scholarly journals pH-Dependent Chiral Recognition of D- and L-Arginine Derived Polyamidoamino Acids by Self-Assembled Sodium Deoxycholate

Polymers ◽  
2020 ◽  
Vol 12 (4) ◽  
pp. 900 ◽  
Author(s):  
Federica Lazzari ◽  
Bruce D. Alexander ◽  
Robert M. Dalgliesh ◽  
Jenny Alongi ◽  
Elisabetta Ranucci ◽  
...  

D- and L-arginine-based polyamidoamino acids, called D- and L-ARGO7, retain the chirality and acid/base properties of the parent α-amino acids and show pH-dependent self-structuring in water. The ability of the ARGO7 chiral isomers to selectively interact with chiral biomolecules and/or surfaces was studied by choosing sodium deoxycholate (NaDC) as a model chiral biomolecule for its ability to self-assembly into globular micelles, showing enantio-selectivity. To this purpose, mixtures of NaDC with D-, L- or D,L-ARGO7, respectively, in water were analysed by circular dichroism (CD) spectroscopy and small-angle neutron scattering (SANS) at different levels of acidity expressed in terms of pD and concentrations. Differences in the CD spectra indicated chiral discrimination for NaDC/ARGO7 mixtures in the gel phase (pD 7.30) but not in the solution phase (pD 9.06). SANS measurements confirmed large scale structural perturbation induced by this chiral discrimination in the gel phase yet no modulation of the structure in the solution phase. Together, these techniques shed light on the mechanism by which ARGO7 stereoisomers modify the morphology of NaDC micelles as a function of pH. This work demonstrates chirality-dependent interactions that drive structural evolution and phase behaviour of NaDC, opening the way for designing novel smart drug delivery systems.

2016 ◽  
Vol 7 (13) ◽  
pp. 2410-2418 ◽  
Author(s):  
Dongsook Chang ◽  
Bradley D. Olsen

Bioconjugates of a red fluorescent protein mCherry and a zwitterionic polymer (PDMAPS) are self-assembled into nanostructured materials. The concentrated solution phase behaviour is studied to elucidate the effect of high charge density along the polymer backbone.


Biomedicines ◽  
2021 ◽  
Vol 9 (3) ◽  
pp. 294
Author(s):  
Raffaele Pugliese ◽  
Anna Arnoldi ◽  
Carmen Lammi

Naturally occurring food peptides are frequently used in the life sciences due to their beneficial effects through their impact on specific biochemical pathways. Furthermore, they are often leveraged for applications in areas as diverse as bioengineering, medicine, agriculture, and even fashion. However, progress toward understanding their self-assembling properties as functional materials are often hindered by their long aromatic and charged residue-enriched sequences encrypted in the parent protein sequence. In this study, we elucidate the nanostructure and the hierarchical self-assembly propensity of a lupin-derived peptide which belongs to the α-conglutin (11S globulin, legumin-like protein), with a straightforward N-terminal biotinylated oligoglycine tag-based methodology for controlling the nanostructures, biomechanics, and biological features. Extensive characterization was performed via Circular Dichroism (CD) spectroscopy, Fourier Transform Infrared spectroscopy (FT-IR), rheological measurements, and Atomic Force Microscopy (AFM) analyses. By using the biotin tag, we obtained a thixotropic lupin-derived peptide hydrogel (named BT13) with tunable mechanical properties (from 2 to 11 kPa), without impairing its spontaneous formation of β-sheet secondary structures. Lastly, we demonstrated that this hydrogel has antioxidant activity. Altogether, our findings address multiple challenges associated with the development of naturally occurring food peptide-based hydrogels, offering a new tool to both fine tune the mechanical properties and tailor the antioxidant activities, providing new research directions across food chemistry, biochemistry, and bioengineering.


Author(s):  
Zhengting Zhang ◽  
Guiyun Yi ◽  
Xiaodong Wang ◽  
Peng Li ◽  
Zhuoyan Wan ◽  
...  

Soft Matter ◽  
2021 ◽  
Vol 17 (11) ◽  
pp. 3096-3104
Author(s):  
Valeria Castelletto ◽  
Jani Seitsonen ◽  
Janne Ruokolainen ◽  
Ian W. Hamley

A designed surfactant-like peptide is shown, using a combination of cryogenic-transmission electron microscopy and small-angle X-ray scattering, to have remarkable pH-dependent self-assembly properties.


Polymers ◽  
2021 ◽  
Vol 13 (7) ◽  
pp. 1094
Author(s):  
Bastian Klose ◽  
Daniel Kremer ◽  
Merve Aksit ◽  
Kasper P. van der Zwan ◽  
Klaus Kreger ◽  
...  

Polystyrene foams have become more and more important owing to their lightweight potential and their insulation properties. Progress in this field is expected to be realized by foams featuring a microcellular morphology. However, large-scale processing of low-density foams with a closed-cell structure and volume expansion ratio of larger than 10, exhibiting a homogenous morphology with a mean cell size of approximately 10 µm, remains challenging. Here, we report on a series of 4,4′-diphenylmethane substituted bisamides, which we refer to as kinked bisamides, acting as efficient supramolecular foam cell nucleating agents for polystyrene. Self-assembly experiments from solution showed that these bisamides form supramolecular fibrillary or ribbon-like nanoobjects. These kinked bisamides can be dissolved at elevated temperatures in a large concentration range, forming dispersed nano-objects upon cooling. Batch foaming experiments using 1.0 wt.% of a selected kinked bisamide revealed that the mean cell size can be as low as 3.5 µm. To demonstrate the applicability of kinked bisamides in a high-throughput continuous foam process, we performed foam extrusion. Using 0.5 wt.% of a kinked bisamide yielded polymer foams with a foam density of 71 kg/m3 and a homogeneous microcellular morphology with cell sizes of ≈10 µm, which is two orders of magnitude lower compared to the neat polystyrene reference foam with a comparable foam density.


2018 ◽  
Vol 146 (12) ◽  
pp. 4279-4302 ◽  
Author(s):  
Alex M. Kowaleski ◽  
Jenni L. Evans

Abstract An ensemble of 72 Weather Research and Forecasting (WRF) Model simulations is evaluated to examine the relationship between the track of Hurricane Sandy (2012) and its structural evolution. Initial and boundary conditions are obtained from ECMWF and GEFS ensemble forecasts initialized at 0000 UTC 25 October. The 5-day WRF simulations are initialized at 0000 UTC 27 October, 48 h into the global model forecasts. Tracks and cyclone phase space (CPS) paths from the 72 simulations are partitioned into 6 clusters using regression mixture models; results from the 4 most populous track clusters are examined. The four analyzed clusters vary in mean landfall location from southern New Jersey to Maine. Extratropical transition timing is the clearest difference among clusters; more eastward clusters show later Sandy–midlatitude trough interaction, warm seclusion formation, and extratropical transition completion. However, the intercluster variability is much smaller when examined relative to the landfall time of each simulation. In each cluster, a short-lived warm seclusion forms and contracts through landfall while lower-tropospheric potential vorticity concentrates at small radii. Despite the large-scale similarity among the clusters, relevant intercluster differences in landfall-relative extratropical transition are observed. In the easternmost cluster the Sandy–trough interaction is least intense and the warm seclusion decays the most by landfall. In the second most eastward cluster Sandy retains the most intact warm seclusion at landfall because of a slightly later (relative to landfall) and weaker trough interaction compared to the two most westward clusters. Nevertheless, the remarkably similar large-scale evolution of Sandy among the four clusters indicates the high predictability of Sandy’s warm seclusion extratropical transition before landfall.


Polyhedron ◽  
2008 ◽  
Vol 27 (12) ◽  
pp. 2672-2680 ◽  
Author(s):  
Zhao-Peng Qi ◽  
Zheng-Shuai Bai ◽  
Qing Yuan ◽  
Taka-aki Okamura ◽  
Kai Cai ◽  
...  

1999 ◽  
Vol 28 (11) ◽  
pp. 1221-1222 ◽  
Author(s):  
Akio Kishida ◽  
Fusako Seto ◽  
Ken-ichiro Hiwatari ◽  
Takeshi Serizawa ◽  
Youichiro Muraoka ◽  
...  

2005 ◽  
Vol 4 (1) ◽  
pp. 81-91 ◽  
Author(s):  
Martin Nilsson Jacobi ◽  
Steen Rasmussen ◽  
Kolbjørn Tunstrøm

This paper is a discussion on how reaction kinetics and three-dimensional (3D) lattice simulations can be used to elucidate the dynamical properties of micelles as a possible minimal protocell container. We start with a general discussion on the role of molecular self-assembly in prebiotic and contemporary biological systems. A simple reaction kinetic model of a micellation process of amphiphilic molecules in water is then presented and solved analytically. Amphiphilic molecules are polymers with hydrophobic (water-fearing), e.g. hydrocarbon tail groups, and hydrophilic (water-loving) head groups, e.g. fatty acids. By making a few simplifying assumptions an analytical expression for the size distribution of the resulting micelles can be derived. The main part of the paper presents and discusses a lattice gas technique for a more detailed 3D simulation of molecular self-assembly of amphiphilic polymers in aqueous environments. Water molecules, hydrocarbon tail groups and hydrophilic head groups are explicitly represented on a three-dimensional discrete lattice. Molecules move on the lattice proportional to their continuous momentum. Collision rules preserve momentum and kinetic energy. Potential energy from molecular interactions are also included explicitly. The non-trivial thermodynamics of large-scale and long-time dynamics are studied. In this paper we specifically demonstrate how, from a random initial distribution, micelles are formed and grow until they destabilize and can divide. Eventually a steady state of growing and dividing micelles is formed. Towards the end of the paper we discuss the relevance of the presented results to the design of a minimal artificial protocell.


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