Design and application of potentiometric sensors for the determination of mefenamic and phenylanthranilic acids.

Characteristics, performance and applications of potentiometric membrane sensors are described for the determination of mefenamic and phenylanthranilic ions. Ion associates of mefenamic, ClO4-, and phenylanthranilic ions with crystal violet (counter-cation) as ion exchange sites have been used as ionophores in the plasticized one- and two-layer membrane ion-selective electrodes. The LOD is reported to be 8.4 × 10-5 M for mefenamic acid, and 5.1 × 10-5 M for phenylanthranilic acid. The cations of basic dyes (crystal violet) are characterized by significant delocalization of the positive charge and polarizability. This may explain the better selectivity of the developed sensors. These sensors were used for the direct assay of mefenamic and N-phenylanthranilic acids in model solutions and applications studied in commercial pharmaceutical preparations.

Two-step light conversion with quantum dots inside non-linear crystals.

Up-conversion of infrared (IR) to visible light is demonstrated via an unconventional two-step process combining second harmonic generation with photoluminescence. This is achieved in a composite material formed by single crystals of KH2PO4 (KDP), in which CdTe/CdS quantum dots (QDs) are embedded during a crystal growth. The second harmonic generation from the IR laser frequency in KDP takes place, and then, generated light is absorbed by QDs and luminescence is emitted. Compared to the most common up-converting materials based on lanthanide ions, our novel composites use only abundant elements and have several other properties with application potential: the excitation and emission can cover a broader spectral range, and the response is much faster (ns compared to ms) and is strongly dependent on the direction of the incident beam.

Influence of the KBr matrix on the luminescence properties of CdTe quantum dots.

The investigation of the luminescence properties of CdTe/KBr composites with encapsulated quantum dots (QDs) of different sizes was performed and the influence of the KBr matrix on the luminescence properties of CdTe QDs was studied. Encapsulation of nanoparticles by a solid matrix caused a bathochromic shift in the luminescence peak and the shift value was the larger the smaller the size of the quantum dots. Interband quantum transition theory was used to explain the influence of the matrix on the luminescence properties of the capsulated CdTe QDs. Theoretical calculations showed that the observed QD luminescence peak corresponded to a 1 s-1 s electronic transition, and its low-energy shift after the transfer of QDs from dielectric water to the KBr matrix was due to a corresponding decrease in the depths of electrons and holes potential wells.

Synthesis and Properties of Water-Soluble Blue-Emitting Mn-Alloyed CdTe Quantum Dots.

In this work, we prepared CdTe quantum dots, and series of Cd1-xMnxTe-alloyed quantum dots with narrow size distribution by an ion-exchange reaction in water solution. We found that the photoluminescence peaks are shifted to higher energies with the increasing Mn2+ content. So far, this is the first report of blue-emitting CdTe-based quantum dots. By means of cyclic voltammetry, we detected features of electrochemical activity of manganese energy levels formed inside the Cd1-xMnxTe-alloyed quantum dot band gap. This allowed us to estimate their energy position. We also demonstrate paramagnetic behavior for Cd1-xMnxTe-alloyed quantum dots which confirmed the successful ion-exchange reaction.

Synthesis of Au-CdS@CdSe Hybrid Nanoparticles with a Highly Reactive Gold Domain.

We propose a novel route to synthesize semiconductor-gold hybrid nanoparticles directly in water, resulting in much larger gold domains than previous protocols (up to 50 nm) with very reactive surfaces which allow further functionalization. This method advances the possibility of self-assembly into complex structures with catalytic activity toward the reduction of nitro compounds by hydrides. The large size of these gold domains in hybrid particles supports efficient light scattering at the plasmon resonance frequency, making such structures attractive for single-particle studies.

Influence of the Shell Thickness and Ratio Between Core Elements on Photostability of the CdTe/CdS Core/Shell Quantum Dots Embedded in a Polymer Matrix.

This paper reports a study of photooxidation and photomodification processes of the CdTe/CdS quantum dots embedded in a polymer matrix under ambient condition. During the first few minutes of irradiation, the quasi-inverse increase in photoluminescence intensity has been observed indicating the passivation of the nanocrystal surface traps by water molecules. A prolonged irradiation of the polymer film containing CdTe/CdS quantum dots leads to a significant decrease in the photoluminescence intensity together with the "blue shift" of the photoluminescence peak energy associated with quantum dot photooxidation. The mechanisms of the CdTe/CdS core/shell quantum dot photooxidation and photomodification in a polymer matrix are discussed. We have found a correlation between the photostability of the quantum dots and the CdS shell thickness as well as the ratio of core elements.

Highly sensitive plasmonic silver nanorods.

We compare the single-particle plasmonic sensitivity of silver and gold nanorods with similar resonance wavelengths by monitoring the plasmon resonance shift upon changing the environment from water to 12.5% sucrose solution. We find that silver nanoparticles have 1.2 to 2 times higher sensitivity than gold, in good agreement with simulations based on the boundary-elements-method (BEM). To exclude the effect of particle volume on sensitivity, we test gold rods with increasing particle width at a given resonance wavelength. Using the Drude-model of optical properties of metals together with the quasi-static approximation (QSA) for localized surface plasmons, we show that the dominant contribution to higher sensitivity of silver is the lower background polarizability of the d-band electrons and provide a simple formula for the sensitivity. We improve the reversibility of the silver nanorod sensors upon repeated cycles of environmental changes by blocking the high energy parts of the illumination light.

Light-controlled one-sided growth of large plasmonic gold domains on quantum rods observed on the single particle level.

We create large gold domains (up to 15 nm) exclusively on one side of CdS or CdSe/CdS quantum rods by photoreduction of gold ions under anaerobic conditions. Electrons generated in the semiconductor by UV stimulation migrate to one tip where they reduce gold ions. Large gold domains eventually form; these support efficient plasmon oscillations with a light scattering cross section large enough to visualize single hybrid particles in a dark-field microscope during growth in real time.

Synthesis of rod-shaped gold nanorattles with improved plasmon sensitivity and catalytic activity.

We prepared rod-shaped gold nanorattles solid gold nanorods surrounded by a thin gold shell using a galvanic replacement process starting with silver-coated gold nanorods. These structures are very promising candidates for catalytic applications and optimized plasmon sensors. They combine the advantages of rods (low plasmon resonance frequency, large polarizability, small damping) with the high surface area of hollow structures. The plasmon sensitivity to changes in the dielectric environment is up to 50% higher for gold nanorattles compared to gold nanorods with the same resonance frequency and 6x higher than for plasmons in spherical gold nanoparticles. The catalytic activity measured for the reduction of p-nitrophenol is 4x larger than for bare gold nanorods.

Mapping the polarization pattern of plasmon modes reveals nanoparticle symmetry.

We study the wavelength and polarization dependent plasmon resonances of single silver and gold nanorods, triangles, cubes, and dimers with a novel single particle spectroscopy method (RotPOL). In RotPOL, a rotating wedge-shaped polarizer encodes the full polarization information of each particle within one image. This reveals the symmetry of the particles and their plasmon modes, allows analyzing inhomogeneous samples and the monitoring of particle shape changes during growth in situ.

Plasmonic focusing reduces ensemble linewidth of silver-coated gold nanorods.

Silver coating gold nanorods reduces the ensemble plasmon line width by changing the relation connecting particle shape and plasmon resonance wavelength. This change, we term "plasmonic focusing", leads to less variation of resonance wavelengths for the same particle size distribution. We also find smaller single particle linewidth comparing resonances at the same wavelength but show that this does not contribute to the ensemble linewidth narrowing.