CHARACTERIZATION AND COMPARISON OF SPECIATED ATMOSPHERIC CARBONACEOUS PARTICULATES AND THEIR POLYCYCLIC AROMATIC HYDROCARBON CONTENTS IN THE CONTEXT OF THE PASO DEL NORTE AIRSHED ALONG THE U.S.-MEXICO BORDER

Carbonaceous particulate matter (PM) was collected by both thermal precipitation and glass fiber filters from specific combustion sources and examined by transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM). PM from various natural gas burner combustion regimes (NGPM), burning tires (TPM), a heavy duty diesel truck (DPM), wood burning (WPM), candle burning (CPM), along with commercial black carbon (BC) powder and multiwall carbon nanotube (MWCNT) aggregates material exhibited similarities in PM microstructure, and average primary spherule diameters. The spherule structures consisted of curved graphene fragments and intercalated polycyclic aromatic hydrocarbons (PAH). PAH concentrations were measured and compared for these PMs, including PAH diagnostic ratios. An analysis of PAH carcinogenicity either as a carcinogenicity index or a potency equivalency factor from literature data indicated that only the TPM PAH content would pose any significant long term, carcinogenicity threat.     

Effect of Maleic‐Anhydride Grafting on the Physical and Mechanical Properties of Poly(L‐lactic acid)/Starch Blends

MA is grafted onto both PLLA and starch in an internal mixer in the presence of DCP in a one‐step reactive compatibilization process. The effect of maleation of MA on the physical and mechanical properties and morphology of the blends was assessed. The onset decomposition temperature of the PLLA/starch blends decreased as the starch content increases due to the lower thermal stability of starch and the low effect of the maleation reaction on the thermal stability of the blends. PLLA/starch blends without grafted MA showed higher crystallinity as the starch content increased. Reactive compatibilized blends with less than 20 wt% starch had higher storage modulus, indicating that the compatibility between the two phases was improved.

     

Influence of very long aging on the relaxation behavior of flame‐retardant printed circuit board epoxy composites under mechatronic conditions

Very long aging times, up to 15,100 h (629 days) at 110°C, were achieved on flame‐retardant printed circuit board laminates commonly used in automotive design. This composite was fabricated from glass fibers embedded in an epoxy resin. Aging was performed in an oven under an air atmosphere at a temperature lower than the glass‐transition temperature. Temperature‐modulated differential scanning calorimetric analysis was used to investigate the influence of such aging on the glass‐transition phenomena. A new amorphous phase appeared during aging. By extending the analysis to samples collected at different thicknesses, we demonstrated the existence of a time‐dependent gradient of the properties. A skin–core structure was evidenced, and this slowed down oxidation and allowed physical aging to occur in the bulk sample. An exponential law described the variations of the glass‐transition of the new external compound. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 786‐792, 2013     

Synthesis and Theoretical Study of New Guanylated Cyclophosphazenes and Their Use in the CO2 Fixation into Styrene Carbonate

Three new guanylated cyclophosphazenes G1–G3 have been synthesized through the catalytic guanylation of three different bi, tetra and hexa (p-aminophenoxy)-cyclophosphazenes by using N,N’-diisopropylcarbodiimide as guanylating agent, ZnEt₂ as catalyst and dry tetrahydrofuran as solvent. The resulting products have been characterized by ¹H, ¹³C{¹H} and ³¹P{¹H} NMR spectroscopy. The hexaguanylated cyclophosphazenes exhibit a deep purple colour, unusual for this type of compounds. The electronic structure of these compounds was investigated by carrying out density functional calculations at PBE-D3(BJ)/TZP level of theory. The molecular structural analysis reveals that aromatic rings are stacked and time dependent density functional calculations show that a charge transfer electronic transition occurs between the aromatic rings which absorb light around 500–700 nm. Finally, the catalytic usefulness of guanylated cyclophosphazene compounds G1–G3 has been proven by the preparation of styrene carbonate from the reaction between styrene oxide and carbon dioxide.

     

Arsenical grafted membranes for immobilization of thioredoxin-like proteins

In this work, we describe the cografting of glycidyl methacrylate and dimethyl acrylamide onto a macroporous polysulfone polymer. Aminophenyl arsenical compounds were covalently attached to the copolymer through epoxy ring add-on reactions followed by a 2-mercaptoethanol activation. Thioredoxin and thioredoxin-fusion proteins were immobilized onto this surface and detected by specific antibody recognition. Preservation of native protein folding was confirmed by the detection of the enzymatic activity of an unstable fusion protein. Immobilized fusion protein onto the modified material maintains the enzymatic activity for a longer time, up to two weeks, against the free protein under the same storage conditions that remains active for 2 days.     

Performance of Φ-Sulfo Fatty Methyl Ester Sulfonate Versus Linear Alkylbenzene Sulfonate,Secondary Alkane Sulfonate and α-Sulfo Fatty Methyl Ester Sulfonate

Sulfoxidation of fatty acid methyl esters with SO_2, O₂ and ultraviolet light of appropriate wavelength, has led to the synthesis of methyl esters sulfonates or sulfoxylates, known as Φ-MES, because of the possible random position of SO₃ group in the alkyl chain. Aqueous solutions based on the sulfoxylated methyl ester of palmitic acid (Φ-MES C16) have been studied and compared to the leading types of surfactants used today: linear alkylbenzene sulfonate (LAS) secondary alkane sulfonate (SAS) and α-sulfo fatty methyl ester sulfonate (α-MES) with regard to solubility, performance and skin compatibility. The experimental results obtained indicate that Φ-MES C16 can be regarded as a potential component of detergent formulations and most likely also of body care products.

(De)stabilization of Alpha-Synuclein Fibrillary Aggregation by Charged and Uncharged Surfactants

Parkinson’s disease (PD) is the second most common neurodegenerative disorder. An important hallmark of PD involves the pathological aggregation of proteins in structures known as Lewy bodies. The major component of these proteinaceous inclusions is alpha (α)-synuclein. In different conditions, α-synuclein can assume conformations rich in either α-helix or β-sheets. The mechanisms of α-synuclein misfolding, aggregation, and fibrillation remain unknown, but it is thought that β-sheet conformation of α-synuclein is responsible for its associated toxic mechanisms. To gain fundamental insights into the process of α-synuclein misfolding and aggregation, the secondary structure of this protein in the presence of charged and non-charged surfactant solutions was characterized. The selected surfactants were (anionic) sodium dodecyl sulphate (SDS), (cationic) cetyltrimethylammonium chloride (CTAC), and (uncharged) octyl β-D-glucopyranoside (OG). The effect of surfactants in α-synuclein misfolding was assessed by ultra-structural analyses, in vitro aggregation assays, and secondary structure analyses. The α-synuclein aggregation in the presence of negatively charged SDS suggests that SDS-monomer complexes stimulate the aggregation process. A reduction in the electrostatic repulsion between N- and C-terminal and in the hydrophobic interactions between the NAC (non-amyloid beta component) region and the C-terminal seems to be important to undergo aggregation. Fourier transform infrared spectroscopy (FTIR) measurements show that β-sheet structures comprise the assembly of the fibrils.     

Synthesis and Biological Activity of New Brassinosteroid Analogs of Type 24-Nor-5β-Cholane and 23-Benzoate Function in the Side Chain

Brassinosteroids are polyhydroxysteroids that are involved in different plants’ biological functions, such as growth, development and resistance to biotic and external stresses. Because of its low abundance in plants, much effort has been dedicated to the synthesis and characterization of brassinosteroids analogs. Herein, we report the synthesis of brassinosteroid 24-nor-5β-cholane type analogs with 23-benzoate function and 22,23-benzoate groups. The synthesis was accomplished with high reaction yields in a four-step synthesis route and using hyodeoxycholic acid as starting material. All synthesized analogs were tested using the rice lamina inclination test to assess their growth-promoting activity and compare it with those obtained for brassinolide, which was used as a positive control. The results indicate that the diasteroisomeric mixture of monobenzoylated derivatives exhibit the highest activity at the lowest tested concentrations (1 × 10⁻⁸ and 1 × 10⁻⁷ M), being even more active than brassinolide. Therefore, a simple synthetic procedure with high reaction yields that use a very accessible starting material provides brassinosteroid synthetic analogs with promising effects on plant growth. This exploratory study suggests that brassinosteroid analogs with similar chemical structures could be a good alternative to natural brassinosteroids.     

Liquid Metal Based Island‐Bridge Architectures for All Printed Stretchable Electrochemical Devices

The adoption of epidermal electronics into everyday life requires new design and fabrication paradigms, transitioning away from traditional rigid, bulky electronics towards soft devices that adapt with high intimacy to the human body. Here, a new strategy is reported for fabricating achieving highly stretchable “island‐bridge” (IB) electrochemical devices based on thick‐film printing process involving merging the deterministic IB architecture with stress‐enduring composite silver (Ag) inks based on eutectic gallium‐indium particles (EGaInPs) as dynamic electrical anchors within the inside the percolated network. The fabrication of free‐standing soft Ag‐EGaInPs‐based serpentine “bridges” enables the printed microstructures to maintain mechanical and electrical properties under an extreme (≈800%) strain. Coupling these highly stretchable “bridges” with rigid multifunctional “island” electrodes allows the realization of electrochemical devices that can sustain high mechanical deformation while displaying an extremely attractive and stable electrochemical performance. The advantages and practical utility of the new printed Ag‐liquid metal‐based island‐bridge designs are discussed and illustrated using a wearable biofuel cell. Such new scalable and tunable fabrication strategy will allow to incorporate a wide range of materials into a single device towards a wide range of applications in wearable electronics.     

Influence of training system on chromatic characteristics and phenolic composition in red wines

Chromatic characteristics and phenolic composition of red wines elaborated from Sousón and Brancellao grapes (Vitis vinifera L.), whose vines were trained in cordon and Guyot systems, were determined. This comparison was possible because there were no significant differences between yields for each one. Hue was the only significantly different chromatic parameter for both training systems and cultivars. In Sousón cultivar, saturation, colour intensity and red percentage were greater for Guyot system. Sousón cultivar trained in Guyot system and Brancellao cultivar trained in cordon system were characterized by higher total anthocyanin concentration. However, greater ionization index and flavanols reagent with dimethyl aminocinemaldehyde were associated with Guyot and cordon systems, respectively, independently on cultivar. Furthermore, gentisic acid, as well as malvidin-3-glucoside, petunidin-3-acetylglucoside and malvidin-3-caffeoylglucoside in less extension, permitted to differentiate training systems in both Sousón and Brancellao cultivars. Principal component analysis was also performed for a better understanding of the differences found.