Insights into the Complexity of Weak Intermolecular Interactions Interfering in Host–Guest Systems

The recognition properties of heteroditopic hemicryptophane hosts towards anions, cations, and neutral pairs, combining both cation–π and anion–π interaction sites, were investigated to probe the complexity of interfering weak intermolecular interactions. It is suggested from NMR experiments, and supported by CASSCF/CASPT2 calculations, that the binding constants of anions can be modulated by a factor of up to 100 by varying the fluorination sites on the electron‐poor aromatic rings. Interestingly, this subtle chemical modification can also reverse the sign of cooperativity in ion‐pair recognition. Wavefunction calculations highlight how short‐ and long‐range interactions interfere in this recognition process, suggesting that a disruption of anion–π interactions can occur in the presence of a co‐bound cation. Such molecules can be viewed as prototypes for examining complex processes controlled by the competition of weak interactions.     

Drying Effects on Chemical Composition and Antioxidant Activity of Lippia thymoides Essential Oil,a Natural Source of Thymol

Leaves of Lippia thymoides (Verbenaceae) were dried in an oven at 40, 50 and 60 °C and the kinetic of drying and the influence of the drying process on the chemical composition, yield, and DPPH radical scavenging activity of the obtained essential oils were evaluated. The composition of the essential oils was determined with gas chromatography-mass spectrometry and gas chromatography-flame ionization detection analyses. The influence of drying on the chemical composition of the essential oils of L. thymoides was evaluated by multivariate analysis, and their antioxidant activity was investigated via the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. The Midilli model was the most appropriate to describe the behavior of drying kinetic data of L. thymoides leaves. Thymol was the major compound for all analyzed conditions; the maximum content was obtained from fresh leaves (62.78 ± 0.63%). The essential oils showed DPPH radical scavenging activity with an average of 73.10 ± 12.08%, and the fresh leaves showed higher inhibition (89.97 ± 0.31%). This is the first study to evaluate the influence of drying on the chemical composition and antioxidant activity of L. thymoides essential oils rich in thymol.     

Chemical Composition and Antioxidant Activity of Essential Oils from Eugenia patrisii Vahl,E. punicifolia (Kunth) DC., and Myrcia tomentosa (Aubl.) DC., Leaf of Family Myrtaceae

Essential oils (EOs) were extracted from Eugenia patrisii, E. punicifolia, and Myrcia tomentosa, specimens A and B, using hydrodistillation. Gas chromatography coupled with mass spectrometry (GC/MS) was used to identify the volatile constituents present, and the antioxidant capacity of EOs was determined using diphenylpicryl-hydrazyl (DPPH) and trolox equivalent antioxidant capacity (TEAC) assays. For E. patrisii, germacrene D (20.03%), bicyclogermacrene (11.82%), and (E)-caryophyllene (11.04%) were identified as the major constituents of the EOs extracted from specimen A, whereas specimen B primarily comprised γ-elemene (25.89%), germacrene B (8.11%), and (E)-caryophyllene (10.76%). The EOs of E. punicifolia specimen A contained β-Elemene (25.12%), (E)-caryophyllene (13.11%), and bicyclogermacrene (9.88%), while specimen B was composed of (E)-caryophyllene (11.47%), bicyclogermacrene (5.86%), β-pinene (5.86%), and γ-muurolene (5.55%). The specimen A of M. tomentosa was characterized by γ-elemene (12.52%), germacrene D (11.45%), and (E)-caryophyllene (10.22%), while specimen B contained spathulenol (40.70%), α-zingiberene (9.58%), and γ-elemene (6.89%). Additionally, the chemical composition of the EOs was qualitatively and quantitatively affected by the collection period. Furthermore, the EOs of the studied specimens, especially specimen A of E. punicifolia, showed a greater antioxidant activity in DPPH rather than TEAC, as represented by a significantly high inhibition percentage (408.0%).     

Chemical Composition of Volatile Compounds in Apis mellifera Propolis from the Northeast Region of Pará State,Brazil

Propolis is a balsamic product obtained from vegetable resins by exotic Africanized bees Apis mellifera L., transported and processed by them, originating from the activity that explores and maintains these individuals. Because of its vegetable and natural origins, propolis is a complex mixture of different compound classes; among them are the volatile compounds present in the aroma. In this sense, in the present study we evaluated the volatile fraction of propolis present in the aroma obtained by distillation and simultaneous extraction, and its chemical composition was determined using coupled gas chromatography, mass spectrometry, and flame ionization detection. The majority of compounds were sesquiterpene and hydrocarbons, comprising 8.2–22.19% α-copaene and 6.2–21.7% β-caryophyllene, with additional compounds identified in greater concentrations. Multivariate analysis showed that samples collected from one region may have different chemical compositions, which may be related to the location of the resin’s production. This may be related to other bee products.     

Rapid optimized separation of bromide in serum samples with capillary zone electrophoresis by using glycerol as additive to the background electrolyte

After decades of neglect, bromide has recently been re-introduced in therapy as an effective anti-epileptic drug. The present paper describes the methodological optimization and validation of a method based on capillary zone electrophoresis for the rapid determination of bromide in serum using a high-viscosity buffer and a short capillary (10 cm). The optimized running buffer was composed of 90 mM sodium tetraborate, 10 mM sodium chloride, pH 9.24 and 25% glycerol. The separation was carried out at 25 kV at a temperature of 20 °C. Detection was by direct UV absorption at 200 nm wavelength. The limit of detection (signal-to-noise ratio = 5) in serum was 0.017 mM. The precision of the method was verified in blank serum samples spiked with bromide, obtaining intra-day and day-to-day tests, relative standard deviation values ≤0.2% in terms of migration times and values <2% in terms of peaks areas, respectively.     

Design and electro-optical characterization of Si-based resonant cavity light emitting devices at 850 nm

We report on the fabrication and characterization of Si/SiO₂ Fabry-Perot microcavities. These structures are used to enhance the external quantum efficiency along the cavity axis and the spectral purity of emission from silicon rich oxide films that are used as active media to fabricate a Si based RCLED (resonant cavity light emitting devices). A new structure to electrically pump the active media in the resonant cavity has been designed. These structures are fabricated by chemical vapour deposition on a silicon substrate. The microcavities are tuned at 850 nm and present a quality factor ranging from 17 to 150 depending on the number of pairs constituting the dielectric mirrors. An enhancement of the electro and photoluminescence (PL) signal of 20 times is achieved for the selected emission wavelength. These cavities are characterized by TEM analysis to evaluate film uniformity, thicknesses and the densification after annealing processes for temperature ranging from 800 to 1100 °C. The electrical properties of the active media are analyzed. The electroluminescence spectral features are compared with PL spectra correlated with the quality factor of the cavities. The photometric diagram shows also a high directionality of the emitted light within a 30° cone from the sample normal.     

Preparation and Characterization of Compositions Based on PbO-MgO-Nb2O5 Using the Sol-Gel Method

Lead Magnesium Niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), is an important relaxor ferroelectric material. A significant problem exists, however, in the preparation of this material: it is very difficult to prepare pure phase, without the presence of a pyrochlore impurity phase which degrades the dielectric properties. Depending on the processing conditions, the amount of pyrochlore phase varies.Considering the ternary diagram PbO-MgO-Nb₂O₅, different compositions have been prepared by a simple sol-gel method at room temperature using Pb(CH₃COO)₂, Mg(CH₃COO)₂, Nb(OC₂H₅)₅ as precursors. After the heat treatment, the samples obtained were analyzed by XRD and EPMA with the purpose of studying the compositions formed.From the analysis of these results, it seems to be that the appearance of pyrochlore can be related to the reactivity of the MgO and/or the presence of other phases of the binary system PbO-Nb₂O₅. An excess of Pb and Mg is necessary for compositions to be formed near the PMN. The control of the amount of these two elements is very important because an excess of MgO would lead to rich compositions in Mg as a secondary phase.     

Antioxidant capacity and larvicidal and antifungal activities of essential oils and extracts from Piper krukoffii

The leaves and twigs of Piper krukoffii, collected in the Carajás National Forest, north Brazil, yielded essential oils (2.0% and 0.8%), the main constituents of which were myristicin (40.3% and 26.7%), apiole (25.4% and 34.1%) and elemicin (2.8% and 3.0%). The antioxidant activities of the oils, methanol extract and its sub-fractions were evaluated. The DPPH EC50 values varied from the ethyl acetate sub-fraction (73.4 +/- 3.7 microg/mL) to the methanol extract (24.9 +/- 0.8 microg/mL), and the ABTS TEAC values ranged in the same order from 265.7 to 349.2 microMol TE/g. These results indicated a significant antioxidant activity for the plant. The lignans (-)-kusunokin, yatein, (-)-hinokin and cubebin were identified in the methanol extract. The hydro-methanolic sub-fraction showed a high value for total phenol content (106.5 +/- 0.7 mg GAE/g), as well as 1H NMR signals for sugar moieties. Crude extracts and sub-fractions were also able to inhibit beta-carotene bleaching, varying from 22.4 to 47.1%. The oils from the leaves and twigs showed strong larvicidal (21.4 and 3.6 microg/mL) and fungicide (0.5 and 0.1 microg/mL) activities.     

Synthesis and reactivity of a ferrocene-derived PCP-pincer ligand

The 1,3-bis(diphosphinomethyl)ferrocene 3 readily reacts with [(C2H4)2RhCl]2 to form an equilibrating pair of diastereomers 8a and 8b by C-H insertion into the ferrocene.