Worm-globule transition of amphiphilic pH-responsive heterografted bottlebrushes at air-water interface.

Heterografted molecular bottlebrushes (MBBs) with side chains composed of poly(n-butyl acrylate) (PnBA) and pH-responsive poly(2-(N,N-diethylamino)ethyl methacrylate) (PDEAEMA, pKa = 7.4) have been shown to be efficient, robust, and responsive emulsifiers. However, it remains unknown how they respond to external stimuli at interfaces. In this work, the shape-changing behavior of six hetero- and homografted MBBs at air-water interfaces in response to pH changes and lateral compression was investigated using a Langmuir-Blodgett trough and atomic force microscopy. At a surface pressure of 0.5 mN m-1, PDEAEMA-containing MBBs showed no worm-globule transitions when the pH was increased from 4.0 to 10.0, at which PDEAEMA becomes insoluble in water. Upon lateral compression at pH 4.0, MBBs with a mole fraction of PDEAEMA side chains (xPDEAEMA) < 0.50 underwent pronounced worm-globule shape transitions; there was an increasing tendency for bottlebrushes to become connected with increasing xPDEAEMA. At xPDEAEMA = 0.76, the molecules remained wormlike even at high compression. These observations were presumably caused by the increased electrostatic repulsion between protonated PDEAEMA side chains in the subphase with increasing xPDEAEMA, hindering the shape change. At pH 10.0, MBBs with xPDEAEMA < 0.50 showed a lower tendency to change their wormlike morphologies upon compression than at pH 4.0. No shape transition was observed when xPDEAEMA > 0.50, attributed to the relatively high affinity toward water and the rigidity of PDEAEMA. This study revealed the shape-changing behavior of amphiphilic pH-responsive MBBs at air-water interfaces, which could be useful for future design of multicomponent MBBs for potential applications.

Amphiphilic Heterografted Molecular Bottlebrushes with Tertiary Amine-Containing Side Chains as Efficient and Robust pH-Responsive Emulsifiers.

By combining the unique characteristics of molecular bottlebrushes (MBBs) and the properties of stimuli-responsive polymers, we show that MBBs with randomly grafted poly(n-butyl acrylate) and pH-responsive poly(2-(N,N-diethylamino)ethyl methacrylate) (PDEAEMA) side chains are efficient and robust pH-responsive emulsifiers. Water-in-toluene emulsions were formed at pH 4.0 and disrupted by increasing the pH to 10.0. The emulsion generation and disruption was reversible over the ten cycles investigated, and the bottlebrushes remained intact. The exceptional emulsion stability stemmed from the high interfacial binding energy of MBBs, imparted by their large molecular size and Janus architecture at the interface, as evidenced by the interfacial jamming and wrinkling of the assemblies upon reducing the interfacial area. At pH 10.0, PDEAEMA became water-insoluble, and the MBBs desorbed from the interface, causing de-emulsification. Consequently, we have shown that the judicious design of MBBs can generate properties of particle emulsifiers from their large size, while the responsiveness of the MBBs enables more potential applications.

Adaptable Multivalent Hairy Inorganic Nanoparticles.

We report a polymer brush-based approach for fabricating multivalent patchy nanoparticles (NPs) with the number of nanodomains (valency) from 6 to 10, potentially from 1 to 10, by exploiting the lateral microphase separation of binary mixed homopolymer brushes grafted on NPs with a radius comparable to the polymer sizes. Well-defined mixed brushes were grown on 20.4 nm silica NPs by two-step surface-initiated reversible deactivation radical polymerizations and microphase separated laterally upon casting from a good solvent, producing multivalent NPs on 2D surfaces. A linear relationship between valency and average core size for the corresponding valency was observed. The mixed brush NPs exhibited abilities to form "bonds" through the overlap of nanodomains and to change the valency when interacting with adjacent NPs. This method could open up a new avenue for studying patchy NPs.

Effects of temperature on chaotropic anion-induced shape transitions of star molecular bottlebrushes with heterografted poly(ethylene oxide) and poly(N,N-dialkylaminoethyl methacrylate) side chains in acidic water.

This article reports a study of the effects of temperature on chaotropic anion (CA)-induced star-globule shape transitions in acidic water of three-arm star bottlebrushes composed of heterografted poly(ethylene oxide) (PEO) and either poly(2-(N,N-dimethylamino)ethyl methacrylate) (PDMAEMA) or poly(2-(N,N-diethylamino)ethyl methacrylate) (PDEAEMA) (the brushes denoted as SMB-11 and -22, respectively). The brush polymers were synthesized by grafting alkyne-end-functionalized PEO and PDMAEMA or PDEAEMA onto an azide-bearing three-arm star backbone polymer using the copper(i)-catalyzed alkyne-azide cycloaddition reaction. Six anions were studied for their effects on the conformations of SMB-11 and -22 in acidic water: super CAs [Fe(CN)6]3- and [Fe(CN)6]4-, moderate CAs PF6- and ClO4-, weak CA I-, and for comparison, kosmotropic anion SO42-. At 25 °C, the addition of super and moderate CAs induced shape transitions of SMB-11 and -22 in pH 4.50 water from a starlike to a collapsed globular state stabilized by PEO side chains, which was driven by the ion pairing of protonated tertiary amine groups with CAs and the chaotropic effect. The shape changes occurred at much lower salt concentrations for super CAs than moderate CAs. Upon heating from near room temperature to 70 °C, the super CA-collapsed brushes remained in the globular state, whereas the moderate CA-collapsed brushes underwent reversible globule-to-star shape transitions. The transition temperature increased with increasing salt concentration and was found to be higher for SMB-22 at the same salt concentration, presumably caused by the chaotropic effect. In contrast, I- and SO42- had small effects on the conformations of SMB-11 and -22 at 25 °C in the studied salt concentration range, and only small and gradual size variations were observed upon heating to 70 °C. The results reported here may have potential uses in the design of stimuli-responsive systems for substance encapsulation and release.

Elevated troponin and jarisch-herxheimer reaction in tick-borne relapsing Fever: a case report.

We describe a patient with fever and borreliosis in the Northwestern Washington State, USA. The patient exhibited a classic Jarisch-Herxheimer reaction of tachycardia, hypotension, and thrombocytopenia following antimicrobial therapy, and she also developed an elevated serum cardiac troponin during therapy.

The Bogorol family of antibiotics: template-based structure elucidation and a new approach to positioning enantiomeric pairs of amino acids.

The sequence positions of d and l Leu and Lys residues in bogorol A (1) have been defined by a simple and novel approach that utilizes small amounts of sample and focuses on detecting the order in which amino acids are liberated from the parent peptide during acid-catalyzed hydrolysis. This technique builds on a previously established relationship between the steric and electronic features of amino acids and their predilection for acidic liberation from polypeptides via dipeptides. The results, which complete the structure of bogorol A, have been confirmed by traditional degradation experiments. Utilizing the knowledge of the structure of bogorol A (1) as a template, we rapidly elucidated the structures of bogorols B-E (2-5) via analysis of ESI-MS and ESI-MS/MS data and GC analysis of degradation products. The bogorol cationic peptide antibiotics contain a number of unusual structural features, which include the reduction of the C-terminal residue to valinol, an N-terminal residue of 2-hydroxy-3-methylpentanoic acid, the incorporation of four d amino acids, and the presence of a dehydroamino acid. Bogorols show selective and relatively potent activity against methicillin-resistant Staphylococcus aureus and vancomycin-resistant Enterococcus spp., as well as moderate activity against Escherichia coli.

Tupuseleiamides and basiliskamides, new acyldipeptides and antifungal polyketides produced in culture by a Bacillus laterosporus isolate obtained from a tropical marine habitat.

Laboratory cultures of PNG 276, a Bacillus laterosporus isolate obtained from coastal waters off Papua New Guinea, have been shown to produce the novel metabolites basiliskamide A (1), basiliskamide B (2), tupuseleiamide A (3), and tupusleiamide B (4). The structures of 1 to 4 were elucidated by analysis of spectroscopic data and chemical degradation. Basiliskamides A (1) and B (2) show potent in vitro anti-Candida activity.