs behave quite differently in the presence of heavy-metal ions, in that multiple sensitivity to Cu2+, Pb2+ and As(III) was observed through comparable quenching of the fluorescent emission and different variations of the transmittance spectrum. By dynamic light scattering measurements and transmission electron microscope (TEM) images we confirmed, for the first time in metal sensing, that this response is due to multiple complexation and subsequent aggregation of UFQDs. Nonetheless, the explanation of the distinct behaviour of transmittance in the presence of As(III) and the formation of precipitate with Pb2+ require further studies. These differences, however, also make it possible to discriminate between the three metal ions in view of the implementation of a selective multiple sensor.

Towards high-performance, low-cost quartz sensors with high-density, well-separated, vertically aligned ZnO nanowires by low-temperature, seed-less, single-step, double-sided growth.

Resonant sensors with nanostructured surfaces have long been considered as an emergent platform for high-sensitivity transduction because of the potentially very large sensing areas. Nevertheless, until now only complex, time-consuming, expensive and sub-optimal fabrication procedures have been described; in fact, especially with reference to in-liquid applications, very few devices have been reported. Here, we first demonstrate that, by immersing standard, ultra-low-cost quartz resonators with un-polished silver electrodes in a conventional zinc nitrate/HMTA equimolar nutrient solution, the gentle contamination from the metallic package allows direct growth on the electrodes of arrays of high-density (up to 10 µm⁻²) and well-separated (no fusion at the roots) ZnO nanowires without any seed layer or thermal annealing. The combination of high-density and good separation is ideal for increasing the sensing area; moreover, this uniquely simple, single-step process is suitable for conventional, ultra-low-cost and high-frequency quartzes, and results in devices that are already packaged and ready to use. As an additional advantage, the process parameters can be effectively optimized by measuring the quartz admittance before and after growth. As a preliminary test, we show that the sensitivity to the liquid properties of high-frequency (i.e. high sensitivity) quartzes can be further increased by nearly one order of magnitude and thus show the highest ever reported frequency shifts of an admittance resonance in response to immersion in both ethanol and water.

Dimensional accuracy of pickup implant impression: an in vitro comparison of novel modular versus standard custom trays.

PURPOSE: The purpose of this in vitro study was to compare the dimensional accuracy of the pickup impression technique using a modular individual tray (MIT) and using a standard individual tray (ST) for multiple internal-connection implants. The roles of both materials and geometric misfits were considered. MATERIALS AND METHODS: First, because the MIT relies on the stiffness and elasticity of acrylic resin material, a preliminary investigation of the resin volume contraction during curing and polymerization was done. Then, two sets of specimens were tested to compare the accuracy of the MIT (test group) to that of the ST (control group). The linear and angular displacements of the transfer copings were measured and compared during three different stages of the impression procedure. Experimental measurements were performed with a computerized coordinate measuring machine. RESULTS: The curing dynamic of the acrylic resin was strongly dependent on the physical properties of the acrylic material and the powder/liquid ratio. Specifically, an increase in the powder/liquid ratio accelerated resin polymerization (curing time decreases by 70%) and reduced the final volume contraction by 45%. However, the total shrinkage never exceeded the elastic limits of the material; hence, it did not affect the coping's stability. In the test group, linear errors were reduced by 55% and angular errors were reduced by 65%. CONCLUSIONS: Linear and angular displacements of the transfer copings were significantly reduced with the MIT technique, which led to higher dimensional accuracy versus the ST group. The MIT approach, in combination with a thin and uniform amount of acrylic resin in the pickup impression technique, showed no significant permanent distortions in multiple misalignment internal-connection implants compared to the ST technique.

Effects of progressive halogen substitution on the photoluminescence properties of an erbium-porphyrin complex.

We have investigated the photoluminescence properties of porphyrin-based erbium and gadolinium complexes at different levels of halogen substitution. Both the intensity and the decay time of the erbium near-infrared emission correlate with the degree of the halogenation. Conversely, no clear correlation is found with the triplet-state energy levels nor with the intensity of the residual visible emission. Such findings confirm that the key role in the low efficiency of the near-infrared emission is played by the nonradiative quenching of the erbium emitting level due to the vibrational modes of the surrounding C-H bonds.

Photophysical properties of 1,3,5-tris(2-naphthyl)benzene and related less-arylated compounds: experimental and theoretical investigations.

Recently, a growing interest has concerned compounds characterized by high chemical and photophysical stability and high quantum yield for their possible technological applications. 1,3,5-Tris(2-naphthyl)benzene (N3B), 1,3-bis(2-naphthyl)benzene (N2B), and 2-naphthyl-benzene (N1B) are promising compounds, but they needed a detailed photophysical characterization. In this context, theoretical and experimental investigations have been carried out. Steady-state and decay time fluorescence measurements indicate that the second naphthyl group, added in the meta position of N1B, perturbs the electronic levels, whereas the further naphthyl addition, leading to N3B, does not promote changes in all of the observed properties. The investigated compounds show a biexponential fluorescence decay that has been attributed to a rearrangement involving the exited states S(1) and S(2). The minimum structure corresponding to the S(1) and S(2) states has been obtained at the configuration interaction with single excitations (CIS) level of theory. For the ground-state geometry, a conformational analysis at the Hartree-Fock level has also been carried out. We have evaluated the energy gaps between electronic levels by using Zerner's intermediate neglect of differential overlap (ZINDO) method. The species involved in the fluorescence have been experimentally characterized, and the decay-associated spectra have been obtained.