Adsorption of Co(II), Ni(II), Cu(II), and Zn(II) on hexagonal templated zirconia obtained thorough a sol-gel process: the effects of nanostructure on adsorption features

Using zirconium tetrabutoxide, diaminedecane, and diamineoctane as precursors, a templated hexagonal zirconia matrix is synthesized and characterized by X-ray diffractometry and scanning electron microscopy. The adsorption capacity of such a matrix toward Co(II), Ni(II), Cu(II), and Zn(II) from aqueous solutions is studied. The adsorption affinity of the synthesized hexagonal templated zirconia toward the cations is Cu(II)>Zn(II) >Ni(II)>Co(II). It is also verified that the adsorption of the cations follows a Langmuir and not a Freundlich isotherm. All obtained isotherms are of type I, according to the IUPAC classification. The observed adsorption affinity sequence can be explained by taking into account the velocity constant for the substitution of water molecules into the cation coordination spheres, as well as the Irving-Williams series.     

Chemical Approach to the Optimization of Conditions Using HS-SPME/GC–MS for Characterization of Volatile Compounds in Eugenia brasiliensis Fruit

Grumixama (Eugenia brasiliensis Lam.) is a native fruit of the Brazilian Atlantic Forest, belonging to the Myrtaceae family, which designatesthe most significant number of species with food potential. It stands out due to its phytochemical characteristics because of the presence of polyphenols and volatile organic compounds. Volatile compounds are substances released by foods that give off an aroma and influence flavor. Solid-phase microextraction is a technique that allows for low-cost, fast, and solvent-free extraction, has an affinity for numerous analytes, and is easily coupled to gas chromatography. The objectives of this work were to evaluate the efficiency of different fibers of SPME (solid-phase microextraction) in the extraction of volatile organic compounds from grumixama pulp; optimize a method for extraction time, temperature, and sample weight; and to determine the characteristic volatile profile of this fruit. For the extraction of volatile compounds, three fibers of different polarities were used: polar polyacrylate (PA) fibers, divinylbenzene/carboxyne/polydimethylsiloxane (DVB/CAR/PDMS) semipolar fibers, and polydimethylsiloxane/divinylbenzene (PDMS/DVB). Fourteen volatile organic compounds (VOCs) were identified by DVB/CAR/PDMS, six by PA, and seven by PDMS/DVB through solid-phase microextraction in the headspace mode (SPME-HS). Considering the total number of compounds identified, regardless of the fiber used, and the optimization of the method, Eugenia brasiliensis presented sesquiterpene fractions (85.7%, 83.3%, and 85.7% of total VOCs) higher than the monoterpene fractions (14.3%, 16.7%, and 14.3%) for DVB/CAR/PDMS, PA, and PDMS/DVB, respectively in its composition. In addition, it was possible to verify that the fiber DVB/CAR/PDMS presented a better efficiency due to the larger chromatographic area observed when the grumixama pulp was subjected to conditions of 75 °C, 2.0 g, and an adsorption time of 20 min.     

Hydroxyl Radical Generation and DNA Nuclease Activity: A Mechanistic Study Based on a Surface‐Immobilized Copper Thioether Clip‐Phen Derivative

Coordination compounds of copper have been invoked as major actors in processes involving the reduction of molecular oxygen, mostly with the generation of radical species the assignment for which has, so far, not been fully addressed. In the present work, we have carried out studies in solution and on surfaces to gain insights into the nature of the radical oxygen species (ROS) generated by a copper(II) coordination compound containing a thioether clip‐phen derivative, 1,3‐bis(1,10‐phenanthrolin‐2‐yloxy)‐N‐(4‐(methylthio)benzylidene)propan‐2‐amine (2CP‐Bz‐SMe), enabling its adsorption/immobilization to gold surfaces. Whereas surface plasmon resonance (SPR) and electrochemistry of the adsorbed complex indicated the formation of a dimeric Cu^I intermediate containing molecular oxygen as a bridging ligand, scanning electrochemical microscopy (SECM) and nuclease assays pointed to the generation of a ROS species. Electron paramagnetic resonance (EPR) data reinforced such conclusions, indicating that radical production was dependent on the amount of oxygen and H₂O₂, thus pointing to a mechanism involving a Fenton‐like reaction that results in the production of OH^..     

Experimental NMR and MS study of benzoylguanidines. Investigation of E/Z isomerism

Molecules containing the guanidinic nuclei possess several pharmacological applications, and knowing the preferred isomers of a potential drug is important to understand the way it operates pharmacologically. Benzoylguanidines were synthesized in satisfactory to good yields and characterized by NMR, Electrospray Ionization Mass Spectrometry (ESI‐MS) and Fourrier Transform InfraRed Spectroscopy techniques (FTIR). E/Z isomerism of the guanidines was studied and confirmed by NMR analysis in solution (¹H‐¹³C Heteronuclear Single Quantum Coherence (HSQC) and Heteronuclear Multiple‐Bond Correlation (HMBC), ¹H‐¹⁵N HMBC, ¹H‐¹H Correlation Spectroscopy (COSY) and Nuclear Overhauser Effect Spectroscopy (NOESY) experiments) at low temperatures. Compounds with p‐Cl and p‐Br aniline moiety exist mainly as Z isomer with a small proportion of E isomer, whereas compounds with p‐NO2 moiety showed a decrease in proportion of isomer Z. The results are important for the application of these molecules as enzymatic inhibitors. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis of aggregation pheromone components of cerambycid species through α-hydroxylation of alkylketones

The synthesis of 3-hydroxy-2-hexanone and 2,3-hexanediol, two components of the aggregation pheromone of several cerambycid species, is disclosed in here. Starting from 2-hexanone, through an α-hydroxylation using (diacetoxyiodo)benzene, 3-hydroxy-2-hexanone is obtained in good yield. Further reduction of this compound, gives 2,3-hexanediol in excellent yield. A study of the α-hydroxylation reaction of several alkylketones using an hypervalent iodine reagent is also disclosed in here. The synthesis of optically active compounds (R)- and (S)-3-hydroxy-2-hexanone was achieved starting from 2-hexanone with nitrosobenzene and l- and d-proline respectively, in several reaction media.     

On the effective potential in higher-derivatives superfield theories

We study the one-loop quantum corrections for higher-derivative superfield theories, generalizing the approach for calculating the superfield effective potential. In particular, we calculate the effective potential for two versions of higher-derivative chiral superfield models. We point out that the equivalence of the higher-derivative theory for the chiral superfield and the one without higher derivatives but with an extended number of chiral superfields occurs only when the mass term is contained in the general Lagrangian. The presence of divergences can be taken as an indication of that equivalence.     

Different salinities water characterization by DSC-cooling

Water is a fundamental element of life. Its multiple uses are indispensable for a wide spectrum of human activities. This study aims to characterize water from different salinities obtained in the Cariri region of Paraíba, Brazil. The samples were analyzed using the DSC-coupled to the Peltier system (DSC-Cooling) and physical–chemical water tests performed employing reactive kits, using the Spectroquant Merck^? specific for each test. The calorimetric curves showed crystallization phase transitions with different characteristics in peak format and crystallization temperatures between the samples of different salinities. The calorimetric data obtained in the process of crystallization of water is directly correlated to the physico-chemical parameters of conductivity and total dissolved solids, showing that the analytical technology DSC-cooling/heating is suitable for characterization of different salinities water.     

Radiolabeling of low molecular weight d-galactose-based glycodendrimer with technetium-99m and biodistribution studies

Glycodendrimers are neoglycoconjugates that can be considered as bioisosters of glycoproteins, since they can mimic the multivalent interactions of lectin-carbohydrate. The ability of glycodendrimers to present multivalent interactions with lectins as compared to a monovalent ligand is referred to as “cluster effect”. It is expected that, because of the cluster effect, glycodendrimers would result in a better association with lectins than mono-carbohydrate anchored systems. Radioisotopes are useful to evaluate biodistribution of molecules. This study is important to obtain information about molecule–receptor interactions. Indeed, such study can provide an exquisite tool to evaluate the affinity of certain molecules to specific areas in the body, leading to the development of new radiopharmaceuticals and/or drug delivery systems. Herein, we describe a d-galactose coated low molecular weight PAMAM G0 dendrimer that was successfully radiolabeled with technetium-99m. Biodistribution studies and scintigraphic images were performed in healthy mice. It was observed high liver uptake which was significantly reduced in blocking studies, indicating hepatic specificity. Therefore, low molecular weight glycodendrimer can be considered as useful platform for selective targeting of drugs to the liver and to assess hepatic function.