The Compressibility of pH‐Sensitive Microgels at the Oil–Water Interface: Higher Charge Leads to Less Repulsion

pH‐responsive microgels are unique stabilizers for stimuli‐sensitive emulsions that can be broken on demand by changing the pH value. However, recent experiments have indicated that electrostatic interactions play a different role to that in conventional Pickering emulsions. The influence of charges on the interactions between microgels at the oil–water interface is now described. Compression isotherms of microgels with different charge density and architecture were determined in a Langmuir trough, and counter‐intuitive results were obtained: Charged microgels can be compressed more easily than uncharged microgels. The compressibility of microgels is thus not determined by direct Coulomb repulsion. Instead, the different swelling of the microgels in the charged and the uncharged states is proposed to be the key parameter.     

Surface Design for Immobilization of an Antimicrobial Peptide Mimic for Efficient Anti-Biofouling

Microbial surface attachment negatively impacts a wide range of devices from water purification membranes to biomedical implants. Mimics of antimicrobial peptides (AMPs) constituted from poly(N-substituted glycine) „peptoids“ are of great interest as they resist proteolysis and can inhibit a wide spectrum of microbes. We investigate how terminal modification of a peptoid AMP-mimic and its surface immobilization affect antimicrobial activity. We also demonstrate a convenient surface modification strategy for enabling alkyne–azide „click“ coupling on amino-functionalized surfaces. Our results verified that the N- and C-terminal peptoid structures are not required for antimicrobial activity. Moreover, our peptoid immobilization density and choice of PEG tether resulted in a „volumetric“ spatial separation between AMPs that, compared to past studies, enabled the highest AMP surface activity relative to bacterial attachment. Our analysis suggests the importance of spatial flexibility for membrane activity and that AMP separation may be a controlling parameter for optimizing surface anti-biofouling.     

Direct Visualization of a Mechanochemically Induced Molecular Rearrangement

Recent progress in the field of mechanochemistry has expanded the discovery of mechanically induced chemical transformations to several areas of science. However, a general fundamental understanding of how mechanochemical reactions by ball milling occur has remained unreached. For this, we have now implemented in situ monitoring of a mechanochemically induced molecular rearrangement by synchrotron X‐ray powder diffraction, Raman spectroscopy, and real‐time temperature sensing. The results of this study demonstrate that molecular rearrangements can be accomplished in the solid state by ball milling and how in situ monitoring techniques enable the visualization of changes occurring at the exact instant of a molecular migration. The mechanochemical benzil–benzilic acid rearrangement is the focal point of the study.     

Membrane Proteins Have Distinct Fast Internal Motion and Residual Conformational Entropy

The internal motions of integral membrane proteins have largely eluded comprehensive experimental characterization. Here the fast side‐chain dynamics of the α‐helical sensory rhodopsin II and the β‐barrel outer membrane protein W have been investigated in lipid bilayers and detergent micelles by solution NMR relaxation techniques. Despite their differing topologies, both proteins have a similar distribution of methyl‐bearing side‐chain motion that is largely independent of membrane mimetic. The methyl‐bearing side chains of both proteins are, on average, more dynamic in the ps–ns timescale than any soluble protein characterized to date. Accordingly, both proteins retain an extraordinary residual conformational entropy in the folded state, which provides a counterbalance to the absence of the hydrophobic effect. Furthermore, the high conformational entropy could greatly influence the thermodynamics underlying membrane‐protein functions, including ligand binding, allostery, and signaling.     

Hard domain compression of triblock-copolymer gels by high pressure X-ray small-angle scattering

Small-angle X-ray scattering using synchrotron radiation at pressures up to 700 MPa has been performed on triblock-copolymer gels, polystyrene-rubber-polystyrene with poly(ethylene/butylene) as the rubber mid-blocks. A 2-stage pressure behaviour could be verified by comparison of the experimental data with the Tait-equation and a model of pressure screening.     

“Butterfly”-like patterns of triblock copolymer gels as observed by small-angle neutron scattering

At high (150-1000%) stretching of a physical gel of a triblock copolymer a “butterfly”-type scattering pattern is observed with a pronounced scattering-free strip perpendicular to the stretching direction. The phenomenon is attributed to the cluster character of the physical network in the gel. Stretching brings endblock domains (junction points of the network) closer to each other in the direction perpendicular to the stretching and leads to formation of a layered structure. High connectivity of the network inside the clusters leads to saturation of the deformation within the clusters as manifested by the scattering-free region in the SANS pattern. © 1996 John Wiley & Sons, Inc.     

Phenolic Acids and Flavonoids in Acetonic Extract from Quince (Cydonia oblonga Mill.): Nutraceuticals with Antioxidant and Anti-Inflammatory Potential

Quince (Cydonia oblonga Mill.) is a potential source of polyphenolic compounds related with beneficial biological processes. In this study polyphenols from quince fruit were extracted with aqueous acetone at different ratios. A polyphenol profile was identified and quantified by LC-ESI-QqQ. The antioxidant capacity (ORAC and DPPH) and anti-inflammatory effect (inhibition of COX-2 cyclooxygenase) were evaluated in vitro. The results indicated an effect of the aqueous acetone ratio on the extraction of polyphenolic compounds. The higher extraction yields of polyphenolic compounds were attained with 60–75% aqueous acetone. However, extracts obtained with 85% aqueous acetone promoted higher antioxidant and anti-inflammatory effects. Optimal scaling analysis indicated that hydroxycinnamic acids (quinic and chlorogenic), hydroxybenzoic acids (vanillic and syringic), flavonoids (quercetin and kaempferol), dihydrochalcones (neohesperidin) and flavones (acacetin) are related to the antioxidant activity of quince. While phenolic acids, flavonols (kaempferol-3-O-glucoside and rutin) and flavanols (epicatechin) generated the anti-inflammatory effect by inhibiting 52.3% of the COX-2 enzyme. Therefore, a selective extraction of phenolic mix can reduce oxidative stress or inflammatory processes. This suggests the use of quince as a natural source with significant nutraceutical potential.     

Polymicrobial Biofilm Inhibition Effects of Acetate‐Buffered Chitosan Sponge Delivery Device

Polymicrobial biofilm‐associated implant infections present a challenging clinical problem. Through modifications of lyophilized chitosan sponges, degradable drug delivery devices for antibiotic solution have been fabricated for prevention and treatment of contaminated musculoskeletal wounds. Elution of amikacin, vancomycin, or a combination of both follows a burst release pattern with vancomycin released above minimum inhibitory concentration for Staphylococcus aureus for 72 h and amikacin released above inhibitory concentrations for Pseudomonas aeruginosa for 3 h. Delivery of a vancomycin, amikacin, or a combination of both reduces biofilm formation on polytetrafluoroethylene catheters in an in vivo model of contamination. Release of dual antibiotics from sponges is more effective at preventing biofilm formation than single‐loaded chitosan sponges. Treatment of pre‐formed biofilm with high‐dose antibiotic release from chitosan sponges shows minimal reduction after 48 h. These results demonstrate infection‐preventive efficacy for antibiotic‐loaded sponges, as well as the need for modifications in the development of advanced materials to enhance treatment efficacy in removing established biofilm.

     

Observation of noncovalent complexes to the avidin tetramer by electrospray ionization mass spectrometry

Intact avidin-biotin and avidin-biotin maleimide noncovalent complexes have been observed by electrospray ionization mass spectrometry (ESI-MS) by using an extended mass range quadrupole mass spectrometer. By utilizing mild ES1 interface conditions, the expected solution behavior of four biotin or biotin maleimide molecules noncovalently binding to each avidin tetramer can be preserved in the gas phase. The ESI-MS results show the appropriate mass additions of 973 ± 60 Da for biotin and 1802 ± 40 Da for biotin maleimide to the avidin tetramer species. These results support the hypothesis that substantial retention of higher order structure is possible in the gas phase by using gentle ESI conditions.