Linear and nonlinear optical properties of cationic bipyridyl iridium(III) complexes: tunable and photoswitchable?

A series of cationic Ir(III) substituted bipyridyl ()(N(∧)N (N(∧)N-bpy) complexes incorporating electron-donor and -acceptor substituents, [Ir(C(∧)N-ppy-R')(2)(N(∧)N-bpy-CH═CH-C(6)H(4)-R)][X] (X(-) = PF(6)(-) or C(12)H(25)SO(3)(-)), 2 (a, R = NEt(2) and R' = Me; b, R = O-Oct and R' = Me; c, R = NO(2) and R' = C(6)H(13); C(∧)N-ppy = cyclometalated 2-phenylpyridine, [Ir(C(∧)N-ppy-Me)(2)(N(∧)N-bpy-CH═CH-thienyl-Me)][PF(6)], 2d, and the dithienylethene (DTE)-containing complex 2e have been synthesized and characterized, and their absorption, luminescence, and quadratic nonlinear optical (NLO) properties are reported. Density functional theory (DFT) and time-dependent-DFT (TD-DFT) calculations on the complexes facilitate a detailed assignment of the excited states involved in the absorption and emission processes. All five complexes are luminescent in a rigid glass at 77 K, displaying vibronically structured spectra with long lifetimes (14-90 μs), attributed to triplet states localized on the styryl-appended bipyridines. The second-order NLO properties of 2a-d and related complexes 1a-d with 1,10-phenanthrolines have been investigated by both electric field induced second harmonic generation (EFISH) and harmonic light scattering (HLS) techniques. They are characterized by high negative EFISH μβ values which decrease when the ion pair strength between the cation and the counterion (PF(6)(-), C(12)H(25)SO(3)(-)) increases. The EFISH response is mainly controlled by metal-to-ligand charge-transfer/ligand-to-ligand charge-transfer (MLCT/L'LCT) processes. A combination of HLS and EFISH techniques is used to evaluate both the dipolar and octupolar contributions to the total quadratic hyperpolarizability, demonstrating that the major contribution is controlled by the octupolar part. The incorporation of a photochromic DTE unit into the N(∧)N-bpy ligand (complex 2e) allows the luminescence to be switched ON or OFF. The photocyclisation of the DTE unit can be triggered by using either UV (365 nm) or visible light (430 nm), leading to an efficient quenching of the ligand-based 77 K luminescence, which can be restored upon irradiation of the closed form at 715 nm. In contrast, no significant modification of the EFISH μβ value is observed upon photocyclization, suggesting that the quadratic NLO response is dominated by the MLCT/L'LCT processes, rather than by the intraligand excited states localized on the substituted bipyridine ligand.     

Thermal behavior of residues (sludge) originating from the sugarcane industry

The Brazilian sugarcane industry shows a great amount of generated sludge which should be utilized adequately. Two sludge samples, aerobic and anaerobic, were collected. Both were evaluated by thermogravimetry and differential thermal analysis (DTA) as well as X-ray power diffraction. These compounds show variations of mass between 30 and 140 °C due to the dehydration stage. The DTA curves show that the compounds have an exothermic reaction between 450 and 550 °C, which indicates that this can be used as an energy source. Details concerning the kinetic parameters of the dehydration and thermal decomposition have also been described here. The kinetic study of these stages was evaluated in open crucibles under nitrogen atmosphere. The obtained data were evaluated with the isoconversional kinetic method. The results show that different activation energies were obtained for thermal decomposition.     

Ionic liquids as recycling solvents for the synthesis of magnetic nanoparticles

This work describes an easy synthesis (one pot) of MFe(2)O(4) (M = Co, Fe, Mn, and Ni) magnetic nanoparticles MNPs by the thermal decomposition of Fe(Acac)(3)/M(Acac)(2) by using BMI·NTf(2) (1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) or BMI·PF(6) (1-n-butyl-3-methylimidazolium hexafluorophosphate) ionic liquids (ILs) as recycling solvents and oleylamine as the reducing and surface modifier agent. The effects of reaction temperature and reaction time on the features of the magnetic nanomaterials (size and magnetic properties) were investigated. The growth of the MNPs is easily controlled in the IL by adjusting the reaction temperature and time, as inferred from Fe(3)O(4) MNPs obtained at 150 °C, 200 °C and 250 °C with mean diameters of 8, 10 and 15 nm, respectively. However, the thermal decomposition of Fe(Acac)(3) performed in a conventional high boiling point solvent (diphenyl ether, bp 259 °C), under a similar Fe to oleylamine molar ratio used in the IL synthesis, does not follow the same growth mechanism and rendered only smaller NPs of 5 nm mean diameter. All MNPs are covered by at least one monolayer of oleylamine making them readily dispersible in non-polar solvents. Besides the influence on the nanoparticles growth, which is important for the preparation of highly crystalline MNPs, the IL was easily recycled and has been used in at least 20 successive syntheses.     

Efficient crystallization induced emissive materials based on a simple push-pull molecular structure

Solid state luminescent materials are the subject of ever growing interest both from a scientific and a technological point of view. Aggregation caused quenching (ACQ) processes however represent an obstacle to the development of most luminogens in the condensed phase. This is why particularly fascinating are those materials showing higher emission intensity in the solid state than in solution. Here we report on three 4-dialkylamino-2-benzylidene malonic acid dialkyl esters, very simple push-pull molecules, which are hardly emissive in solution and in the amorphous phase but become good emitters in the crystalline phase according to what has been indicated as crystallization induced emission (CIE). Thanks to combined emission and NMR spectroscopies at different temperatures on the prototype compound 4-dimethylamino-2-benzylidene malonic acid dimethyl ester in solution, we give full evidence that a restricted intramolecular rotation (RIR) phenomenon, in particular the hindered rotation around the aryl main axis of the compound, is at the origin of this behaviour. In addition, solid state photophysical and X-ray diffraction structural characterization allow us to identify J-dimeric interactions as responsible for the particularly intense emission of two of the three compounds. Moreover, by exploiting the compounds' acidochromic properties, applications in sensors and optoelectronics are envisaged.     

Activity of Cuban propolis extracts on Leishmania amazonensis and Trichomonas vaginalis

In this paper we analyzed the antiprotozoal effects of eighteen Cuban propolis extracts (brown, red and yellow type) collected in different geographic areas, using Leishmania amazonensis (as a model of intracellular protozoa) and Trichomonas vaginalis (as a model of extracellular protozoa). All evaluated propolis extracts caused inhibitory effect on intracellular amastigotes of L. amazonensis. However, cytotoxicity on peritoneal macrophages from BALB/c mice was observed. Only five samples decreased the viability of T. vaginalis trophozoites at concentrations lower than 10 microg/mL. No correlation between the type of propolis and antiprotozoal activity was found. Cuban propolis extracts demonstrated activity against both intracellular and extracellular protozoa model, as well as the potentialities of propolis as a natural source to obtain new antiprotozoal agents.     

A Bus Driver Scheduling Problem: a?new mathematical model and a GRASP approximate solution

This paper addresses the problem of determining the best scheduling for Bus Drivers, a $\mathcal{NP}$ -hard problem consisting of finding the minimum number of drivers to cover a set of Pieces-Of-Work (POWs) subject to a variety of rules and regulations that must be enforced such as spreadover and working time. This problem is known in literature as Crew Scheduling Problem and, in particular in public transportation, it is designated as Bus Driver Scheduling Problem. We propose a new mathematical formulation of a Bus Driver Scheduling Problem under special constraints imposed by Italian transportation rules. Unfortunately, this model can only be usefully applied to small or medium size problem instances. For large instances, a Greedy Randomized Adaptive Search Procedure (GRASP) is proposed. Results are reported for a set of real-word problems and comparison is made with an exact method. Moreover, we report a comparison of the computational results obtained with our GRASP procedure with the results obtained by Huisman et al. (Transp. Sci. 39(4):491?C502, 2005).     

Finite element acoustic simulation based shape optimization of a muffler

This paper describes a methodology which combines finite element analysis and Zoutendijk’s feasible directions method for mufflers shape design. The main goal is to obtain the dimensions of the acoustic muffler with the transmission loss (TL), being maximized in the frequency range of interest. The improved four parameters method is used for TL evaluations and the Helmholtz’s equation is solved numerically with the finite element method (FEM). The quadratic triangular finite element meshes are adequately constructed to control the pollution error and the optimization problem is solved using the Zoutendijk’s feasible directions method due to robustness and efficiency for problems with nonlinear constraints. Numeric experiments performed with circular expansion chambers with extended inlet and outlet show results for constrained and unconstrained shape optimization.