Bright thermal (blackbody) emission of visible light from LnO2 (Ln = Pr, Tb), photoinduced by a NIR 980 nm laser.

The increasing demand for renewable energy has been promoting a rapid development of photovoltaic technologies. Given this, photoinduced thermal emission is being explored with the aim of improving solar cell performance by converting low-energy IR photons into visible light. Here, we report the light-induced blackbody emission from LnO2 (Ln = Pr and Tb) as a potential emitter for thermophotovoltaic applications. Lanthanide dioxides display broad IR absorption and a direct optical band gap of 1.49 (PrO2) and 1.51 eV (TbO2). These materials achieve a maximum temperature of ∼1500 K under a power density excitation of 160 W cm-2 and display a stable bright light emission. Thermal emission can be tuned from laser power density modulation.

Multifunctional System Polyaniline-Decorated ZIF-8 Nanoparticles as a New Chemo-Photothermal Platform for Cancer Therapy.

Polyaniline-decorated ZIF-8 nanoparticles (nPANI@nZIF-8) were easily synthesized and employed as a multifunctional system for the delivery of the antitumor drug 5-fluorouracil (5-FU). Because of the storage ability of the network ZIF-8, 68% of the total amount of the 5-FU drug was released at pH 5.2. The system exhibits absorption in the near-infrared (NIR) region and can be used in the photothermal therapy owing to the presence of nPANI, which has a strong NIR uptake. This absorption causes local hyperthermia by aiding in the diffusion of the drug molecules contained by the polymer into nPANI@nZIF-8/5-FU achieving a greater release of the 5-FU drug, about 80% activated by an NIR laser (λ = 980 nm). This hyperthermia reached about 70 °C (200 µL, 1 mg mL-1 nPANI@nZIF-8), which was directly proportional to the concentration of the material. Therefore, our work can aid in the construction of new chemo-photothermal platforms that may be employed in cancer therapy.

Random Lasing at Localization Transition in a Colloidal Suspension (TiO2@Silica).

Anderson localization of light and random lasing in this critical regime is an open research frontier, which besides being a basic research topic could also lead to important applications. This article investigates the random laser action at the localization transition in a strongly disordered scattering medium composed of a colloidal suspension of core-shell nanoparticles (TiO2@Silica) in ethanol solution of Rhodamine 6G. The classical superfluorescence band of the random laser was measured separately by collecting the emission at the back of the samples, showing a linear dependence with pumping fluence without gain depletion. However, frontal collection showed saturation of the absorption and emission. Narrow peaks of approximately equal intensity are observed on top of the classical superfluorescence band, indicating suppression of the interaction between the peaks modes. The linewidth of these peaks is lower than that of the passive modes of the scattering medium. A method called fraction of absorbed pumping allowed us to infer that this peak's mode (localized modes) is confined to a shallow region near the input-pumping border.

Anderson localization of light in a colloidal suspension (TiO2@silica).

In recent years, there has been dramatic progress in the photonics field in disordered media, ranging from applications in solar collectors, photocatalyzers, random lasing, and other novel photonic functions, to investigations into fundamental topics, such as light confinement and other phenomena involving photon interactions. This paper reports several pieces of experimental evidence of localization transition in a strongly disordered scattering medium composed of a colloidal suspension of core-shell nanoparticles (TiO2@silica) in ethanol solution. We demonstrate the crossover from a diffusive transport to a localization transition regime as the nanoparticle concentration is increased, and that an enhanced absorption effect arises at localization transition.

Synthesis of Ag@Silica Nanoparticles by Assisted Laser Ablation.

This paper reports the synthesis of silver nanoparticles coated with porous silica (Ag@Silica NPs) using an assisted laser ablation method. This method is a chemical synthesis where one of the reagents (the reducer agent) is introduced in nanometer form by laser ablation of a solid target submerged in an aqueous solution. In a first step, a silicon wafer immersed in water solution was laser ablated for several minutes. Subsequently, an AgNO3 aliquot was added to the aqueous solution. The redox reaction between the silver ions and ablation products leads to a colloidal suspension of core-shell Ag@Silica NPs. The influence of the laser pulse energy, laser wavelength, ablation time, and Ag(+) concentration on the size and optical properties of the Ag@Silica NPs was investigated. Furthermore, the colloidal suspensions were studied by UV-VIS-NIR spectroscopy, X-Ray diffraction, and high-resolution transmission electron microscopy (HRTEM).

Desorption/ionization efficiencies of triacylglycerols and phospholipids via EASI-MS.

Knowledge of the major effects governing desorption/ionization efficiency is required for the development and application of ambient mass spectrometry. Although all triacylglycerols (TAG) have the same favorable protonation and cationization sites, their desorption/ionization efficiencies can vary dramatically during easy ambient sonic-spray ionization because of structural differences in the carbon chain. To quantify this somewhat surprising and drastic effect, we have performed a systematic investigation of desorption/ionization efficiencies as a function of unsaturation and length for TAG as well as for diacylglycerols, monoacylglycerols and several phospholipids (PL). Affinities for Na(+) as a function of unsaturation level have also been assayed via comprehensive metadynamics calculations to understand the influence of this phenomenon on the ionization efficiency. The results suggest that dipole-dipole interactions within a carbon chain tuned by unsaturation sites govern ionization efficiency of TAG and PL.

Baseline resolution of isomers by traveling wave ion mobility mass spectrometry: investigating the effects of polarizable drift gases and ionic charge distribution.

We have studied the behavior of isomers and analogues by traveling wave ion mobility mass spectrometry (TWIM-MS) using drift-gases with varying masses and polarizabilities. Despite the reduced length of the cell (18 cm), a pair of constitutional isomers, N-butylaniline and para-butylaniline, with theoretical collision cross-section values in helium (ΩHe ) differing by as little as 1.2 Å(2) (1.5%) but possessing contrasting charge distribution, showed baseline peak-to-peak resolution (Rp-p ) for their protonated molecules, using carbon dioxide (CO2), nitrous oxide (N2O) and ethene (C2H4 ) as the TWIM drift-gas. Near baseline Rp-p was also obtained in CO2 for a group of protonated haloanilines (para-chloroaniline, para-bromoaniline and para-iodoaniline) which display contrasting masses and theoretical ΩHe , which differ by as much as 15.7 Å(2) (19.5%) but similar charge distributions. The deprotonated isomeric pair of trans-oleic acid and cis-oleic acid possessing nearly identical theoretical ΩHe and ΩN2 as well as similar charge distributions, remained unresolved. Interestingly, an inversion of drift-times were observed for the 1,3-dialkylimidazolium ions when comparing He, N2 and N2O. Using density functional theory as a means of examining the ions electronic structure, and He and N2-based trajectory method algorithm, we discuss the effect of the long-range charge induced dipole attractive and short-range Van der Waals forces involved in the TWIM separation in drift-gases of differing polarizabilities. We therefore propose that examining the electronic structure of the ions under investigation may potentially indicate whether the use of more polarizable drift-gases could improve separation and the overall success of TWIM-MS analysis.

Novel core-shell (TiO2@Silica) nanoparticles for scattering medium in a random laser: higher efficiency, lower laser threshold and lower photodegradation.

There has been growing interest in scattering media in recent years, due to their potential applications as solar collectors, photocatalyzers, random lasers and other novel optical devices. Here, we have introduced a novel core-shell scattering medium for a random laser composed of TiO2@Silica nanoparticles. Higher efficiency, lower laser threshold and long photobleaching lifetime in random lasers were demonstrated. This has introduced a new method or parameter (fraction of absorbed pumping), which opens a new avenue to characterize and study the scattering media. Optical chemical and colloidal stabilities were combined by coating a suitable silica shell onto TiO2 nanoparticles.

Investigating the potential of metal-organic framework material as an adsorbent for matrix solid-phase dispersion extraction of pesticides during analysis of dehydrated Hyptis pectinata medicinal plant by GC/MS.

Metal-organic frameworks aluminum terephthalate MIL-53 and Cu-benzene-1,3,5-tricarboxylate (BTC) were tested for extraction of pyrimethanil, ametryn, dichlofluanid, tetraconazole, flumetralin, kresoximmethyl, and tebuconazole from the medicinal plant Hyptis pectinata, with analysis using GC/MS in the selected ion monitoring mode. Experiments carried out at different fortification levels (0.1, 0.5, and 1.0 microg/g) resulted in recoveries in the range 61 to 107% with RSD values between 3 and 12% for the metal-organic framework materials. Detection and quantification limits ranged from 0.02 to 0.07 and 0.05 to 0.1 microg/g, respectively, for the different pesticides studied. The method developed was linear over the range tested (0.04-20.0 microg/g), with correlation coefficients ranging from 0.9987 to 0.9998. Comparison of MIL-53 and Cu-BTC with C18-bonded silica showed good performance of the MIL-53 metal-organic framework as a sorbent for the pesticides tested.

Corrole isomers: intrinsic gas-phase shapes via traveling wave ion mobility mass spectrometry and dissociation chemistries via tandem mass spectrometry.

Corrole and four of its isomers with subtle structural changes promoted by exchange of nitrogen and carbon atoms in the corrole ring have been studied by traveling wave ion mobility mass spectrometry and collision induced dissociation experiments. Significant differences in shapes and charge distributions for their protonated molecules were found to lead to contrasting gas phase mobilities, most particularly for corrorin, the most "confused" isomer. Accordingly, corrorin was predicted by B3LYP/6-31g(d,p) and collisional cross section calculations to display the most compact tri-dimensional structure, whereas NCC4 and corrole were found to be the most planar isomers. Better resolution between the corrole isomers was achieved using the more polarizable and massive CO(2) as the drift gas. Sequential losses of HF molecules were found to dominate the dissociation chemistry of the protonated molecules of these corrole isomers, but their unique structures caused contrasting labilities towards CID, whereas NCC4 showed a peculiar and structurally diagnostic loss of NH(3), allowing its prompt differentiation from the other isomers.

Protomers: formation, separation and characterization via travelling wave ion mobility mass spectrometry.

Travelling wave ion mobility mass spectrometry (TWIM-MS) with post-TWIM and pre-TWIM collision-induced dissociation (CID) experiments were used to form, separate and characterize protomers sampled directly from solutions or generated in the gas phase via CID. When in solution equilibria, these species were transferred to the gas phase via electrospray ionization, and then separated by TWIM-MS. CID performed after TWIM separation (post-TWIM) allowed the characterization of both protomers via structurally diagnostic fragments. Protonated aniline (1) sampled from solution was found to be constituted of a ca. 5:1 mixture of two gaseous protomers, that is, the N-protonated (1a) and ring protonated (1b) molecules, respectively. When dissociated, 1a nearly exclusively loses NH(3) , whereas 1b displays a much diverse set of fragments. When formed via CID, varying populations of 1a and 1b were detected. Two co-existing protomers of two isomeric porphyrins were also separated and characterized via post-TWIM CID. A deprotonated porphyrin sampled from a basic methanolic solution was found to be constituted predominantly of the protomer arising from deprotonation at the carboxyl group, which dissociates promptly by CO(2) loss, but a CID-resistant protomer arising from deprotonation at a porphyrinic ring NH was also detected and characterized. The doubly deprotonated porphyrin was found to be constituted predominantly of a single protomer arising from deprotonation of two carboxyl groups.

Wood typification by Venturi easy ambient sonic spray ionization mass spectrometry: the case of the endangered Mahogany tree.

Venturi easy ambient sonic spray ionization mass spectrometry in both its liquid (V(L) -EASI-MS) and solid sample modes (V(S) -EASI-MS) is shown to provide nearly immediate and secure typification of woods, as demonstrated for Mahogany, an endangered and most valuable type of tropical wood. This reddish wood displays unique phytochemical markers (phragmalin-type limonoids) which are rapidly detected from the wood surface by V(S) -EASI-MS or from a simple methanol extract of a tiny wood chip by V(L) -EASI-MS. Unique profiles were obtained for Mahogany (Swietenia macrophylla) whereas genuine samples of six other similar types of woods, which are commonly falsified by artificial coloring and commercialized as Mahogany, display also typical but dissimilar pythochemical profiles as compared to that of the authentic wood. Variable and atypical chemical profiles were observed for artificially colored woods. Secure chemical characterization via V(S) -EASI-MS or V(s) -EASI-MS fingerprints of Mahogany and other types of woods with similar appearance should help to control the illegal logging and trade of this and other endangered woods and their falsification, and to create certified standards.

Resolution of isomeric multi-ruthenated porphyrins by travelling wave ion mobility mass spectrometry.

The ability of travelling wave ion mobility mass spectrometry (TWIM-MS) to resolve cationic meta/para and cis/trans isomers of mono-, di-, tri- and tetra-ruthenated supramolecular porphyrins was investigated. All meta isomers were found to be more compact than the para isomers and therefore mixtures of all isomeric pairs could be properly resolved with baseline or close to baseline peak-to-peak resolution (R(p-p)). Di-substituted cis/trans isomers were found, however, to present very similar drift times and could not be resolved. N(2) and CO(2) were tested as the drift gas, and similar α but considerably better values of R(p) and R(p-p) were always observed for CO(2).

Separation of isomeric disaccharides by traveling wave ion mobility mass spectrometry using CO2 as drift gas.

The use of CO(2) as a massive and polarizable drift gas is shown to greatly improve peak-to-peak resolution (R(p-p) ), as compared with N(2) , for the separation of disaccharides in a Synapt G2 traveling wave ion mobility cell. Near or baseline R(p-p) was achieved for three pairs of sodiated molecules of disaccharide isomers, that is, cellobiose and sucrose (R(p-p) = 0.76), maltose and sucrose (R(p-p) = 1.04), and maltose and lactose (R(p-p) = 0.74). Ion mobility mass spectrometry using CO(2) as the drift gas offers therefore an attractive alternative for fast and efficient separation of isomeric disaccharides.

Chemical profile of meta-chlorophenylpiperazine (m-CPP) in ecstasy tablets by easy ambient sonic-spray ionization, X-ray fluorescence, ion mobility mass spectrometry and NMR.

Meta-chlorophenylpiperazine (m-CPP) is a new illicit drug that has been sold as ecstasy tablets. Easy ambient sonic-spray ionization mass spectrometry (EASI-MS) and X-ray fluorescence spectrometry (XRF) are shown to provide relatively simple and selective screening tools to distinguish m-CPP tablets from tablets containing amphetamines (mainly 3,4-methylenedioxymethamphetamine (MDMA)). EASI-MS detects the active ingredients in their protonated forms: [m-CPP + H](+) of m/z 197, [MDMA + H](+) of m/z 194, and [2MDMA + HCl + H](+) of m/z 423 and other ions from excipients directly on the tablet surface, providing distinct chemical fingerprints. XRF identifies Cl, K, Ca, Fe, and Cu as inorganic ingredients present in the m-CPP tablets. In contrast, higher Cl concentrations and a more diverse set of elements (P, Cl, Ca, Fe, Cu, Zn, Pt, V, Hf, Ti, Pt, and Zr) were found in MDMA tablets. Principal component analysis applied to XRF data arranged samples in three groups: m-CPP tablets (four samples), MDMA tablets (twenty three samples), and tablets with no active ingredients (three samples). The EASI-MS and XRF techniques were also evaluated to quantify m-CPP in ecstasy tablets, with concentrations ranging from 4 to 40 mg of m-CPP per tablets. The m-CPP could only be differentiated from its isomers (o-CPP and for the three isomers p-CPP) by traveling wave ion mobility mass spectrometry and NMR measurements.

Intrinsic mobility of gaseous cationic and anionic aggregates of ionic liquids.

Travelling-wave ion mobility mass spectrometry was used to measure the intrinsic mobility of a series of gaseous supra-cation and supra-anion aggregates of several ionic liquids. Close mobilities were observed in a T-wave cell filled with helium at ca. 0.8 mbar for [(DAI)(n+1)(X)(n)](+) (DAI is the 1,3-dialkylimidazolium cation and X is the anion) as compared to the respective anions [(DAI)(n)(X)(n+1)](-) for n=0 to 9. The anomalous behavior reported before in the condensed phase seems therefore to be related to the unique structural organization of pure ionic liquids that provides both polar and non-polar regions with directionality in which the anionic species are more retained than the cationic species in the salt network.

Coordination polymer adsorbent for matrix solid-phase dispersion extraction of pesticides during analysis of dehydrated Hyptis pectinata medicinal plant by GC/MS.

The coordination polymer [Zn(BDC)(H(2)O)(2)](n) was tested for extraction of pyrimethanil, ametryn, dichlofluanid, tetraconazole, flumetralin, kresoxim-methyl and tebuconazole from the medicinal plant Hyptis pectinata, with analysis using gas chromatography-mass spectrometry in selected ion monitoring mode (GC/MS, SIM). Experiments carried out at different fortification levels (0.1, 0.5 and 1.0 µg g(-1)) resulted in recoveries in the range 73-97%, and RSD values were between 5 and 12% for the [Zn(BDC)(H(2)O)(2)](n) sorbent. Detection and quantification limits ranged from 0.02 to 0.07 µg g(-1) and from 0.05 to 0.1 µg g(-1), respectively, for the different pesticides studied. The method developed was linear over the range tested (0.04-14.0 µg g(-1)), with correlation coefficients ranging from 0.9987 to 0.9998. Comparison between [Zn(BDC)(H(2)O)(2)](n) and the commercial phase C(18)-bonded silica showed good performance of the [Zn(BDC)(H(2)O)(2)](n) polymeric sorbent for the pesticides tested.

Potential of a metal-organic framework as a new material for solid-phase extraction of pesticides from lettuce (Lactuca sativa), with analysis by gas chromatography-mass spectrometry.

The metal-organic framework (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] was tested for extraction of pyrimicarb, procymidone, malathion, methyl parathion and α- and ß-endosulfan from lettuce, with analysis using GC/MS in SIM mode. Experiments were carried out in triplicate at two fortification levels (0.1 and 0.5 mg/kg), and resulted in recoveries in the range of 78-107%, with RSD values between 1.6 and 8.0% for (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] sorbent. Detection and quantification limits ranged from 0.02 to 0.05 mg/kg and from 0.05 to 0.10 mg/kg, respectively, for the different pesticides studied. The method developed was linear over the range tested (0.05-10.0 µg/mL), with correlation coefficients ranging from 0.9990 to 0.9997. Comparison between (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] and conventional sorbent (silica gel) showed better performance of the (∞)[(La(0.9)Eu(0.1))(2)(DPA)(3)(H(2)O)(3)] polymeric sorbent for all pesticides tested.

New homotrinuclear lanthanide complexes: synthesis, characterization and spectroscopic study.

This work presents the synthesis and spectroscopic study of new homotrinuclear (TRI) systems for photonics applications. The luminescence spectroscopy shows characteristics transitions of Eu(III) and Tb(III) ions. For the Gd(III) complexes, the triplets states were determined by phosphorescence measurement. The complexes' coordination geometries were calculated using the Sparkle/AM1 model. For the europium systems, the Sparkle/AM1 geometries were used to calculate all details involved in the energy transfer process, and the theoretical quantum yields were determined. From an energy diagram, that estimates triplet levels, it was possible to understand some experimental phenomenon, such as weak luminescence for precursor complex (without heterocyclics ligands), and ligands emission in terbium complexes. Some of these observations can also be explained by the Jablonski diagrams that describe, based on theoretical calculations, all luminescent process. The synthesized complexes showed high values of quantum yield in ethanolic environment: 50% for EuTRIDipy, 26% EuTRITerpy, and 56% for EuTRIPhen complexes.

Analysis of fuels via easy ambient sonic-spray ionization mass spectrometry.

The desorption and ionization of analytes directly from surfaces or natural matrices under ambient conditions has greatly simplified chemical analysis by mass spectrometry. Among the currently available set of such techniques, easy ambient sonic-spray ionization (EASI) is one of the simplest and most easily implemented. Fuels are among the most important and most complex classes of chemical mixtures and a challenge for fast and comprehensive chemical analysis. This review summarizes the applications of EASI-MS for fast, simple and nearly sample-preparation-free analysis of various fuels, focusing in typification, adulteration and quality control.