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71.
Naomi M. Pacalin Lorraine Leon Matthew Tirrell 《The European physical journal. Special topics》2016,225(8-9):1805-1815
Polyelectrolyte complexes (PECs) have a broad range of promising applications as soft materials due to their self-assembly and diversity of structure and chemical composition. Peptide polymer PECs are highly biocompatible and biodegradable, making them particularly useful for encapsulation of food additives and flavors, micellar drug delivery, medical and underwater adhesives, fetal membrane patches, and scaffolds for cell growth in tissue engineering. While parameters affecting PEC formation and stability in regards to charge effects are well researched, little is known about the effects of van der Waals interactions, hydrogen bonding, and secondary structure in these materials. Peptide chirality provides a unique opportunity to manipulate PEC phase to modulate the amount of solid-like (precipitate) or liquid-like (coacervate) character by influencing hydrogen bonding interactions among peptide chains. In previous work, we showed that chiral peptides form solid complexes, while complexes with even one racemic peptide were fluid. This raised the interesting question of how long a homochiral sequence must be to result in solid phase formation. In this work, we designed chiral patterned peptides of polyglutamic acid and polylysine ranging from 50 to 90% L-chiral residues with increasing numbers of sequential L-chiral residues before a chirality change. These polymers were mixed together to form PECs. We observed that 8 or more sequential L-chiral residues are necessary to achieve both the appearance of a precipitate phase and sustained β-sheets in the complex, as determined by optical imaging and FTIR Spectroscopy. Less homochiral content results in formation of a coacervate phase. Thus, we show that chiral sequence can be used to control the phase transition of PECs. Understanding how to manipulate PEC phase using chiral sequence as presented here may enable tuning of the material properties to achieve the desired mechanical strength for coatings and polymer brushes, or the most effective molecular release kinetics for drug delivery applications, for example. 相似文献
72.
Ozma J. D’Souza Ronald J. Mascarenhas Ashis K. Satpati Lorraine V. Aiman Zineb Mekhalif 《Ionics》2016,22(3):405-414
The electrocatalytic oxidation of l-tyrosine (Tyr) was investigated on a carboxylic acid functionalised multi-walled carbon nanotubes modified carbon paste electrode using cyclic voltammetry and amperometry. The surface morphology of the electrodes was studied using field emission (FE)-SEM images, and the interface properties of bare and modified electrodes were investigated by electrochemical impedance spectroscopy (EIS). The influence of the amount of modifier loading and the variation of the pH of the solution on the electrochemical parameters have been investigated. Cyclic voltammetry was carried out to study the electrochemical oxidation mechanism of Tyr, which showed an irreversible oxidation process at a potential of 637.0 mV at modified electrode. The anodic peak current linearly increased with the scan rate, suggesting that the oxidation of Tyr at modified electrode is an adsorption-controlled process. A good linear relationship between the oxidation peak current and the Tyr concentration in the range of 0.8–100.0 μM was obtained in a phosphate buffer solution at pH 7.0 with a detection limit of 14.0?±?1.36 nM (S/N?=?3). The practical utility of the sensor was demonstrated by determining Tyr in spiked cow’s milk and human blood serum. The modified electrode showed excellent reproducibility, long-term stability and antifouling effects. 相似文献
73.
Daniel Duvinage Dr. Lorraine A. Malaspina PD Dr. Simon Grabowsky Dr. Stefan Mebs Prof. Dr. Jens Beckmann 《欧洲无机化学杂志》2023,26(1):e202200482
In a combined experimental and computational study, the molecular and electronic structures of the divalent bis(m-terphenyl)element cations [(2,6-Mes2C6H3)2E]+ of group 13 ( 1 , E=B; 2 , E=Al; 3 , E=Ga; 4 , E=In; 5 , E=Tl) were investigated. The preparation and characterization of 2 , 3 and 5 were previously reported by Wehmschulte's (Organometallics 2004 , 23, 1965–1967; J. Am. Chem. Soc. 2003 , 125, 1470–1471) and our groups (Organometallics 2009 , 28, 6893–6901). The indinium ion 4 was prepared and fully characterized for the first time. Attempts to prepare the borinium ion 1 by fluoride or hydride abstraction were unsuccessful. The electronic structures of 1 – 5 and the stabilization by the bulky m-terphenyl substituents were analyzed using quantum chemical calculations and compared to the divalent bis(m-terphenyl)pnictogenium ions [(2,6-Mes2C6H3)2E]+ of group 15 ( 6 , E=P; 7 , E=As; 8 , E=Sb; 9 , E=Bi) previously investigated by our group (Angew. Chem. Int. Ed. 2018 , 57, 10080–10084). The calculated fluoride ion affinities (FIA) of 1–9 are higher than that of SbF5, which classifies them as Lewis superacids. 相似文献
74.
Sylvie Pailloux Iris Binyamin Lorraine M. Deck Benjamin P. Hay Eileen N. Duesler Lev N. Zakharov W. Scott Kassel Arnold L. Rheingold Robert T. Paine 《Polyhedron》2009,28(18):3979-3984
The lanthanide coordination chemistry of the new ligand 2-hydroxy-2-(1-oxy-pyridin-2-yl)-N,N-diphenyl acetamide (5) has been examined. X-ray crystal structure determinations for the free ligand 5 and for one complex, [La(5)6] (NO3)3·7H2O, have been completed and the latter reveals an unexpected bidentate chelation mode for 5 that involves the amide carbonyl oxygen atom and the 2-hydroxy oxygen atom of each ligand. The six bidentate ligands generate an icosohedral inner coordination sphere. The N-oxide oxygen atom of each ligand also hydrogen bonds with a 2-hydroxyl hydrogen atom in a neighboring ligand molecule in the same molecular unit. 相似文献
75.
Jiajun Wang Rmi Terrasse Jayesh Arun Bafna Lorraine Benier Mathias Winterhalter 《Angewandte Chemie (International ed. in English)》2020,59(22):8517-8521
Multi‐drug resistance in Gram‐negative bacteria is often associated with low permeability of the outer membrane. To investigate the role of membrane channels in the uptake of antibiotics, we present an approach using fusion of native outer membrane vesicles (OMVs) into a planar lipid bilayer, allowing characterization of membrane protein channels in their native environment. Two major membrane channels from E. coli, OmpF and OmpC, were overexpressed from the host and the corresponding OMVs were collected. Each OMV fusion surprisingly revealed only single or few channel activities. The asymmetry of the OMVs translates after fusion into the lipid membrane with the lipopolysaccharides (LPS) dominantly present at the side of OMV addition. Compared to the conventional reconstitution method, the channels fused from OMVs containing LPS have similar conductance but a much broader distribution and significantly lower permeation. We suggest using outer membrane vesicles for functional and structural studies of membrane channels in the native membrane. 相似文献
76.
James A. Brannigan Guy G. Dodson Sarah H. Done Lorraine Hewitt Colin E. McVey Keith S. Wilson 《Applied biochemistry and biotechnology》2000,88(1-3):313-319
Penicillin acylases are used in the pharmaceutical industry for the preparation of antibiotics. The 3-D structure of Penicillin
Gacylase from Escherichia coli has been solved. Here, we present structural data that pertain to the unanswered questions that arose from the original strucutre.
Specificity for the amide portion of substrate was probed by the structure determination of a range of complexes with substitutions
around the phenylacetyl ring of the ligand. Altered substrate specificity mutations derived from an in vivo positive selection
process have also been studied, revealing the structural consequences of mutation at position B71.
Protein processing has been analyzed by the construction of site-directed mutants, which affect this reaction with two distinct
phenotypes. Mutations that allow processing but yield inactive protein provide the structure of an ES complex with a true
substrate, with implications for the enzymatic mechanism and stereospecificity of the reaction. Mutations that preclude processing
have allowed the structure of the precursor, which includes the 54a mino acid linker region normally removed from between
the A and B chains, to be visualized. 相似文献
77.
Development of proneurogenic, neuroprotective small molecules 总被引:1,自引:0,他引:1
MacMillan KS Naidoo J Liang J Melito L Williams NS Morlock L Huntington PJ Estill SJ Longgood J Becker GL McKnight SL Pieper AA De Brabander JK Ready JM 《Journal of the American Chemical Society》2011,133(5):1428-1437
Degeneration of the hippocampus is associated with Alzheimer's disease and occurs very early in the progression of the disease. Current options for treating the cognitive symptoms associated with Alzheimer's are inadequate, giving urgency to the search for novel therapeutic strategies. Pharmacologic agents that safely enhance hippocampal neurogenesis may provide new therapeutic approaches. We discovered the first synthetic molecule, named P7C3, which protects newborn neurons from apoptotic cell death, and thus promotes neurogenesis in mice and rats in the subgranular zone of the hippocampal dentate gyrus, the site of normal neurogenesis in adult mammals. We describe the results of a medicinal chemistry campaign to optimize the potency, toxicity profile, and stability of P7C3. Systematic variation of nearly every position of the lead compound revealed elements conducive toward increases in activity and regions subject to modification. We have discovered compounds that are orally available, nontoxic, stable in mice, rats, and cell culture, and capable of penetrating the blood-brain barrier. The most potent compounds are active at nanomolar concentrations. Finally, we have identified derivatives that may facilitate mode-of-action studies through affinity chromatography or photo-cross-linking. 相似文献
78.
Brewer DD Shibuta T Francis L Kumar S Tsapatsis M 《Langmuir : the ACS journal of surfaces and colloids》2011,27(18):11660-11670
Operating conditions for the deposition of monolayer and bilayer particulate coatings from aqueous 20-nm-diameter silica dispersions are identified in the context of a drag-out operation assisted by forced convection. The dry film thickness, uniformity, and morphology are assessed within an operating window parametrized by the capillary number and silica dispersion weight fraction. Three film deposition regimes with respect to the capillary number are observed: convective film deposition at low process rates, film entrainment at moderate process rates, and a thin-film transition regime at intermediate process rates. Locally ordered particulate films of variable layering thickness, including (i) a discontinuous submonolayer or (ii) a mixed submonolayer and monolayer, (iii) a mixed monolayer and bilayer, and (iv) multilayers, are dominant under convective deposition conditions. A map of morphologies is presented within the capillary number-weight fraction operating window, where monolayer and mixed monolayer-bilayer films are demonstrated in the thin-film transition regime at an intermediate dispersion weight fraction. A complementary map of the morphologies formed by the drag-out of 110 nm silica dispersions reveals a broader applicability to this type of operability diagram. These operating maps are constructed using model silica dispersions and are therefore relevant to particulate coatings of other inorganic materials. 相似文献
79.
This study documents the vocal characteristics of an actor before and after a series of eight performances involving extended voice use. The hypothesis was that this type of extended voice use would result in symptoms of vocal abuse and that damage to the actor's voice would be evident in measures made after the performance series. Three pre-performance and three post-performance speech samples were gathered and analyzed using the CSL and Visipitch II. Measurements taken included maximum phonational range; maximum sustained phonation; fundamental frequency during reading; maximum intensity levels; sound pressure levels for soft, moderate, and loud productions of sustained /a/; and perturbation including jitter, shimmer, harmonics-to-noise ratio, and an s/z ratio. Pre- and post-performance samples of the “Rainbow passage” and sustained vowel phonation were rated by a group of blinded listeners that included professional voice trainers and speech pathologists. In addition, sample lines from the performance were played for the listeners to judge whether this technique would result in symptoms of vocal abuse. Eleven out of 12 professional voice trainers rated that this technique would result in symptoms of vocal abuse. The data revealed post-performance improvement in phonational range, maximum intensity levels, perturbation measures, and s/z ratio. Measures of maximum sustained phonation, fundamental frequency, and sound pressure levels remained stable. Videoendoscopy revealed normal function of the larynx and vocal folds. 相似文献
80.