Magnetic nanoparticles coated with polyaniline to stabilize immobilized trypsin

It is reported the synthesis of magnetic nanoparticles via the chemical co-precipitation of Fe ³⁺ ions and their preparation by coating them with polyaniline. The electronic micrograph analysis showed that the mean diameter for the nanoparticles is ～15 nm. FTIR, powder X-ray diffraction and Mössbauer spectroscopy were used to understand the chemical, crystallographic and ⁵⁷Fe hyperfine structures for the two samples. The nanoparticles, which exhibited magnetic behavior with relatively high spontaneous magnetization at room temperature, were identified as being mainly formed by maghemite (γFe₂O₃). The coated magnetic nanoparticles (sample labeled “mPANI”) presented a real ability to bind biological molecules such as trypsin, forming the magnetic enzyme derivative (sample “mPANIG-Trypsin”). The amount of protein and specific activity of the immobilized trypsin were found to be 13±5 μg of protein/mg of mPANI (49.3 % of immobilized protein) and 24.1±0.7 U/mg of immobilized protein, respectively. After 48 days of storage at 4 ^°C, the activity of the immobilized trypsin was found to be 89 % of its initial activity. This simple, fast and low-cost procedure was revealed to be a promising way to prepare mPANI nanoparticles if technological applications addressed to covalently link biomolecules are envisaged. This route yields chemically stable derivatives, which can be easily recovered from the reaction mixture with a magnetic field and recyclable reused.     

Uptake of Europium(III) from Water using Magnetite Nanoparticles

It is demonstrated that colloidal magnetite nanoparticles can be used as nanosorbents for lanthanide ions dissolved in water. In particular, a series of experiments are performed for the removal of Eu(III) in distinct analytical conditions and by applying an external magnet to collect the sorbents previously dispersed in water samples. Furthermore, strategies for surface chemistry functionalization are also investigated, aiming to investigate the effect of this parameter on the removal capacity of the Fe₃O₄ nanoparticles. The supernatant solutions are monitored for the remaining amount of Eu(III) by fluorescence emission measurements in the presence of 2,6‐pyridinedicarboxylic acid as a sensitizer. The results demonstrate that neat Fe₃O₄ nanoparticles are capable of capturing lanthanide ions (III) from aqueous solutions (pH 7), without need of surface modification, and for subsequent removal by magnetic separation. During the removal, efficiency is increased after modifying the particles' surfaces with silica and 3‐aminopropyltrimethoxysilane; in alkaline medium (pH 10), there is complete removal regardless the type of nanosorbent used. This has been explained by the formation of insoluble Eu(III) species that adsorb strongly to the nanosorbents surfaces allowing their subsequent magnetic separation.     

Selective synthesis of 4-thiomethyl-1,3-dioxolan-2-ones under microwave irradiation using an environmentally benign KF/Al2O3/PEG-400 system

Research on Chemical Intermediates - We describe a simple and rapid method for selective synthesis of 4-thiomethyl-1,3-dioxolan-2-ones promoted by KF/Al2O3 using PEG-400 as solvent under microwave...     

Paper spray mass spectrometry and PLS-DA improved by variable selection for the forensic discrimination of beers

Paper spray mass spectrometry (PS-MS) combined with partial least squares discriminant analysis (PLS-DA) was applied for the first time in a forensic context to a fast and effective differentiation of beers. Eight different brands of American standard lager beers produced by four different breweries (141 samples from 55 batches) were studied with the aim at performing a differentiation according to their market prices. The three leader brands in the Brazilian beer market, which have been subject to fraud, were modeled as the higher-price class, while the five brands most used for counterfeiting were modeled as the lower-price class. Parameters affecting the paper spray ionization were examined and optimized. The best MS signal stability and intensity was obtained while using the positive ion mode, with PS(+) mass spectra characterized by intense pairs of signals corresponding to sodium and potassium adducts of malto-oligosaccharides. Discrimination was not apparent neither by using visual inspection nor principal component analysis (PCA). However, supervised classification models provided high rates of sensitivity and specificity. A PLS-DA model using full scan mass spectra were improved by variable selection with ordered predictors selection (OPS), providing 100% of reliability rate and reducing the number of variables from 1701 to 60. This model was interpreted by detecting fifteen variables as the most significant VIP (variable importance in projection) scores, which were therefore considered diagnostic ions for this type of beer counterfeit.     

Influence of Structural Features on the Cellular Uptake Behavior of Non‐Targeted Polyester‐Based Nanocarriers

The development of delivery systems efficiently uptaken by cells is of due importance since sites of drug action are generally localized in subcellular compartments. Herein, naked and core–shell polymeric nanoparticles (NPs) have been produced from poly(lactic‐co‐glycolic acid)—PLGA, poly(ethylene oxide)‐b‐poly(ε‐caprolactone)—PEO‐b‐PCL, and poly(ethylene oxide)‐b‐poly(lactic acid)—PEO‐b‐PLA. The nanostructures are characterized and the cellular uptake behavior is evaluated. The data evidence that cellular uptake is enhanced as the length of the hydrophilic PEO‐stabilizing shell reduces and that high negative surface charge restricts cellular uptake. Furthermore, NPs of higher degree of hydrophobicity (PEO‐b‐PCL) are more efficiently internalized as compared to PEO‐b‐PLA NPs. Accordingly, taking into account our recent published results 1 and the findings of the current investigation, there should be a compromise regarding protein fouling and cellular uptake as resistance to nonspecific protein adsorption and enhanced cellular uptake are respectively directly and inversely related to the length of the PEO‐stabilizing shell.

     

Partial least squares model and design of experiments toward the analysis of the metabolome of Jatropha gossypifolia leaves: Extraction and chromatographic fingerprint optimization

A major challenge in metabolomic studies is how to extract and analyze an entire metabolome. So far, no single method was able to clearly complete this task in an efficient and reproducible way. In this work we proposed a sequential strategy for the extraction and chromatographic separation of metabolites from leaves Jatropha gossypifolia using a design of experiments and partial least square model. The effect of 14 different solvents on extraction process was evaluated and an optimized separation condition on liquid chromatography was estimated considering mobile phase composition and analysis time. The initial conditions of extraction using methanol and separation in 30 min between 5 and 100% water/methanol (1:1 v/v) with 0.1% of acetic acid, 20 μL sample volume, 3.0 mL min^?1 flow rate and 25°C column temperature led to 107 chromatographic peaks. After the optimization strategy using i‐propanol/chloroform (1:1 v/v) for extraction, linear gradient elution of 60 min between 5 and 100% water/(acetonitrile/methanol 68:32 v/v with 0.1% of acetic acid), 30 μL sample volume, 2.0 mL min^?1 flow rate, and 30°C column temperature, we detected 140 chromatographic peaks, 30.84% more peaks compared to initial method. This is a reliable strategy using a limited number of experiments for metabolomics protocols.     

Theoretical characterization of the chemical bonds of some three-membered ring compounds through QTAIM theory

Structural Chemistry - In this paper, we investigate the nature of the carbonyl and the intraring C–C, C–N, C–O, N–N, O–O and N–O bonds of cyclopropanone and the...