Influence of Concentration of Thiol-Substituted Poly(dimethylsiloxane)s on the Properties, Phases, and Swelling Behaviors of Their Crosslinked Disulfides

A simple, efficient procedure has been employed to effect intra- and inter-chain crosslinking of two commercially available thiolated poly(dimethylsiloxane) copolymers (T-PDMS) with 4–6% or 13–17% of mercaptopropyl side-chains. The thiol functional groups were converted to disulfides (D-PDMS) in chloroform solutions of I2. Importantly, the conditions employed avoid over-oxidation to other types of sulfur-containing species, and the concentration of T-PDMS during the crosslinking reaction dictated the rheological properties and liquid or solid nature of the D-PDMS. The procedure for obtaining the crosslinked copolymers is simpler than other approaches in the literature used to crosslink polysiloxane backbones and to modulate their properties. By changing the concentration of T-PDMS during the treatment with I2, the degree of intra- and inter-chain crosslinking can be controlled (as assessed qualitatively by the solid or liquid nature of the products and their viscoelastic properties). For each of the T-PDMS materials, there is a concentration threshold, above which products are solids, and below which they are oils. Liquid and solid materials were characterized using 1H and 13C solution-state and 13C solid-state NMR spectroscopy, respectively. They indicate greater than 90% conversion of thiols to disulfides in the presence of excess I2. The rheological behavior of the liquid products, solvent swelling ability of solid products, and the thermal stability of the reactants and products are described. Furthermore, the solid products exhibit some of the highest swelling values reported in the literature for poly(dimethylsiloxane) (PDMS) materials. As assessed by thermal gravimetric analyses, the disulfide-crosslinked materials are more stable thermally than the corresponding thiols

Structural Characterization of the S-glycosylated Bacteriocin ASM1 from Lactobacillus plantarum

In order to protect their environmental niche, most bacteria secret antimicrobial substances designed to target specific bacterial strains that are often closely related to the producer strain. Bacteriocins, small, ribosomally synthesised antimicrobial peptides, comprise a class of such substances and can either inhibit (bacteriostatic) or kill (bactericidal) target cells. Glycocins are a class of bacteriocin that are post-translationally modified by one or more carbohydrate moieties that are either β-O-linked to either a serine or threonine and/or β-S-linked to a cysteine. The solution nuclear magnetic resonance structure (NMR) of the glycocin ASM1 (produced by Lactobacillus plantarum A-1), an orthologue of GccF, has been determined. In both structures, the disulfide bonds are essential for activity and restrict the mobility of the N-acetyl-glucosamine (GlcNAc) attached to Ser-18 (O-linked), compared to the much more flexible GlcNAc moiety on Cys-43 (S-linked). Interestingly, despite 88% sequence identity, the helical structure of ASM1 is less pronounced which appears to be consistent with the far ultra-violet circular dichroism (UV CD) spectra

Effect of transfer agent, temperature and initial monomer concentration on branching in poly(acrylic acid) : a study by 13C NMR spectroscopy and capillary electrophoresis

Branching has been investigated in poly(acrylic acid) synthesized by conventional radical polymerization with and without chain transfer agent (CTA) at different temperatures and initial monomer concentrations. The average number of branches per monomer unit (i.e. degree of branching) was quantified by solution-state 13C NMR spectroscopy. The heterogeneity of branching (dispersity of the electrophoretic mobility distributions) was measured by capillary electrophoresis in the critical conditions (CE-CC). The degree of branching (DB) increases with the reaction temperature due to a rise in the frequency of reactions leading to branches, while the heterogeneity of branching remains steady. DB is lower in polymer synthesized with CTA. This decrease is due to either the CTA quenching the mid-chain radicals or a reduction of the rate of chain transfer to polymer relative to (chain-end) propagation. No influence of initial monomer concentration on DB and on the heterogeneity of branching was observed

Microbial Mat Communities along an Oxygen Gradient in a Perennially Ice-Covered Antarctic Lake.

Lake Fryxell is a perennially ice-covered lake in the McMurdo Dry Valleys, Antarctica, with a sharp oxycline in a water column that is density stabilized by a gradient in salt concentration. Dissolved oxygen falls from 20 mg liter(-1) to undetectable over one vertical meter from 8.9- to 9.9-m depth. We provide the first description of the benthic mat community that falls within this oxygen gradient on the sloping floor of the lake, using a combination of micro- and macroscopic morphological descriptions, pigment analysis, and 16S rRNA gene bacterial community analysis. Our work focused on three macroscopic mat morphologies that were associated with different parts of the oxygen gradient: (i) "cuspate pinnacles" in the upper hyperoxic zone, which displayed complex topography and were dominated by phycoerythrin-rich cyanobacteria attributable to the genus Leptolyngbya and a diverse but sparse assemblage of pennate diatoms; (ii) a less topographically complex "ridge-pit" mat located immediately above the oxic-anoxic transition containing Leptolyngbya and an increasing abundance of diatoms; and (iii) flat prostrate mats in the upper anoxic zone, dominated by a green cyanobacterium phylogenetically identified as Phormidium pseudopriestleyi and a single diatom, Diadesmis contenta. Zonation of bacteria was by lake depth and by depth into individual mats. Deeper mats had higher abundances of bacteriochlorophylls and anoxygenic phototrophs, including Chlorobi and Chloroflexi. This suggests that microbial communities form assemblages specific to niche-like locations. Mat morphologies, underpinned by cyanobacterial and diatom composition, are the result of local habitat conditions likely defined by irradiance and oxygen and sulfide concentrations

Natural Tooth Pontic: An Instant Esthetic Option for Periodontally Compromised Teeth—A Case Series

Sudden tooth loss in the esthetic zone of the maxillary or mandibular anterior region can be due to trauma, periodontal disease, or endodontic failure. The treatment options for replacing the missing tooth can vary between removable prosthesis, tooth-supported prosthesis, and implant-supported prosthesis. Irrespective of the final treatment, the first line of management would be to provisionally restore the patient’s esthetic appearance at the earliest, while functionally stabilizing the compromised arch. Using the patient’s own natural tooth as a pontic offers the benefits of being the right size, shape, and color and provides exact repositioning in its original intraoral three-dimensional position. Additionally, using the patient’s platelet concentrate (platelet rich fibrin) facilitates early wound healing and preservation of alveolar ridge shape following tooth extraction. The abutment teeth can also be preserved with minimal or no preparation, thus keeping the technique reversible, and can be completed at the chair side thereby avoiding laboratory costs. This helps the patient better tolerate the effect of tooth loss psychologically. The article describes a successful, immediate, and viable technique for rehabilitation of three different patients requiring replacement of a single periodontally compromised tooth in an esthetic region