Biopolymer Skeleton Produced by Rhizobium radiobacter: Stoichiometric Alternation of Glycosidic and Amidic Bonds in the Lipopolysaccharide O‐Antigen

The lipopolysaccharide (LPS) O‐antigen structure of the plant pathogen Rhizobium radiobacter strain TT9 and its possible role in a plant‐microbe interaction was investigated. The analyses disclosed the presence of two O‐antigens, named Poly1 and Poly2. The repetitive unit of Poly2 constitutes a 4‐α‐l ‐rhamnose linked to a 3‐α‐d ‐fucose residue. Surprisingly, Poly1 turned out to be a novel type of biopolymer in which the repeating unit is formed by a monosaccharide and an amino‐acid derivative, so that the polymer has alternating glycosidic and amidic bonds joining the two units: 4‐amino‐4‐deoxy‐3‐O‐methyl‐d ‐fucose and (2′R,3′R,4′S)‐N‐methyl‐3′,4′‐dihydroxy‐3′‐methyl‐5′‐oxoproline). Differently from the O‐antigens of LPSs from other pathogenic Gram‐negative bacteria, these two O‐antigens do not activate the oxidative burst, an early innate immune response in the model plant Arabidopsis thaliana, explaining at least in part the ability of this R. radiobacter strain to avoid host defenses during a plant infection process.     

New convolutions and their applicability to integral equations of Wiener-Hopf plus Hankel type

We propose four new convolutions exhibiting convenient factorization properties associated with two finite interval integral transformations of Fourier-type together with their norm inequalities. Moreover, we study the solvability of a class of integral equations of Wiener-Hopf plus Hankel type (on finite intervals) with the help of the factorization identities of such convolutions. Fourier-type series are used to produce the solution formula of such equations, and a Shannon-type sampling formula is also obtained.     

New Polyurethane/Docosane Microcapsules as Phase‐Change Materials for Thermal Energy Storage

Polyurethane microcapsules were prepared by mini‐emulsion interfacial polymerization for encapsulation of phase‐change material (n‐docosane) for energy storage. Three steps were followed with the aim to optimize synthesis conditions of the microcapsules. First, polyurethane microcapsules based on silicone oil core as an inert template with different silicone oil/poly(ethylene glycol)/4,4′‐diphenylmethane diisocyanate wt % ratio were synthesized. The surface morphology of the capsules was analyzed by scanning electronic microscopy (SEM) and the chemical nature of the shell was monitored by Fourier transform infrared spectroscopy (FT‐IR). Capsules with the silicone oil/poly(ethylene glycol)/4,4′‐diphenylmethane diisocyanate 10/20/20 wt % ratio showed the best morphological features and shell stability with average particle size about 4 μm, and were selected for the microencapsulation of the n‐docosane. In the second stage, half of the composition of silicone oil was replaced with n‐docosane and, finally, the whole silicone oil content was replaced with docosane following the same synthetic procedure used for silicone oil containing capsules. Thermal and cycling stability of the capsules were investigated by thermal gravimetric analysis (TGA) and the phase‐change behavior was evaluated by differential scanning calorimetry (DSC).     

Regioselective Acceptorless Dehydrogenative Coupling of N‐Heterocycles toward Functionalized Quinolines,Phenanthrolines, and Indoles

A new strategy has been developed for the oxidant‐ and base‐free dehydrogenative coupling of N‐heterocycles at mild conditions. Under the action of an iridium catalyst, N‐heterocycles undergo multiple sp³ C? H activation steps, generating a nucleophilic enamine that reacts in situ with various electrophiles to give highly functionalized products. The dehydrogenative coupling can be cascaded with Friedel–Crafts addition, resulting in a double functionalization of the N‐heterocycles.     

Reactivity with Amines of Bis(cyanamide) and Bis(cyanoguanidine) Complexes of the Iron Triad

Treatment of bis(cyanamide) [M(N≡CNEt₂)₂L₄](BPh₄)₂ and bis(cyanoguanidine) [M{N≡CN(H)C(NH₂)=NH}₂L₄](BPh₄)₂ complexes [M = Fe, Ru, Os; L = P(OEt)₃] with an excess of amine RNH₂ (R = nPr, iPr) affords mixed‐ligand complexes with cyanamide and amine [M(NH₂R)(N≡CNEt₂)L₄](BPh₄)₂ ( 1a – 5a ) and [M(NH₂R){N≡CN(H)C(NH₂)=NH}L₄](BPh₄)₂ ( 1b , 2b ). The complexes were characterized by spectroscopy and X‐ray crystal structure determination of [M(NH₂iPr)(N≡CNEt₂){P(OEt)₃}₄](BPh₄)₂ [M = Ru ( 3a ), Os ( 5a )].     

Scaling Up DNA Origami Lattice Assembly

The surface-assisted hierarchical assembly of DNA origami nanostructures is a promising route to fabricate regular nanoscale lattices. In this work, the scalability of this approach is explored and the formation of a homogeneous polycrystalline DNA origami lattice at the mica-electrolyte interface over a total surface area of 18.75 cm² is demonstrated. The topological analysis of more than 50 individual AFM images recorded at random locations over the sample surface showed only minuscule and random variations in the quality and order of the assembled lattice. The analysis of more than 450 fluorescence microscopy images of a quantum dot-decorated DNA origami lattice further revealed a very homogeneous surface coverage over cm² areas with only minor boundary effects at the substrate edges. At total DNA costs of € 0.12 per cm², this large-scale nanopatterning technique holds great promise for the fabrication of functional surfaces.     

Addition of Surfactants and Non-Hydrolytic Proteins and Their Influence on Enzymatic Hydrolysis of Pretreated Sugarcane Bagasse

Poly(ethylene glycol) (PEG 4000) and bovine serum albumin (BSA) were investigated with the purpose of evaluating their influence on enzymatic hydrolysis of sugarcane bagasse. Effects of these supplements were assayed for different enzymatic cocktails (Trichoderma harzianum and Penicillium funiculosum) that acted on lignocellulosic material submitted to different pretreatment methods with varying solid (25 and 100 g/L) and protein (7.5 and 20 mg/g cellulose) loadings. The highest levels of glucose release were achieved using partially delignified cellulignin as substrate, along with the T. harzianum cocktail: increases of 14 and 18 % for 25 g/L solid loadings and of 33 and 43 % for 100 g/L solid loadings were reached for BSA and PEG supplementation, respectively. Addition of these supplements could maintain hydrolysis yield even for higher solid loadings, but for higher enzymatic cocktail protein loadings, increases in glucose release were not observed. Results indicate that synergism might occur among these additives and cellulase and xylanases. The use of these supplements, besides depending on factors such as pretreatment method of sugarcane bagasse, enzymatic cocktails composition, and solid and protein loadings, may not always lead to positive effects on the hydrolysis of lignocellulosic material, making it necessary further statistical studies, according to process conditions.