A mild high yielding synthesis of oxazole-4-carboxylate derivatives

Several 2,5-disubstituted oxazole-4-carboxylates were prepared in high yields from the methyl esters of N-acyl-β-halodehydroaminobutyric acid derivatives by treatment with a 2% solution of DBU in acetonitrile. The scope of this reaction was investigated and it was found that dehydrodipeptides having a β-bromodehydroaminobutyric acid residue gave the corresponding oxazoles in good yields. The photophysical properties of some of the oxazoles prepared were studied in four solvents of different polarity. All compounds have reasonable high fluorescence quantum yields and a moderate solvent sensitivity, which makes them good candidates to be used as fluorescent probes. One of the fluorescent oxazoles prepared was inserted after cleavage of the methyl ester into two model peptides using a conventional solution phase strategy. The photophysical properties of the labelled peptides were studied in ethanol and water and compared with those of the oxazole. The results obtained showed that the oxazole maintains a good fluorescence level and the same solvent sensitivity when linked to a peptide chain.     

The effects of lignin removal and drying on the porosity and enzymatic hydrolysis of sugarcane bagasse

The porosity of lignocellulosic materials is a key feature for the enzymatic hydrolysis of the constituent polysaccharides, being affected by its drying and lignin content. Here we evaluated the influence of both parameters in the porosity of sugarcane bagasse, using raw and chlorite-delignified samples. A fraction of these samples was air dried at room temperature and the remainder one was kept wet. All the samples were subjected to porometry (solute exclusion technique), determination of water retention value and assessment of enzymatic saccharification of polysaccharides. Samples with higher lignin contents had lower porosities and exhibited worse enzymatic conversions of polysaccharides. Mild drying collapsed only the smaller pores, which already were inaccessible to enzymes, and therefore did not affect the efficiencies of saccharification. Our results show that the lignin content plays an important role in the porosity of the material and that its removal improves the enzymatic saccharification of the constituent polysaccharides.     

Growth of vertically aligned carbon nanotubes on carbon fiber: thermal and electrochemical treatments

Composite electrodes of vertically aligned carbon nanotubes (VACNT) were synthesized on carbon fiber (CF) substrate by pyrolysis of camphor/ferrocene using a SiO₂ interlayer as a barrier against metal diffusion into the substrate. Two treatments were used to remove iron from CF/VACNT structure: thermal annealing at high temperature under inert atmosphere and electrochemical oxidation in H₂SO₄ solution. The composites were characterized by scanning electron microscopy and Raman scattering spectroscopy. Besides, the electrochemical behavior of CF/VACNT was analyzed by cyclic voltammetry and charge/discharge tests. CF/VACNT composite submitted to the electrochemical oxidation showed the best electrochemical performance, with high specific capacitance, which makes it very attractive as electrode for supercapacitors.     

Calorimetric and computational study of the thermochemistry of phenoxyphenols

Thermodynamic properties of 3- and 4-phenoxyphenol have been determined by using a combination of calorimetric and effusion techniques as well as by high-level ab initio molecular orbital calculations. The standard (p° = 0.1 MPa) molar enthalpies of formation in the condensed and gas states, Δ(f)H(m)°(cr or l) and Δ(f)H(m)°(g), at T = 298.15 K, of 3- and 4-phenoxyphenol were derived from their energies of combustion in oxygen, measured by a static bomb calorimeter, and from the enthalpies of vaporization or sublimation derived respectively by Calvet microcalorimetry for the 3-phenoxyphenol and by Knudsen effusion technique for the 4-phenoxyphenol. The theoretically estimated gas-phase enthalpies of formation were calculated from high-level ab initio molecular orbital calculations at the G3(MP2)//B3LYP level of theory. Furthermore, this composite approach was also used to obtain information about the gas-phase acidities, gas-phase basicities, proton and electron affinities, adiabatic ionization enthalpies, and, finally, O?H bond dissociation enthalpies. The good agreement between the G3MP2B3-derived values and the experimental gas-phase enthalpies of formation for the 3- and 4-phenoxyphenol gives confidence to the estimate concerning the 2-phenoxyphenol isomer, which was not experimentally studied, and to the estimates concerning the radical and the anion. Additionally, the experimental values of gas-phase enthalpies of formation were also compared with estimates based on the empirical scheme developed by Cox.     

Construction and evaluation of a flow injection micro-analyser based on urethane-acrylate resin

A flow injection micro-analyser with an integrated injection device and photometric detection is described. Channels measuring 205-295 μm depth by 265-290 μm maximum width were manufactured by deep UV lithography on two layers of urethane-acrylate oligomers-based photoresist. Hypodermic syringe needles (450 μm diameter) were connected to the channels for introduction of solutions into the system. Plastic optical fibres were connected to the ends of a 5.0 mm long channel, in order to conduct the light from and to a homemade photometer. The device has a total volume of 7.0 μL and three different sample volumes (0.09, 0.22 and 0.30 μL) can be inserted into the system by choosing the appropriate loop of the hydrodynamic injection approach. The micro-analyser, designed as a single line manifold, was evaluated by determining chloride in waters (mercuric thiocyanate method), and chromium (VI) in wastewater and total chromium in metallic alloys (diphenylcarbazide method). For chloride determination two micro-pumps were employed to impel the solutions, while for chromium determination this task was performed by a conventional peristaltic pump. The results obtained in all determinations did not differ significantly from the reference methods at a confidence level of 95%. In the chloride determination, a flow rate of 50 μL min⁻¹ was used, providing a sample frequency of 45 injection h⁻¹, generating ca. 0.7 mg of Hg(II) after an 8-h working day (ca. 20 mL of solution). This result suggests the potential of the micro-analyser towards the reduction of waste, following the philosophy of Green Chemistry.     

Asymmetric synthesis of (-)-1-hydroxyquinolizidinone, a common intermediate for the syntheses of (-)-homopumiliotoxin 223G and (-)-epiquinamide

The short and efficient asymmetric synthesis of (-)-1-hydroxyquinolizidinone was achieved in seven steps and 25.2% overall yield from readily available 5-chloropentanal. It is a key intermediate in the formal syntheses of (-)-homopumilotoxin 223G and (-)-epiquinamide.     

Theoretical calculation of electronic circular dichroism of the rotationally restricted 3,8'-biflavonoid morelloflavone

Theoretical calculation of electronic circular dichroism (ECD) of the rotationally restricted 3,8'-biflavonoid (+)-morelloflavone using time dependent density functional theory (TDDFT), performed at 298 K at B3LYP-SCRF/6-31G*//B3LYP/6-31G* level with COSMO model, permitted unequivocal assignment of its 2R,3S absolute configuration. The experimentally observed Cotton effect (CE) around 290 nm is contributed by the acetophenone pi --> pi* transition of the ABC-flavanone moiety and the electronic transition within the DEF-flavone moiety, while another diagnostic positive CE around 350 nm is attributable to the electronic interaction between the ABC-flavanone moiety and the DEF-flavone moiety, as well as the electronic transition within the DEF-flavone moiety. The remarkable differences of the calculated ECD of its two rotamers indicate that the rotational restrictions significantly affect the ECD of 3,8'-biflavonoids. Empirical ECD rules derived from monomeric flavonoids may not be applicable to configurational assignment of complex 3,8'-biflavonoids. This study has provided new insights in interpreting the experimentally observed ECD spectra of this class of compounds.     

Molybdenum determination in iron matrices by ICP-AES after separation and preconcentration using polyurethane foam

A procedure is proposed for the separation and determination of molybdenum in iron matrices by a batch process. It is based on the solid-phase extraction of the molybdenum(V) ion as thiocyanate complex on polyurethane (PU) foam. The extraction parameters were optimized. Using 0.20 mol L-1 hydrochloric acid, a thiocyanate concentration of 0.10 mol L-1, 100 mg of polyurethane foam and shaking time of 10 min, molybdenum (5-400 micrograms) can be separated and preconcentrated from large amounts of iron (10 mg). Desorption was carried out instantaneously by conc. nitric acid or acetone. Distribution coefficients, sorption capacity of the PU foam and coefficients of variation were also evaluated. The effect of some ions on the separation procedure was assessed. Iron(III) should be reduced to iron(II). The proposed procedure was used to determine molybdenum in standard iron matrices such as steel and pure iron. The achieved results did not show significant differences with certified values.     

Monodisperse magnetic poly(glycidyl methacrylate) microspheres for isolation of autoantibodies with affinity for the 46 kDa form of unconventional Myo1C present in autoimmune patients

Monodisperse nonmagnetic macroporous poly(glycidyl methacrylate) (PGMA) microspheres were synthesized by multistep swelling polymerization of glycidyl methacrylate, ethylene dimethacrylate and 2-[(methoxycarbonyl)methoxy]ethyl methacrylate (MCMEMA). This was followed (a) by ammonolysis to modify the microspheres with amino groups, and (b) by incorporation of iron oxide (γ-Fe₂O₃) into the pores to render the particles magnetic. The resulting porous and magnetic microspheres were characterized by scanning and transmission electron microscopy (SEM and TEM), atomic absorption and Fourier transform infrared spectroscopy (AAS and FTIR), elemental analysis, vibrating magnetometry, mercury porosimetry and Brunauer-Emmett-Teller adsorption/desorption isotherms. The microspheres are meso- and macroporous, typically 5 μm in diameter, contain 0.9 mM · g^?1 of amino groups and 14 wt.% of iron according to elemental analysis and AAS, respectively. The particles were conjugated to p46/Myo1C protein, a potential biomarker of autoimmune diseases, to isolate specific autoantibodies in the blood of patients suffering from multiple sclerosis (MS). The p46/Myo1C loaded microspheres are shown to enable the preconcentration of minute quantities of specific immunoglobulins prior to their quantification via SDS-PAGE. The immunoglobulin M (IgM) with affinity to Myo1C was detected in MS patients.

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Graphical abstract Monodisperse magnetic poly(glycidyl methacrylate) microspheres were synthesized, conjugated with 46 kDa form of unconventional Myo1C protein (p46/Myo1C) via carbodiimide (DIC) chemistry, and specific autoantibodies isolated from blood of multiple sclerosis (MS) patients; immunoglobulin M (IgM) level increased in MS patients.

     

Quantifying Electronic Effects in QM and QM/MM Biomolecular Modeling with the Fukui Function

Multi-scale quantum-mechanical/molecular-mechanical(QM/MM) and large-scale QM simulation provide valuable insight into enzyme mechanism and structure-property relationships. Analysis of the electron density afforded through these methods can enhance our understanding of how the enzyme environment modulates reactivity at the enzyme active site. From this perspective, tools from conceptual density functional theory to interrogate electron densities can provide added insight into enzyme function. We recently introduced the highly parallelizable Fukui shift analysis(FSA) method, which identifies how frontier states of an active site are altered by the presence of an additional QM residue to identify when QM treatment of a residue is essential as a result of quantum-mechanically affecting the behavior of the active site. We now demonstrate and analyze distance and residue dependence of Fukui function shifts in pairs of residues representing different non-covalent interactions. We also show how the interpretation of the Fukui function as a measure of relative nucleophilicity provides insight into enzymes that carry out S_N2 methyl transfer. The FSA method represents a promising approach for the systematic, unbiased determination of quantum mechanical effects in enzymes and for other complex systems that necessitate multi-scale modeling.