Concise synthesis of di- and trisaccharides related to the O-antigens from Shigella flexneri serotypes 6 and 6a,based on late stage mono-O-acetylation and/or site-selective oxidation

Shigella flexneri serotypes 6 and 6a are closely related bacteria causing shigellosis in humans. Their O-antigens are {→4)-β-d-GalpA-(1→3)-β-d-GalpNAc-(1→2)-[3Ac/4Ac]-α-l-Rhap-(1→2)-α-l-Rhap-(1→}_n acidic polysaccharides ({AB_AcCD}_n), which only differ in the degree of O-acetylation. A concise synthesis of two disaccharides (BC, B_AcC) and four trisaccharides, representing portions and/or analogs of the O-antigens, is described. A protected intermediate compatible with late stage 3_C-O-acetylation, and/or galactosyl (A°) to galacturonic acid (A) conversion, was designed and assembled from trichloroacetimidate and thioglycoside donors tuned for high yielding glycosylation and excellent stereocontrol. The galacturonic moiety was efficiently introduced from galactose using a TEMPO/NaOCl/NaClO₂-based oxidation protocol optimized for full compatibility with sensitive moieties, such as allyl ethers and acetates. Final Pd/C-mediated deprotection provided the targets, including the propyl glycoside AB_AcC, its non O-acetylated counterpart ABC, and the non acidic analogs A°B_AcC and A°BC. The BC and ABC oligosaccharides are also portions of the O-antigen from Escherichia coli O147, which causes diarrhea in pigs.     

Janus carbosilane/phosphorhydrazone dendrimers synthesized by the ‘click’ Staudinger reaction

The first association of carbosilane dendrons (having a phosphine at the focal point) with phosphorhydrazone dendrons (having a thiophosphoryl azide at the focal point) has been successfully carried out by ‘Staudinger click’ reaction. The corresponding Janus dendrimers possess the characteristics of both components; they are oily as the carbosilane dendrons, and they can be easily functionalized as the phosphorhydrazone dendrons.     

Biodegradation study of plasticised corn flour/poly(butylene succinate-co-butylene adipate) blends

Plasticised corn flour/poly(butylene succinate-co-butylene adipate) (PBSA) materials were prepared by extrusion and injection in order to study the impact of PBSA ratio on their physicochemical properties and biodegradability. Scanning electron microscopy observations showed that corn flour and PBSA are incompatible. Three types of morphology have been observed: (i) starch dispersed in a PBSA matrix, (ii) a “co-continuous-like” morphology of starch and PBSA, and (iii) PBSA dispersed in a starch matrix. As expected, the extent of plasticised corn flour starch hydrolysis by amylolytic enzymes decreased when the amount of PBSA increased. Addition of a lipase to hydrolyse PBSA ester bonds enhanced enzymatic hydrolysis of starch by amylolytic enzymes in materials where PBSA formed a continuous phase. This suggests that PBSA formed a barrier restricting the access of amylolytic enzymes to starch. This was consistent with aerobic and anaerobic biodegradation assays, which also showed lower biodegradability of materials containing a majority of PBSA.     

Heteroleptic Tin(II) Initiators for the Ring‐Opening (Co)Polymerization of Lactide and Trimethylene Carbonate: Mechanistic Insights from Experiments and Computations

The tin(II) complexes {LO^x}Sn(X) ({LO^x}^?=aminophenolate ancillary) containing amido ( 1 – 4 ), chloro ( 5 ), or lactyl ( 6 ) coligands (X) promote the ring‐opening polymerization (ROP) of cyclic esters. Complex 6 , which models the first insertion of L ‐lactide, initiates the living ROP of L ‐LA on its own, but the amido derivatives 1 – 4 require the addition of alcohol to do so. Upon addition of one to ten equivalents of iPrOH, precatalysts 1 – 4 promote the ROP of trimethylene carbonate (TMC); yet, hardly any activity is observed if tert‐butyl (R)‐lactate is used instead of iPrOH. Strong inhibition of the reactivity of TMC is also detected for the simultaneous copolymerization of L ‐LA and TMC, or for the block copolymerization of TMC after that of L ‐LA. Experimental and computational data for the {LO^x}Sn(OR) complexes (OR=lactyl or lactidyl) replicating the active species during the tin(II)‐mediated ROP of L ‐LA demonstrate that the formation of a five‐membered chelate is largely favored over that of an eight‐membered one, and that it constitutes the resting state of the catalyst during this (co)polymerization. Comprehensive DFT calculations show that, out of the four possible monomer insertion sequences during simultaneous copolymerization of L ‐LA and TMC: 1) TMC then TMC, 2) TMC then L ‐LA, 3) L ‐LA then L ‐LA, and 4) L ‐LA then TMC, the first three are possible. By contrast, insertion of L ‐LA followed by that of TMC (i.e., insertion sequence 4) is endothermic by +1.1 kcal mol^?1, which compares unfavorably with consecutive insertions of two L ‐LA units (i.e., insertion sequence 3) (?10.2 kcal mol^?1). The copolymerization of L ‐LA and TMC thus proceeds under thermodynamic control.     

Chain-extending of Hydroxytelechelic Polybutadiene: Synthesis and Characterization

Extension of hydroxytelechelic polybutadiene oligomers ( 3200 g/mol) is performed in mild conditions, in order to avoid backbone modifications, using succinic anhydride or methylenedicyclohexyl diisocyanate. The two routes present significative extension of the initial oligomers. Extension through the anhydride route, in the presence of DCC and DMAP, leads to new hydroxytelechelic oligomers ( 8000 g/mol). Extension through the diisocyanate route, catalyzed by DBTL at 65°C leads to hydroxytelechelic oligomers of higher average molecular weight ( 20000 g/mol). New materials are characterized by FTIR/¹H-NMR and changes in their Tg according to , are discussed. The influence of reaction time on the length of the macromolecular chains is also studied.     

Differentiation of Linear and Cyclic Polymer Architectures by MALDI Tandem Mass Spectrometry (MALDI-MS2)

[M + Ag]⁺ ions from cyclic and linear polystyrenes and polybutadienes, formed by matrix-assisted laser desorption ionization (MALDI), give rise to significantly different fragmentation patterns in tandem mass spectrometry (MS²) experiments. In both cases, fragmentation starts with homolytic cleavage at the weakest bond, usually a C–C bond, to generate two radicals. From linear structures, the separated radicals depolymerize extensively by monomer losses and backbiting rearrangements, leading to low-mass radical ions and much less abundant medium- and high-mass closed-shell fragments that contain one of the original end groups, along with internal fragments. With cyclic structures, depolymerization is less efficient, as it can readily be terminated by intramolecular H-atom transfer between the still interconnected radical sites (disproportionation). These differences in fragmentation reactivity result in substantially different fragment ion distributions in the MS² spectra. Simple inspection of the relative intensities of low- versus high-mass fragments permits conclusive determination of the macromolecular architecture, while full spectral interpretation reveals the individual end groups of linear polymers or the identity of the linker used to form the cyclic polymer.

Small Changes Have Consequences: Lessons from Tetrabenzyltitanium and ‐zirconium Surface Organometallic Chemistry

Homoleptic benzyl derivatives of titanium and zirconium have been grafted onto silica that was dehydroxylated at 200 and 700 °C, thereby affording bi‐grafted and mono‐grafted single‐site species, respectively, as shown by a combination of experimental techniques (IR, MAS NMR, EXAFS, and elemental analysis) and theoretical calculations. Marked differences between these compounds and their neopentyl analogues are discussed and rationalized by using DFT. These differences were assigned to the selectivity of the grafting process, which, depending on the structure of the molecular precursors, led to different outcomes in terms of the mono‐ versus bi‐grafted species for the same surface concentration of silanol species. The benzylzirconium derivatives were active towards ethylene polymerization in the absence of an activator and the bi‐grafted species displayed higher activity than their mono‐grafted analogues. In contrast, the benzyltitanium and neopentylzirconium counterparts were not active under similar reaction conditions.     

Iα → Iβ transition of cellulose under ultrasonic radiation

Aqueous suspensions of dispersed Glaucocystis cellulose microfibrils were sonicated at 4 °C for 3 h, using 24 kHz ultrasonic waves. This treatment induced a variety of ultrastructural defects, as the microfibrils became not only shortened, but also presented substantial damage materialized by kinks and subfibrillation. Upon analysis by X-ray diffraction and ¹³C solid-state NMR spectroscopy, it was found that the initial sample that contained 90 % of cellulose I_α allomorph became, to a large extent, unexpectedly converted into the I_β phase, while the loss of crystallinity was only moderate during the sonication treatment.