Aline Tavares

Copper determination in biological materials by ETAAS using W–Rh permanent modifier

A tungsten-rhodium treatment on the integrated platform of a transversely heated graphite atomiser was used as a permanent chemical modifier for the determination of copper in biological materials by using digested samples as well as slurry sampling in electrothermal atomic absorption spectrometry. The W-Rh permanent modifier was as efficient as Pd+Mg(NO(3))(2) conventional modifier for obtaining good Cu thermal stabilisation in the digested and slurry samples. The permanent W-Rh modifier remained stable by approximately 300 and 250 firings when 20 mul of digested sample and 20 mul of slurry were delivered into the atomiser, respectively. In addition, the permanent modifier increased the tube lifetime up to 1370 and 744 analytical measurements in the digested and slurry samples, respectively. Also, when the W-Rh permanent modifier was employed, there was less variation of the slope of the analytical curves during the total atomiser lifetime, resulting in a decreased need of re-calibration during routine analysis, increasing the sample throughput, and consequently diminishing the variable analytical costs. Detection limits obtained with W-Rh permanent modifier were 0.64 and 0.33 mug g(-1) Cu for digested (dilution factor 100 ml g(-1)) and 1.0% m/v slurries of biological materials, respectively. Results for the determination of copper in the samples were in agreement with those obtained with decomposed sample solutions by using Pd+Mg(NO(3)), since no statistical differences were found after applying the paired t-test at the 95% level.

Synthesis of liquid-crystalline 3,5-diarylisoxazolines

The synthesis and mesomorphic properties of new liquid-crystalline 3,5-disubstituted isoxazolines are presented and discussed. These isoxazoline derivatives have been synthesised by reacting oximes with the appropriate 4-substituted styrene dipolarophiles in the presence of N-chlorosuccinimide and pyridine. The isoxazolines 3a–d and 7a–g prepared by this methodology are used as scaffolds for further molecular derivation through a molecular elongation strategy. The selected scaffolds 3a–b and 7f–g were transformed into liquid crystals (LCs) by the addition of an arylacetylene group at the C3 or C5 carbon atoms on the isoxazoline ring by a Sonogashira reaction. The relevant LC compounds 14a–c, 15, 16, 17 and 18a–c were synthesised in fair to good yields. The final compounds display both nematic and smectic A liquid-crystalline phases.

Synthesis and thermal behavior of new liquid crystals arylaldoxime esters

We report the synthesis of a series of liquid-crystalline materials based on arylaldoxime esters and the characterization of these materials by 1H, 13C NMR, ATR/FT-IR spectroscopy and elemental analysis. The chemical stability and liquid-crystalline as well as photophysical properties of the compounds are described being dependent on the heating/cooling cycles. The changes in chemical stability and the liquid crystals properties of arylaldoxime esters were observed during these thermal cycles by IR analysis. All samples underwent a thermal degradation yielding the corresponding nitriles and carboxylic acid as evidenced by IR and 1H NMR spectra. Due to the decomposition process, information about the mesomorphic behaviour is lost. The UV-Vis absorption spectra in solution display three absorption bands between 230 and 340 nm. The fluorescence spectra exhibit a broad and structureless emission band located at 430 nm. Ab initio calculations were performed to obtain information on the molecular structure and properties of the title compounds.

Liquid-crystalline coumarin derivatives: contribution to the tailoring of metal-free sensitizers for solar cells

ABSTRACT Coumarins have been used in a wide range of applications, such as dye-sensitised solar cells, laser dyes and optical sensors. In order to further explore the properties of these materials, three new coumarin derivatives were obtained with different terminal arylalkyne linkages to the 6-position of the coumarin core. The synthesised materials were characterised by NMR, absorption and emission spectroscopy, and the liquid crystal properties were investigated through differential scanning calorimetry and polarised optical microscopy. In addition, dye-sensitised solar cells were assembled to evaluate the photoelectrochemical properties of the materials. Only the coumarin with a naphthyl group exhibited stable smectic A and nematic mesophases. All the coumarins were photoemissive in the range 420–461 nm. The adsorption of these dyes on TiO2 was observed by UV–vis spectroscopy; in addition, by incident photon-to-electron conversion efficiency and I–V curves, photocurrent generation was observed. GRAPHICAL ABSTRACT

Implications of flexible spacer rotational processes on the liquid crystal behavior of 4,5-dihydroisoxazole benzoate dimers

The synthesis of some novel non-symmetric liquid crystal dimers, {3-[4-(octyloxyphenyl)]-4,5-dihydroisoxazol-5-yl}alkyl 4-(decyloxy)benzoates (5a–d) and 4-{3-[4-(octyloxyphenyl)]-4,5-dihydroisoxazol-5-yl}alkyl 4-{[6-(octyloxy)naphthalen-2-yl]ethynyl}benzoate (9a–d), are reported. The liquid-crystalline properties, theoretical calculations based on the conformational aspects of the flexible alkyl spacer and X-ray experiments are discussed. The syntheses of the key intermediates, 2-{3-[4-(octyloxy)phenyl]-4,5-dihydroisoxazol-5-yl}alkanol (3a–d), presenting the flexible alkyl spacer were achieved through [3+2] cycloaddition reactions between nitrile oxides, which were generated in situ by oxidation of the respective aromatic oximes, and dipolarophile alkenols (CH2CH(CH2)nOH, n = 1, 2, 3, and 4). The benzoates 5a–d were synthesized through esterification of 3a–d and p-n-decyloxybenzoic acid (4). The esters 9a–d were synthesized through derivatization of isoxazolines 3a–d into 4-{3-[4-(octyloxyphenyl)]-4,5-dihydroisoxazol-5-yl}alkyl 4-bromobenzoate (7a–d) followed by a Sonogashira reaction with 2-ethynyl-6-octyloxynaphthalene (8). 5a and 5b showed a monotropic smectic C phase. 9a/c displayed a enantiotropic nematic (N) mesophase, whereas 9b/d showed a monotropic nematic mesophase. No mesophase was observed for 7a–d. An odd–even effect was observed for 5a–d and 9a–d associated with the crystal to isotropic phase transition and crystal to nematic phase, respectively, as the length of the spacer was increased from 1 to 4 carbon atoms. The transitional properties were higher for odd-numbered members (n = 1 and 3) for all of the series studied. The X-ray data of compounds 5a and 5b are in agreement with polarizing optical microscopy observations with the assignment of an SmC mesophase. Density functional theory calculations using the B3LYP hybrid functional with the level 6-311G(d,p) basis set were performed for molecules 5a–d to correlate the conformation of the flexible spacer and the transitional properties. The conformational analysis showed that the most stable conformation for 5a–d is one where all of the carbon atoms of the flexible spacer are orientated at 180° (antiperiplanar orientation) except for 5a because the spacer is too short. The odd-numbered members have a more bent shape and are less elongated molecules than the even-numbered members. Thus, mesomorphic behavior is dictated by the conformational constraint imposed by the flexible spacer on the mesogenic groups.

The 2:1 cycloadducts from [3+2] 1,3-dipolar cycloaddition of nitrile oxide and vinylacetic acid. Synthesis and liquid crystal behaviour

Four liquid crystals (LC) 3,7a-bis(4-alkyloxyphenyl)-7,7a-dihydro-6H-isoxazolo[2,3-d][1,2,4]oxadiazol-6-yl)acetic acid (7a–d) were synthesised and the mesomorphic behaviour reported. The LCs were characterised as 2:1 bisadducts, which were obtained from a double [3 + 2] 1,3-dipolar cycloaddition. In the first step, the cycloaddition of 4-alkyloxyphenylnitrile oxide (4a–d) and vinylacetic acid (5) gave the initial unobserved 1:1 cycloadducts 2-[3-(4-alkyloxyphenyl)-4,5-dihydroisoxazol-5-yl]acetic acid (6a–d). In the second step, the addition of a second equivalent of 4 to 6 yielded the 2:1 bisadducts 7a–d without any traces of 6. All compounds 7a–d were unstable during the transition from the mesophase to the isotropic state upon first heating as evidenced by the large peaks in the differential scanning calorimetry traces. Due to the chemical instability of the compounds upon heating, the transition temperature related to the smectic C to smectic A transitions was acquired by means of an image processing method. X-Ray diffraction experiments were also used to analyse the liquid-crystalline phases. A theoretical calculation was performed using density functional theory (DFT) methods at the PBE1PBE/6-311+G(2d,p) level (with solvent effect) in order to get information about the energetic profile of the 2:1 cycloaddition. DFT studies revealed that the cycloaddition process is controlled by the HOMO(dipolarophile) – LUMO(1,3-dipole), and that the double [3 + 2] 1,3-dipolar cycloaddition reaction is quite possible.