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The chemiluminescence of several naphthalene-based luminol analogues is characterized and compared with that of luminol. The compounds produce a strong greenish or green-yellow chemiluminescence in alkaline aqueous and nonaqueous solutions by reaction with hydrogen peroxide in the presence of hexacyanoferrate (III). The results point to the possibility of increasing the sensitivity of analytical methods currently based on luminol. The photophysics of the oxidation products is also studied. The solubility of some of the new compounds in aqueous solution is significantly increased using a nonionic surfactant Triton X-100. Increase of the chemiluminescence intensity in aqueous micellar media was observed. The location of the oxidation product 3-aminophthalate in the external hydrophilic shell of the micelle was established using its intrinsic fluorescence by iodide. The described luminol analogues may prove of interest in forensic and other applications.

A large amount of waste printed circuit boards (WPCBs) that contain valuable metals, namely gold and copper, are produced annually. WPCBs are constituted by a multi-layer structure reinforced by a brominated epoxy resin (BER), which is very difficult to separate into the metallic and non-metallic components. The main aim of this work was to evaluate the ability of microwave for assisting in the delamination of WPCBs by organic swelling of the BER. Additionally, its performance was compared with other strategies (thermostatic and ultrasonic baths) previously described in the literature. Firstly, a library of solvents [dimethyl formamide (DMF), dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), cyclohexanone (CH), γ-butyrolactone (GBL), tetrahydrofurfuryl alcohol (TFA) and dimethyl malonate (DM)] was selected based on the calculation of Hansen solubility parameters plus others exclusion parameters and their performance to detach all components of WPCBs (25 mm2) was tested by microwave (200 °C for 10 min), thermostatic (153 °C for 10 min) and ultrasonic (60 °C for 25 h) baths. Microwave showed to be the most efficient approach and the delamination order for WPCBs was: NMP > DMSO > DMF > DMAc. Subsequent optimization of key parameters (dimensions of WPCBs and reaction time) were obtained: dimensions of 225 mm2 using NMP (solid/liquid ratio of 300 g/L) at 200 °C with 2 cycles of 10 min. In conclusion, microwave-assisted swelling revealed to be more efficient and faster process to delaminate WPCBs into metallic and non-metallic components, which are important advantages when envisaging a future industrial waste management implementation.

Phasor plots (plots of the Fourier sine transform vs. the Fourier cosine transform, for one or several angular frequencies) of the fluorescence intensity decay are being increasingly used in studies of homogeneous and heterogeneous systems. In this work, the phasor approach is applied to monomer-excimer systems with a focus on mixed decays, i.e. decays with both monomer and excimer contributions. The phasors of mixed decays fall on a straight line delimited by the excimer and monomer phasors. With a fixed concentration, and by continuously increasing the emission wavelength, the phasor moves from pure monomer to pure excimer. At a certain intermediate wavelength, which is concentration-dependent, the phasor crosses the universal semicircle and the decay becomes single exponential. This is an interesting case of an exponential decay not corresponding to a single fluorescent species. All results are demonstrated experimentally with pyrene in methylcyclohexane at room temperature, for which a full phasor picture emerges, combining in a single diagram monomer, excimer and mixed decays measured at several concentrations, showing the graphical power of the phasor approach.

We calculate the superfluid weight and the polarization amplitude for the one-dimensional bosonic Hubbard model focusing on the strong-coupling regime. Other than analytic calculations we apply two methods: variational Monte Carlo based on the Baeriswyl wave function and exact diagonalization. The former gives zero superfluid response at integer filling, while the latter gives a superfluid response at finite hopping. From the polarization amplitude we derive the variance and the associated size scaling exponent. Again, the variational study does not produce a finite superfluid weight at integer filling (size scaling exponent is near one), but the Fourier transform of the polarization amplitude behaves in a similar way to the result of exact diagonalization, with a peak at small hopping, and suddenly decreasing at the insulator-superfluid transition. On the other hand, exact diagonalization studies result in a finite spread of the total position which increases with the size of the system. In the superfluid phase the size scaling exponent is two as expected. Importantly, our work addresses the ambiguities that arise in the calculation of the superfluid weight in variational calculations, and we comment on the prediction of Anderson about the superfluid response of the model at integer filling., Comment: rewritten, somewhat shortened in response to the critique of a referee

The intrinsic electronic absorption and fluorescence properties of several multifluorophoric dihomooxacalix[4]arenes are studied. The contributions of phenyl and/or benzyl groups (lower rim) and p-tert-butylphenyl ethers (upper rim) to the absorption and fluorescence are established. Fluorescence titrations were undertaken to investigate the calixarene complexes with nitrate and hydrogen sulfate. A comparison with UV-Vis titrations in the same concentration range showed that similar values for the association constants are obtained by both techniques. Fluorescence is thus demonstrated to be a good method for the determination of calixarene–anion association constants.

The purpose of this chapter is to summarize the state of art of fluorescence-based explosive sensors in a simple way, focusing especially on the research progress. Importantly, the advances in this field are organized in the different strategies and improvements in the exploitation of fluorescence explosives detection. Mechanisms of fluorescence explosives detection are reviewed, not only fluorescence-quenching-based mechanisms but also some novel mechanism which are applied in explosives detection. We also focused our discussion on several fluorescent probes that can be used for the detection of explosives, in this way the discussion is organized based on their structures. Some design and data treatment requirements for obtaining an optical sensor are discussed, including statistical analysis and signal modelling. At the end of the chapter, future directions and perspectives are presented and discussed.

Phasor plots of the fluorescence intensity decay (plots of the Fourier sine transform versus the Fourier cosine transform, for one or several angular frequencies) are being increasingly used in studies of homogeneous and heterogeneous systems. In this work, the phasor approach is applied to monomer-excimer kinetics. The results obtained allow a clear visualization of the information contained in the decays. The monomer phasor falls inside the universal circle, whereas the excimer phasor lies outside it, but within the double-exponential outer boundary curve. The monomer and excimer phasors, along with those corresponding to the two exponential components of the decays, fall on a common straight line and obey the generalized lever rule. The clockwise trajectories described by both phasors upon monomer concentration increase are identified. The phasor approach allows discussing in a single graphic not only the effect of concentration but also that of rate constants, including the evolution from irreversible kinetics to fast excited-state equilibrium upon a temperature increase. The obtained results are applied to the fluorescence decays of pyrene monomer and excimer in methylcyclohexane at room temperature. A straightforward method of monomer-excimer lifetime data analysis based on linear plots is also introduced.

Phasor plots of the fluorescence intensity decay (plots of the Fourier sine transform vs the Fourier cosine transform, for one or several angular frequencies) are being increasingly used, namely, in fluorescence lifetime imaging microscopy (FLIM) of cells, tissues, and surfaces, but are also relevant for the characterization of homogeneous (e.g., solution) systems. In this work, the construction of the phasor plot using time domain data is discussed, including the effect of the instrument response function (IRF). A deconvolution method in the Fourier space is described. The results obtained are applied to fluorescence decays of aqueous fluorescein (basic form) in the presence of concentrated potassium iodide. The effect of the impulse is clearly shown, in accordance with model predictions. Deconvolution in the Fourier space works well for lifetimes at least 1 order of magnitude higher than the IRF time width.

Three anionic fluorene-based alternating conjugated polyelectrolytes (CPEs) have been synthesized that have 9,9-bis(4-phenoxy-butylsulfonate) fluorene-2,7-diyl and 1,4-phenylene (PBS-PFP), 4,4′-biphenylene (PBS-PFP2), or 4,4″-p-terphenylene (PBS-PFP3) groups, and the effect of the length of the oligophenylene spacer on their aggregation and photophysics has been studied. All form metastable dispersions in water, but can be solubilized using methanol, acetonitrile, or dioxane as cosolvents. This leads to increases in their emission intensities and blue shifts in fluorescence maxima due to break-up of aggregates. In addition, the emission maximum shifts to the blue and the loss of vibronic structure are observed when the number of phenylene rings is increased. Debsity Functional Theory (DFT) calculations suggest that this is due to increasing conformational flexibility as the number of phenylene rings increases. This is supported by increasing amplitude in the fast component in the fluorescence decay. The nonionic surfactant n-dodecylpentaoxyethylene glycol ether (C12E5) also breaks up aggregates, as seen by changes in fluorescence intensity and maximum. However, the loss in vibrational structure is less pronounced in this case, possibly due to a more rigid environment in the mixed surfactant-CPE aggregates. Further information on the aggregates formed with C12E5 was obtained by electrical conductivity measurements, which showed an initial increase in specific conductivity upon addition of surfactants, while at higher surfactant/CPE molar ratios a plateau was observed. The specific conductance in the plateau region decreased in the order PBS-PFP3 < PBS-PFP2 < PBS-PFP, in agreement with the change in charge density on the CPE. The reverse process of aggregate formation has been studied by injecting small volumes of solutions of CPEs dissolved at the molecular level in a good solvent system (50% methanol-water) into the poor solvent, water. Aggregation was monitored by changes in both fluorescence and light scattering. The rate of aggregation increases with hydrophobicity and concentration of sodium chloride but is only weakly dependent on temperature.

Novel near-infrared luminescent compounds based on platinum(II) 4,5,6,7-tetrahydropyrazolo[1,5-a]pyridine-fused chlorins are described. These compounds have high photostability and display light emission, in particular simultaneous fluorescence and phosphorescence emission in solution at room temperature, in the biologically relevant 700–850 nm red and near-infrared (NIR) spectral region, making them excellent materials for biological imaging. The simultaneous presence of fluorescence and phosphorescence emission at room temperature, with the phosphorescence strongly quenched by oxygen whereas fluorescence remains unaffected, allows these compounds to be used as ratiometric oxygen sensors in chemical and biological media. Both steady-state (fluorescence vs phosphorescence intensities) and dynamic (dependence of phosphorescence lifetimes upon oxygen concentration) luminescence approaches can be used. Photocytotoxicity studies against human melanocytic melanoma cells (A375) indicate that these compounds dis...

Films of neat and plasticized biodegradable poly(lactic acid) (PLA) matrices containing anionic conjugated polyelectrolytes, poly[9,9-bis(4-phenoxybutylsulfonate)]fluorene-2,7-diyl-alt-arylenes, with 1,4-phenylene and 4,4″-p-terphenylene, respectively, as arylene groups or a neutral poly(9,9-dialkylfluorene) for comparison were prepared by solution casting. These films were characterized using differential scanning calorimetry, thermogravimetry, scanning electron microscopy and fluorescence spectroscopy. In addition, the effects of plasticizer on the thermal properties and the oxygen permeability of the PLA films were measured through the oxygen transmission rate. Results show that it is possible to obtain thin, optically transparent and luminescent films with potential in oxygen sensing, exhibiting good thermal and photochemical stability. At high polyelectrolyte content, evidence is found for phase separation and aggregate formation and it is no longer possible to obtain completely homogeneous films. The possibility of incorporating the cationic metal complex tris(2,2′-bipyridyl)ruthenium(II) into plasticized PLA films containing conjugated polyelectrolytes for dual-wavelength ratiometric luminescence sensing is also discussed. Copyright © 2012 Society of Chemical Industry

A variational Monte Carlo method for bosonic lattice models is introduced. The method is based on the Baeriswyl projected wavefunction. The Baeriswyl wavefunction consists of a kinetic energy based projection applied to the wavefunction at infinite interaction, and is related to the shadow wavefunction already used in the study of continuous models of bosons. The wavefunction at infinite interaction, and the projector, are represented in coordinate space, leading to an expression for expectation values which can be evaluated via Monte Carlo sampling. We calculate the phase diagram and other properties of the bosonic Hubbard model. The calculated phase diagram is in excellent agreement with known quantum Monte Carlo results. We also analyze correlation functions., minor changes compared to previous version

In this paper we show that the general finite-energy spectral-function expressions provided by the pseudofermion dynamical theory for the one-dimensional Hubbard model lead to the expected low-energy Tomonaga–Luttinger liquid correlation function expressions. Moreover, we use the former general expressions to derive correlation-function asymptotic expansions in space and time which go beyond those obtained by conformal-field theory and bosonization: we derive explicit expressions for the pre-factors of all terms of such expansions and find that they have an universal form, as the corresponding critical exponents. Our results refer to all finite values of the on-site repulsion U and to a chain of length L very large and with periodic boundary conditions for the above model, but are of general nature for many integrable interacting models. The studies of this paper clarify the relation of the low-energy Tomonaga–Luttinger liquid behavior to the scattering mechanisms which control the spectral properties at all energy scales and provide a broader understanding of the unusual properties of quasi-one-dimensional nanostructures, organic conductors, and optical lattices of ultracold fermionic atoms. Furthermore, our results reveal the microscopic mechanisms which are behind the similarities and differences of the low-energy and finite-energy spectral properties of the model metallic phase.

The momentum and energy dependence of the weight distribution in the vicinity of the one-electron spectral-function singular branch lines of the 1D Hubbard model is studied for all values of the electronic density and on-site repulsion $U$. To achieve this goal we use the recently introduced pseudofermion dynamical theory. Our predictions agree quantitatively for the whole momentum and energy bandwidth with the peak dispersions observed by angle-resolved photoelectron spectroscopy in the quasi-1D organic conductor TTF-TCNQ., Comment: Replaced with shortened version; 4 figures

In this paper we derive general expressions for few-electron spectral functions of the one-dimensional Hubbard model for values of the excitation energy in the vicinity of the Mth upper-Hubbard band lower limit. Here M = 1,2,... is the rotated-electron double occupation, which vanishes for the ground state and is a good quantum number for all values of the on-site Coulomb repulsion U. Our studies rely on a combination of symmetries of the model with a recent finite-energy holon and spinon description of the quantum problem. We apply our general scheme to the one-electron addition spectral function, dynamical structure factor and spin singlet Cooper-pair addition spectral function. Our results provide physically interesting information about the finite-energy spectral properties of the many-electron one-dimensional quantum liquid.

Conjugated polymers (CPs) have proved to be promising chemosensory materials for detecting nitroaromatic explosives vapors, as they quickly convert a chemical interaction into an easily-measured high-sensitivity optical output. The nitroaromatic analytes are strongly electron-deficient, whereas the conjugated polymer sensing materials are electron-rich. As a result, the photoexcitation of the CP is followed by electron transfer to the nitroaromatic analyte, resulting in a quenching of the light-emission from the conjugated polymer. The best CP in our studies was found to be poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-bithiophene] (F8T2). It is photostable, has a good absorption between 400 and 450 nm, and a strong and structured fluorescence around 550 nm. Our studies indicate up to 96% quenching of light-emission, accompanied by a marked decrease in the fluorescence lifetime, upon exposure of the films of F8T2 in ethyl cellulose to nitrobenzene (NB) and 1,3-dinitrobenzene (DNB) vapors at room temperature. The effects of the polymeric matrix, plasticizer, and temperature have been studied, and the morphology of films determined by scanning electron microscopy (SEM) and confocal fluorescence microscopy. We have used ink jet printing to produce sensor films containing both sensor element and a fluorescence reference. In addition, a high dynamic range, intensity-based fluorometer, using a laser diode and a filtered photodiode was developed for use with this system.

The Hubbard model is investigated for a halffilled honeycomb lattice, using a variational method. Two trial wave functions are introduced, the Gutzwiller wave function, well suited for describing the “metallic” phase at small U and a complementary wave function for the insulating regime at large values of U. The comparison of the two variational ground states at the mean-field level yields a Mott transition at U c /t ≈ 5:3. In addition, a variational Monte Carlo calculation is performed in order to locate the instability of the “metallic” wave function with respect to antiferromagnetism. The critical value U m/t ≈ 3:7 obtained in this way is considered to be a lower bound for the true critical point for antiferromagnetism, whereas there are good arguments that the mean-field value U c/t ≈ 5:3 represents an upper bound for the Mott transition. Therefore the “metal”- insulator transition for the honeycomb lattice may indeed be simultaneously driven by the antiferromagnetic instability and the Mott phenomenon.

The thermally induced sigmatropic isomerization of the pseudosaccharyl crotyl ether, 3-(E)-but-2-enoxy)-1,2-benzisothiazole 1,1-dioxide (CBID), has been investigated by using temperature dependent infrared spectroscopy, differential scanning calorimetry (DSC), and polarized light thermomicroscopy. The reaction can take place in both melted and crystalline phases, affording the product resulting from the [3,3′] migration of the allylic system from O to N, 2-(E)-1-methylprop-2-en-1,2-benzisothiazol-3(2H)-one 1,1-dioxide (CBIOD). In the melt, the activation energy of the process was determined as being 49.1±5.3 kJ mol−1, with k=(22.2±0.6)×104 s−1 at 140 °C. In the solid state, at 110 °C, the rate constant drops by one order of magnitude [k=(1.46±0.07)×104 s−1]. The enthalpy of reaction, determined by DSC, is ΔrxH=−27.0±0.8 kJ mol−1. Assignments were proposed for the infrared spectra of the observed neat condensed phases of the two compounds.

We study the electronic structure of the quasi-one-dimensional organic conductor TTF-TCNQ by means of density-functional band theory, Hubbard model calculations, and angle-resolved photoelectron spectroscopy (ARPES). The experimental spectra reveal significant quantitative and qualitative discrepancies to band theory. We demonstrate that the dispersive behavior as well as the temperature-dependence of the spectra can be consistently explained by the finite-energy physics of the one-dimensional Hubbard model at metallic doping. The model description can even be made quantitative, if one accounts for an enhanced hopping integral at the surface, most likely caused by a relaxation of the topmost molecular layer. Within this interpretation the ARPES data provide spectroscopic evidence for the existence of spin-charge separation on an energy scale of the conduction band width. The failure of the one-dimensional Hubbard model for the {\it low-energy} spectral behavior is attributed to interchain coupling and the additional effect of electron-phonon interaction., 18 pages, 9 figures

We study the spin excitations and the transverse susceptibility of a two-dimensional antiferromagnet doped with a small concentration of holes in the t-J model. The motion of holes generates a renormalization of the magnetic properties. The Green's functions are calculated in the self-consistent Born approximation. It is shown that the long-wavelength spin waves are significantly softened and the shorter-wavelength spin waves become strongly damped as the doping increases. The spin wave velocity is reduced by the coherent motion of holes, and not increased as has been claimed elsewhere. The transverse susceptibility is found to increase considerably with doping, also as a result of coherent hole motion. Our results are in agreement with experimental data for the doped copper oxide superconductors., 20 pages

Naphthalene analogues of luminol with several types of substituents were prepared. All molecules exhibit a strong green chemiluminescence in aqueous solution, which is catalysed by iron, pointing to the possibility of increasing the sensitivity of analytical methods currently based on luminol.