Treatment of chromium effluent by adsorption on chitosan activated with ionic liquids

This study proposes, verifies, and refines the use of biopolymers treated with two new ionic liquids (ILs) (sec-butylammonium acetate and n-octylammonium acetate), as a platform for chromium adsorption. The ILs were synthesized, characterized, and applied to chitosan treatment. Analyzing the size distribution of microparticles of chitosan and chitosan activated with ILs (sec-butylammonium acetate and n-octylammonium acetate), we observed that a little decrease in the particle size occurred with the activation of chitosan (176 ± 0.02 μm to 167 ± 0.054 and 168.5 ± 0.05 μm, respectively), as well as changes in the X-ray diffraction FTIR_ATR spectra. Further studies were performed using the best adsorbent – chitosan treated with sec-butylammonium acetate. In this case, the chromium VI concentration in the sample was reduced by more than 99% when using chitosan treated with IL sec-butylammonium acetate. The best reaction time was determined as 1 h, which allowed a chromium adsorption of 99.1% and the adsorption kinetic data were best represented by the second-order model (k₂ = 11.7258 g mg^?1 min^?1). The maximum adsorption capacity was obtained using the Langmuir isotherm model (20.833 mg g^?1 at pH 4 during 1 h, using 1.0 g of chitosan), and the adsorption efficiency was enhanced at 25 °C by the Freundlich isotherm model, in which the constants KF and n were determined as 0.875 mg L^?1 and 1.610, respectively.     

Characterization of isomeric cationic porphyrins with β-pyrrolic substituents by electrospray mass spectrometry: The singular behavior of a potential virus photoinactivator

Electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (ESI-MS/MS) have been used to differentiate the 2- and 4-methylpyridyl isomers of free-base and metallated cationic beta-vinylpyridylporphyrins. The analysis by ESI-MS/MS of the deuterated analogs and semiempirical calculations of structural and electronic parameters were also undertaken. The two free-base isomers are easily differentiated by ESI-MS/MS but the presence of a metallic center renders differentiation of the metallated isomers less effective. The data acquired show that of all the studied compounds, the free-base 2-methylpyridyl isomer, which was operative in the in vitro photoinactivation of Herpes simples virus, has a different gas-phase behavior. Local distortion of the macrocycle due to the presence of the beta-vinylpyridyl substituent occurs for all the compounds, but a different electron density distribution can account for the observed gas-phase behavior of this potential virus photoinactivator.     

Development of Triazoles and Triazolium Salts Based on AZT and Their Anti-Viral Activity against HIV-1

We report herein a set of 3′-azido-3′-deoxythymidine (AZT) derivatives based on triazoles and triazolium salts for HIV-1 infection. The compounds were synthesized via click chemistry with Cu(I) and Ru(II) catalysts. Triazolium salts were synthesized by reaction with methyl iodide or methyl triflate in good yields. The antiviral activity of the compounds was tested using two methodologies: In method one the activity was measured on infected cells; in method two a pre-exposure prophylaxis experimental model was employed. For method one the activity of the compounds was moderate, and in general the triazolium salts showed a decreased activity in relation to their triazole precursors. With method two the antiviral activity was higher. All compounds were able to decrease the infection, with two compounds able to clear almost all the infection, while a lower antiviral activity was noted for the triazolium salts. These results suggest that these drugs could play an important role in the development of pre-exposure prophylaxis therapies.     

Pigment study by Raman microscopy of 23 paintings by the Portuguese artist Henrique Pousão (1859–1884)

Twenty‐three paintings by Henrique Pousão—a 19th century Portuguese painter—belonging to the collection of Museu Nacional Soares dos Reis, Porto, Portugal, were analysed by Raman microscopy. The fine focus of a 100× objective allowed the visualisation and individual identification of small grains. As a result, thirty‐seven compounds, namely, anatase, barium white, basic lead sulfate, brochantite, cadmium red, cadmium yellow, calcium carbonate, carbon‐based black, celadonite, chrome green, chrome orange, chrome yellow, cobalt blue, cochineal lake, copper sulfide, emerald green, iron(III) oxyhydroxide, iron(III) oxide, kaolinite, lead antimonate yellow, lead carbonate, lead white, lead sulfate, madder lake, malachite, Prussian blue, quartz, realgar/pararealgar, red lead, rutile, Scheele's green, strontium yellow, ultramarine blue, vermilion, viridian, zinc white and zinc yellow, were identified. Not all these compounds are pigments; some are extenders, others trace components and others probably products of reactions between pigments. Special attention was given to the Raman characterisation of celadonite, chrome orange, basic lead sulfate and lead antimonate yellow. Complementary techniques were used to confirm the identities of certain pigments and to characterise reference samples. Pousão, whose work has not previously been studied spectroscopically, was found to have used a remarkably wide range of pigments over his painting periods, without showing significant preference for any particular set of pigments. Copyright © 2007 John Wiley & Sons, Ltd.     

Formulation studies on a topical gel of tretinoin�Cdimethyl-beta-cyclodextrin complex

The aim of this work was to develop and characterize a 0.05% tretinoin hydrogel formulations in which tretinoin is free or complexed with dimethyl-beta-cyclodextrin in order to compare the main advantages of its complexation. Theoretically, the complexation will mainly allow to: overcome drug low solubility in water and low stability; enhance the drug release by promoting skin absorption and alleviate of drug inducing local irritation. The hydrogels prepared were both microbiological and physically stable during 30 days. However, the chemical stability was less encouraging. The complexed tretinoin gel had also a higher releasing profile than the free tretinoin gel. This study has demonstrated that it is possible to obtain a microbiological and physically stable gel formulation with good releasing profile.     

Borohydrido rare earth based coordinative chain transfer copolymerization: A convenient tool for tuning the microstructure of isoprene/styrene copolymers

A series of lanthanum and neodymium borohydrido complexes comprising the trisborohydrides Nd(BH₄)₃(THF)₃ ( 1a ) and La(BH₄)₃(THF)₃ ( 1b ) and the half‐lanthanidocenes Cp*Nd(BH₄)₂(THF)₂ ( 2a ) (Cp* = C₅Me₅) and Cp*La(BH₄)₂(THF)₂ ( 2b ) has been assessed for the chain transfer copolymerization of isoprene and styrene. A transmetalation process is occurring efficiently with the borohydride complexes in the presence of magnesium dialkyl. The transmetalation is accompanied by (i) a gradual decrease of the 1,4‐trans stereoselectivity of the reaction at the benefit of 3,4‐selectivity and (ii) an increase in the quantity of styrene inserted in the copolymer. This can be at least partially attributed to a magnesium induced co‐oligomerization of isoprene and styrene. By combining dialkylmagnesium and trialkylaluminum, a 1,4‐trans stereospecific reversible coordinative chain transfer copolymerization of isoprene and styrene is observed when the half‐lanthanocene 2b is used as precatalyst. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

(E)-3-(meso-Octamethylcalix[4]pyrrol-2-yl)propenal: a versatile precursor for calix[4]pyrrole-based chromogenic anion sensors

The synthesis of (E)-3-(meso-octamethylcalix[4]pyrrol-2-yl)propenal and its use in Knoevenagel reactions are described. The resulting compounds display sharp changes in color in the presence of fluoride, acetate, and dihydrogen phosphate anions.     

Thermochemistry is not a lower bound to the activation energy of endothermic reactions: a kinetic study of the gas-phase reaction of atomic chlorine with ammonia

The rate constant for Cl + NH3 --> HCl + NH2 has been measured over 290-570 K by the time-resolved resonance fluorescence technique. Ground-state Cl atoms were generated by 193 nm excimer laser photolysis of CCl4 and reacted under pseudo-first-order conditions with excess NH3. The forward rate constant was fit by the expression k1 = (1.08 +/- 0.05) x 10(-11) exp(-11.47 +/- 0.16 kJ mol(-1)/RT) cm3 molecule(-1) s(-1), where the uncertainties in the Arrhenius parameters are +/-1 sigma and the 95% confidence limits for k1 are +/-11%. To rationalize the activation energy, which is 7.4 kJ mol(-1) below the endothermicity in the middle of the 1/T range, the potential energy surface was characterized with MPWB1K/6-31++G(2df,2p) theory. The products NH2 + HCl form a hydrogen-bonded adduct, separated from Cl + NH3 by a transition state lower in energy than the products. The rate constant for the reverse process k(-1) was derived via modified transition state theory, and the computed k(-1) exhibits a negative activation energy, which in combination with the experimental equilibrium constant yields k1 in fair accord with experiment.     

Synthesis and Antiprotozoal Profile of 3,4,5-Trisubstituted Isoxazoles

A series of 60 4-aminomethyl 5-aryl-3-substituted isoxazoles were synthesized by an efficient method and evaluated in vitro against Leishmania amazonensis and Trypanosoma cruzi, protozoa that cause the neglected tropical diseases leishmaniasis and Chagas disease, respectively. Thirteen compounds exhibited a selective index greater than 10. The series of 3-N-acylhydrazone isoxazole derivatives bearing the bithiophene core exhibited the best antiparasitic effects.     

Thermal stability of P3HT and P3HT:PCBM blends in the molten state

The thermal stability of poly(3-hexylthiophene) (P3HT) in its molten state was investigated in air and nitrogen atmospheres under no illumination conditions, with the aim of testing the feasibility of processing it using polymer melt techniques. A large set of different experimental characterization techniques was used including thermogravimetric analysis (TGA), rotational rheometry, infrared spectroscopy (FTIR-ATR), proton nuclear magnetic resonance spectroscopy (¹H-NMR), gel permeation chromatography (GPC), UV-Vis and fluorescence spectroscopy. The results obtained strongly suggest that the processing of P3HT in its molten state is possible, without noticeable degradation, if carried out under nitrogen atmosphere and if the processing (residence) times are relatively short. Conversely, as expected, in a normal air atmosphere P3HT degrades rapidly at temperatures above its melting point. The effect of PCBM on the thermal stability of P3HT:PCBM blends in the molten state was also studied using TGA, and in air atmosphere PCBM is shown to delay oxidation.