LC-ESI-MS/MS Method for the Profiling of Glycerophospholipids and its Application to the Analysis of Tobacco Hairy Roots as Early Indicators of Phenol Pollution

The growing impact of organic and inorganic pollutants on the environment has led to the development of numerous strategies to counteract this effect. Among all, green technologies such as phytoremediation, has won relevance for its low cost as well as being an eco-friendly and sustainable process. In the past years, tobacco hairy roots (HRs) have become a good example of the effectiveness of plants as a tool for removing different pollutants. In this sense, the understanding of the intracellular mechanisms involved in the phytoremediation process has become of great interest. Glycerophospholipids (GLPs) are a key factor on intracellular signaling, given that they can activate different pathways, despite there is not enough information available about their levels and fluctuation under certain stress conditions. The aim of this work was to develop of a new chromatographic method coupled to electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) with selected reaction monitoring (SRM) and data dependent scan detection for the evaluation of GLP profile after the exposure to phenol, to get a better understanding of lipids turnover and their effect on signaling pathways. This highly sensitive method allows the identification, separation and quantification in less than a 20 min-run of the eleven most relevant GPL species present in hairy tobacco root extracts after phenol exposure, and is suitable for evaluating small changes in GPL levels.

     

Proximity-assisted cycloaddition reactions--facile Lewis acid-mediated synthesis of diversely functionalized bicyclic tetrazoles

Aliphatic azidonitriles separated by three or four carbon atoms undergo facile Lewis acid-induced cycloadditions to give bicyclic tetrazoles, even at 0 degrees C. Extension to 3-azido-2-aryl-1,3-dioxolanes and the corresponding 1,3-dioxanes in the presence of TMSCN and BF3.OEt2 leads to a series of diversely functionalized novel oxabicyclic tetrazoles. The reactions represent new aspects of proximity-assisted dipolar cycloadditions that afford thermodynamically controlled enantiopure products proceeding through discrete oxocarbenium ion intermediates.     

Effects of glycerol and sorbitol on the thermal dependence of the lysis of human erythrocytes by ethanol

In this work, the effects of 1 mol/L glycerol or sorbitol on the thermal dependence (27-47 degrees C) of the lysis of human erythrocytes by ethanol in saline solution (0.154 mol/L NaCl) have been evaluated. Lysis was monitored by measurement of the absorbance at 540 nm. Ethanol produced either lysis or protection against lysis depending on the conditions. These antagonistic effects are attributed to the existence of expanded (R) and compacted (T) erythrocytes, present under conditions of low and high osmolarity, respectively. The transitions of lysis of the R state and formation and lysis of the T state were all found to be sigmoidally defined. The ethanol concentration at the midpoint of the lysis transition of the R state (D(50R)) was found to decrease with increasing temperature and osmolarity. In the presence of glycerol or sorbitol, an increase in temperature led to smaller decreases in D(50R) and osmotic protection against lysis. The ethanol concentration at the midpoint of formation (S(50T)) and lysis (D(50T)) of the T state also decreased with increasing temperature and osmolarity. Lysis of R state erythrocytes is determined by the chaotropic action of ethanol, but the formation and lysis of T state erythrocytes are determined by osmotic pressure effects.     

Metallocene Combinations in Ethylene Polymerization: A Cyclic and Differential Pulse Voltammetry Study

A series of metallocenes, namely [Cp₂ZrCl₂], [(MeCp)₂ZrCl₂], [(nBuCp)₂ZrCl₂], [(iBuCp)₂ZrCl₂], [(tBuCp)₂ZrCl₂], [Cp₂TiCl₂], [Et(Ind)₂ZrCl₂], [Et(IndH₄)₂ZrCl₂] and [MeSi₂(Ind)₂ZrCl₂)], were combined in a 1:1 molar ratio within a reactor for ethylene polymerization, with MAO as the cocatalyst. The catalysts were characterized by cyclic and differential pulse voltammetry. The combined systems that showed the highest and lowest activities were combined in 1:3 and 3:1 molar ratios. The catalyst activity in the ethylene polymerization reaction is discussed in terms of the estimated consumption rate, decomposition rate constant and half‐life of the metallocene species formed with MAO in an ethylene atmosphere.

     

Rotamerism, tautomerism, and excited-state intramolecular proton transfer in 2-(4'-N,N-diethylamino-2'-hydroxyphenyl)benzimidazoles: novel benzimidazoles undergoing excited-state intramolecular coupled proton and charge transfer

The solvent and temperature dependence of the phototautomerization of 1-methyl-2-(2'-hydroxyphenyl)benzimidazole (4) and the novel compounds 2-(4'-amino-2'-hydroxyphenyl)benzimidazole (1), 2-(4'-N,N-diethylamino-2'-hydroxyphenyl)benzimidazole (2), and 1-methyl-2-(4'-N,N-diethylamino-2'-hydroxyphenyl)benzimidazole (3), together with the ground-state rotamerism and tautomerism of these new compounds, have been studied by UV-vis absorption spectroscopy and steady-state and time-resolved fluorescence spectroscopy. A solvent-modulated rotameric and tautomeric equilibrium is observed in the ground state for 1, 2, and 3. In cyclohexane, these compounds mainly exist as a planar syn normal form, with the hydroxyl group hydrogen-bonded to the benzimidazole N3. In ethanol, the syn form is in equilibrium with its planar anti rotamer (for 1 and 2), with the phenyl ring rotated 180 degrees about the C2-C1' bond and with a nonplanar rotamer for compound 3. In aqueous solution, a tautomeric equilibrium is established between the anti normal form (or the nonplanar rotamer for 3) and the tautomer (with the hydroxyl proton transferred to the benzimidazole N3). The syn normal form of these compounds undergoes in all the solvents an excited-state intramolecular proton-transfer process from the hydroxyl group to the benzimidazole N3 to yield the excited tautomer. The tautomer fluorescence quantum yield of 2, 3, and 4 shows a temperature-, polarity-, and viscosity-dependent radiationless deactivation, connected with a large-amplitude conformational motion. We conclude that this excited-state conformational change experienced by the tautomer is associated with an intramolecular charge transfer from the deprotonated dialkylaminophenol or phenol (donor) to the protonated benzimidazole (acceptor), affording a nonfluorescent charge-transfer tautomer. Therefore, these compounds undergo an excited-state intramolecular coupled proton- and charge-transfer process.     

Application of thermal analysis in study of binary mixtures with metformin

Thermal analysis is an essential analytical tool in development of new formulations as well as to study the interaction between drugs and excipients. This work aims to investigate the possible interactions between metformin and excipients as microcrystalline cellulose (Microcel MC101®), starch sodium glycolate (Explosol®), sodium croscarmellose (Explosel®), PVP K30, magnesium stearate, starch and lactose, usually employed in pharmaceutical products. TG, DSC and DTA techniques were used for the thermal characterization to track if the thermal properties of the drug substance were modified in the mixture. Disregard of the starch and lactose systems, no changes in thermal behavior of mixtures were found. Thermogravimetric studies (TG) of metformin and its binary mixtures showed different thermal behavior.     

Cubic Pisot unit combinatorial games

Generalized Tribonacci morphisms are defined on a three letters alphabet and generate the so-called generalized Tribonacci words. We present a family of combinatorial removal games on three piles of tokens whose set of \({\mathcal{P}}\) -positions is coded exactly by these generalized Tribonacci words. To obtain this result, we study combinatorial properties of these words like gaps between consecutive identical letters or recursive definitions of these words. β-Numeration systems are then used to show that these games are tractable, i.e., deciding whether a position is a \({\mathcal{P}}\) -position can be checked in polynomial time.     

Development and validation of a method for quantitative determination of econazole nitrate in cream formulation by capillary zone electrophoresis

A simple, fast, inexpensive and reliable capillary zone electrophoresis (CZE) method for the determination of econazole nitrate in cream formulations has been developed and validated. Optimum conditions comprised a pH 2.5 phosphate buffer at 20 mmol L(-1) concentration, +30 kV applied voltage in a 31.5 cm x 50 microm I.D. capillary. Direct UV detection at 200 nm led to an adequate sensitivity without interference from sample excipients. A single extraction step of the cream sample in hydrochloric acid was performed prior to injection. Imidazole (100 microg mL(-1)) was used as internal standard. Econazole nitrate migrates in approximately 1.2 min. The analytical curve presented a coefficient of correlation of 0.9995. Detection and quantitation limits were 1.85 and 5.62 microg mL(-1), respectively. Excellent accuracy and precision were obtained. Recoveries varied from 98.1 to 102.5% and intra- and inter-day precisions, calculated as relative standard deviation (RSD), were better than 2.0%. The proposed CZE method presented advantageous performance characteristics and it can be considered suitable for the quality control of econazole nitrate cream formulations.     

Chemoenzymatic synthesis of both enantiomers of 3-hydroxy-2,2-dimethylcyclohexanone

The stereoselective acetylation of meso-2,2-dimethyl-1,3-cyclohexanediol by vinyl acetate in the presence of three lipases gave the (1R,3S)-monoester in high enantiomeric excess (ee > or = 98%). The hydrolysis of the corresponding meso-diacetate in the presence of Candida antarctica lipase in phosphate buffer provided the opposite enantiomer. Optically active monoacetates were converted to both enantiomers of 3-hydroxy-2,2-dimethylcyclohexanone, a versatile chiral building block.     

A new evanescent wave ammonia sensor based on polyaniline composite

A single-mode TE(0)-TM(0) optical planar waveguide ammonia sensor based on polyaniline/polymethyl methacrylate (PANI/PMMA) composite is designed and developed. The sensing properties of the photonic sensor to ammonia at room temperature are studied. A significant change is observed in the guided light output power of the sensor after it is exposed to ammonia gas. The metrological parameters (sensitivity, response time and recovery time) of the sensor are strongly influenced by the interaction length (length of sensing region). Compared with the conventional optical ammonia sensor based on absorption spectroscopy, the integrated optical sensor is more sensitive to ammonia.