Activation of pentafluorophenylsilanes by weak Lewis bases in reaction with iminium cations

The Lewis base mediated carbon-carbon bond forming reactions between pentafluorophenylsilanes and iminium cations were studied theoretically and experimentally. The complexation of silanes with anionic Lewis bases was analyzed computationally using DFT methods at the B3LYP/6-31+G(d) level. The pentafluorophenyl group was found to exhibit a significant stabilizing effect on the formation of pentacoordinate silicon species, with (C6F5)3SiF and C6F5SiF3 being the strongest Lewis acids. Comparison of geometrical isomers of trigonal bipyramidal siliconates R2(C6F5)SiXY- (R = Me, F, Cl; X, Y = F, Cl, ClO4) revealed that the heteroatoms and the C6F5 group prefer to occupy apical and equatorial positions, respectively. Calculations of C6F5 group transfer processes from silanes to N,N-dimethyliminium cation lead to the following conclusions: (1) when employing weak Lewis bases X- = Cl-, ClO4- as activators, R2(C6F5)SiF are more reactive than R2(C6F5)SiX (X = Cl, ClO4); (2) the C6F5 group is much more reactive in an apical position than in an equatorial position of the siliconate; (3) a solvent greatly increases the reaction barrier by stabilizing the reactants; and (4) the efficiency of C-C bond formation can be improved by rendering the process intramolecular. It was shown experimentally that reactions of (C6F5)3SiF with PhCH=NMe2+TfO- can be promoted by a series of weak Lewis bases, from which the chloride anion was the most effective. Even more facile was the reaction of N-(silyloxyethyl)iminium ion (C6F5)3SiOCH2CH2N(Me)=CHPh+TfO-, likely proceeding via intramolecular transfer of a C6F5 group. The optimal conditions for pentafluorophenylation of iminium ions involved the use of benzyltriethylammonium chloride in refluxing dichloroethane.     

Crystallization Behavior of Poly(3-hydroxybutyrate) (PHB), Poly(ε-caprolactone) (PCL) and Their Blend (50:50 wt.%) Studied by 2D FT-IR Correlation Spectroscopy

Variable-temperature FT-IR spectra of poly(3-hydroxybutyrate) (PHB), poly(ε-caprolactone) (PCL) and a PHB/PCL (50:50 wt.%) blend were analyzed by two-dimensional correlation spectroscopy (2DCOS). For this purpose the ν(CO) region was employed to characterize in some detail the crystallization behavior of the investigated polymer systems during cooling from the melt. The asynchronous 2D correlation spectra clearly captured the existence of three components in the crystallinity-sensitive region of the CO stretching mode for PHB and PCL, respectively: a well-ordered, an inter-mediate and a less ordered crystalline state. Furthermore, by 2DCOS application a sequential order of the observed structural changes could be proposed for the whole temperature range during the crystallization of both polymers. In the case of the PHB/PCL (50:50 wt.%) polymer blend, we have split up the spectral data set in the sub-sets between 200–120 °C and 70–30 °C for a more detailed 2DCOS analysis. In this way we could separate the crystallization process of PHB and PCL in the polymer blend.     

LC-DAD/ESI-MS/MS study of phenolic compounds in ash (Fraxinus excelsior L. and F. americana L.) heartwood. Effect of toasting intensity at cooperage

The phenolic composition of heartwood extracts from Fraxinus excelsior L. and F. americana L., both before and after toasting in cooperage, was studied using LC-DAD/ESI-MS/MS. Low-molecular weight (LMW) phenolic compounds, secoiridoids, phenylethanoid glycosides, dilignols and oligolignols compounds were detected, and 48 were identified, or tentatively characterized, on the basis of their retention time, UV/Vis and MS spectra, and MS fragmentation patterns. Some LMW phenolic compounds like protocatechuic acid and aldehyde, hydroxytyrosol and tyrosol, were unlike to those for oak wood, while ellagic and gallic acid were not found. The toasting of wood resulted in a progressive increase in lignin degradation products with regard to toasting intensity. The levels of some of these compounds in medium-toasted ash woods were much higher than those normally detected in toasted oak, highlighting vanillin levels, thus a more pronounced vanilla character can be expected when using toasted ash wood in the aging wines. Moreover, in seasoned wood, we found a great variety of phenolic compounds which had not been found in oak wood, especially oleuropein, ligstroside and olivil, along with verbascoside and isoverbascoside in F. excelsior, and oleoside in F. americana. Toasting mainly provoked their degradation, thus in medium-toasted wood, only four of them were detected. This resulted in a minor differentiation between toasted ash and oak woods. The absence of tannins in ash wood, which are very important in oak wood, is another peculiar characteristic that should be taken into account when considering its use in cooperage.     

Evaluation of the In Vitro Antiparasitic Effect of the Essential Oil of Cymbopogon winterianus and Its Chemical Composition Analysis

Cymbopogon winterianus, known as “citronella grass”, is an important aromatic and medicinal tropical herbaceous plant. The essential oil of C. winterianus (EOCw) is popularly used to play an important role in improving human health due to its potential as a bioactive component. The present study aimed to identify the components of the essential oil of C. winterianus and verify its leishmanicidal and trypanocidal potential, as well as the cytotoxicity in mammalian cells, in vitro. The EOCw had geraniol (42.13%), citronellal (17.31%), and citronellol (16.91%) as major constituents. The essential oil only exhibited significant cytotoxicity in mammalian fibroblasts at concentrations greater than 250 μg/mL, while regarding antipromastigote and antiepimastigote activities, they presented values considered clinically relevant, since both had LC₅₀ < 62.5 μg/mL. It can be concluded that this is a pioneer study on the potential of the essential oil of C. winterianus and its use against the parasites T. cruzi and L. brasiliensis, and its importance is also based on this fact. Additionally, according to the results, C. winterianus was effective in presenting values of clinical relevance and low toxicity and, therefore, an indicator of popular use.     

Electrophoretic characterization of LNP/AAV-encapsulated nucleic acids: Strengths and weaknesses

The use of nucleic acids (NAs) has revolutionized medical approaches and ushered in a new era of combating various diseases. Accordingly, there is an increasing demand for accurate identification, localization, quantification, and characterization of NAs encapsulated in nonviral or viral vectors. The vast spectrum of molecular dimensions and intra- and intermolecular interactions presents a formidable obstacle for NA analytical development. Typically, the comprehensive analysis of encapsulated NAs, free NAs, and their spatial distribution poses a challenge that is seldom tackled in its complete complexity. The identification of appropriate physicochemical methodologies for large nonencapsulated or encapsulated NAs is particularly intricate and necessitates an evaluation of the analytical outcomes and their appropriateness in addressing critical quality attributes. In this work, we examine the analytics of non-encapsulated or encapsulated large NAs (>500 nucleotides) utilizing capillary electrophoresis (CE) and liquid chromatography (LC) methodologies such as free zone CE, gel CE, affinity CE, and ion pair high-performance liquid chromatography (HPLC). These methodologies create a complete picture of the NA's critical quality attributes, including quantity, identity, purity, and content ratio.     

Insight into the Interaction of Furfural with Metallic Surfaces in the Electrochemical Hydrogenation Process

Electrocatalytic hydrogenation of furfural on metal surfaces has become an important research subject due to the potential of the reaction product 2-methylfuran as a renewable energy resource. Identifying effective determinants in this reaction process requires a thorough investigation of the complex electrode-electrolyte interactions, which considers a variety of the influential components. In this work, in operando electrochemical Raman Spectroscopy and Molecular Dynamics simulations were utilized to investigate different characteristics of the interface layer in the electrocatalytic hydrogenation of furfural. Hereby, the influence of applied potentials, electrode material, and electrolyte composition were investigated in detail. The studied parameters give an insight into furfural's binding situation, molecular orientation, and reaction mechanism.     

Novel diacetylene-containing polymers for second order NLO applications: effect of main chains and structure property relationships

In order to obtain polymers having high second order nonlinear optical (NLO) response, various novel polymers that contain polar dye molecules in side chains and diacetylenic groups in the main chains were synthesized, and their second order NLO properties were studied. Some of these polymers consisting of para-benzoate and para-cinnamate main chains, showed extremely high NLO coefficients, d₃₃ of 200 - 350 pm/V, and the corresponding meta polymers showed much inferior NLO coefficients. The polymers having aliphatic main chains had very little NLO response probably because of their low glass transition temperatures and flexibility of main chains. The high SHG responses of these polymers are attributed to their facile orientation of both chromophores and main chains. In the case of para-polymers, the main chain orientation of alkoxybenzoate and cinnamate along the chromophore is thought to be a reason for their high NLO coefficients.     

Migration and Precipitation of Platinum in Anion-Exchange Membrane Fuel Cells

Despite the recent progress in increasing the power generation of Anion-exchange membrane fuel cells (AEMFCs), their durability is still far lower than that of Proton exchange membrane fuel cells (PEMFCs). Using the complementary techniques of X-ray micro-computed tomography (CT), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) spectroscopy, we have identified Pt ion migration as an important factor to explain the decay in performance of AEMFCs. In alkaline media Pt⁺² ions are easily formed which then either undergo dissolution into the carbon support or migrate to the membrane. In contrast to PEMFCs, where hydrogen cross over reduces the ions forming a vertical “Pt line” within the membrane, the ions in the AEM are trapped by charged groups within the membrane, leading to disintegration of the membrane and failure. Diffusion of the metal components is still observed when the Pt/C of the cathode is substituted with a FeCo−N−C catalyst, but in this case the Fe and Co ions are not trapped within the membrane, but rather migrate into the anode, thereby increasing the stability of the membrane.     

Rodlike Cellulose Microcrystals: Structure,Properties, and Applications

Summary: In this article we present some interesting properties of rodlike cellulose microcrystals (so‐called “whiskers”). These microcrystals can be obtained from different cellulose sources such as wood, cotton, or animal origin. When submitted to acid hydrolysis, the cellulose fibers yield stable aqueous suspensions because of the presence of negative charges on the surface of the microcrystallites during the hydrolysis process. The obtained microcrystals are rod‐shaped particles, the dimensions of which depend on the cellulose origin. For instance, the cotton whiskers have typical dimensions varying from 100 to 300 nm in length, L, and 8 to 10 nm in diameter, d, while those of the tunicate whiskers range from 100 nm to few micrometers in length and 10 to 20 nm in diameter. At very low concentrations, these whiskers are randomly suspended in water and form an isotropic phase. When the concentration reaches a critical value, the whiskers spontaneously display ordered phases showing interesting liquid crystal properties (nematic and chiral nematic). The chiral nematic orders can be retained after evaporation of the solvent (generally water), leaving iridescent films. The reflected color can be controlled by changing either the ionic strength or by applying an electric field. These colloidal particles have been investigated using several techniques including small‐angle neutron scattering (SANS), small angle X‐ray scattering, rheology, and more recently dynamic and static light scattering techniques (DLS and SLS) to highlight their static and dynamic behavior. Because of their geometry, important axis ratio (L/d), and high crystallinity, these rods have been also extensively used to process nanocomposites based on polymer matrices, to reinforce their mechanical properties. All these properties are discussed in this contribution.

Rodlike nanocrystals in aqueous suspension (left, Tunicate, 1 wt.‐%) and film (right), observed between cross‐polarizers.     

Optimisation of the ethylene glycol reduction method for the synthesis of platinum-ceria-carbon materials as catalysts for the methanol oxidation reaction

Journal of Solid State Electrochemistry - Novel platinum-ceria-Ketjenblack carbon bifunctional electrocatalysts with flower-shaped ceria crystals were synthesised for conducting the methanol...