scholarly journals Thermodynamic Origin of Differential Excipient-Lysozyme Interactions

2021 ◽  
Vol 8 ◽  
Author(s):  
Jas Kalayan ◽  
Robin A. Curtis ◽  
Jim Warwicker ◽  
Richard H. Henchman
Keyword(s):  
Free Energy ◽  
Sodium Chloride ◽  
Protein Therapeutics ◽  
Tris Buffer ◽  
Cross Linking ◽  
Water Molecules ◽  
Sodium Ions ◽  
Multiscale Decomposition ◽  
The Cross ◽  
Lysozyme Aggregation

Understanding the intricate interplay of interactions between proteins, excipients, ions and water is important to achieve the effective purification and stable formulation of protein therapeutics. The free energy of lysozyme interacting with two kinds of polyanionic excipients, citrate and tripolyphosphate, together with sodium chloride and TRIS-buffer, are analysed in multiple-walker metadynamics simulations to understand why tripolyphosphate causes lysozyme to precipitate but citrate does not. The resulting multiscale decomposition of energy and entropy components for water, sodium chloride, excipients and lysozyme reveals that lysozyme is more stabilised by the interaction of tripolyphosphate with basic residues. This is accompanied by more sodium ions being released into solution from tripolyphosphate than for citrate, whilst the latter instead has more water molecules released into solution. Even though lysozyme aggregation is not directly probed in this study, these different mechanisms are suspected to drive the cross-linking between lysozyme molecules with vacant basic residues, ultimately leading to precipitation.

scholarly journals Free energy landscapes of sodium ions bound to DMPC–cholesterol membrane surfaces at infinite dilution

2016 ◽  
Vol 18 (13) ◽  
pp. 9036-9041 ◽  
Author(s):  
Jing Yang ◽  
Massimiliano Bonomi ◽  
Carles Calero ◽  
Jordi Martí
Keyword(s):  
Free Energy ◽  
Infinite Dilution ◽  
Sodium Ion ◽  
Water Molecules ◽  
Sodium Ions ◽  
Energy Landscapes ◽  
Membrane Surfaces ◽  
Additional Water ◽  
Free Energy Landscapes ◽  
Typical Configuration

Typical configuration of two DMPC lipids and one cholesterol molecule solvating one sodium ion, together with two additional water molecules.

Molecular orientation of liquid aliphatic hydrocarbons on the surface and at the interface with water

1989 ◽  
Vol 54 (12) ◽  
pp. 3171-3186 ◽  
Author(s):  
Jan Kloubek
Keyword(s):  
Free Energy ◽  
Surface Free Energy ◽  
Molecular Orientation ◽  
Phase Changes ◽  
Aliphatic Hydrocarbons ◽  
Water Molecules ◽  
Free Energies ◽  
Dispersion Component ◽  
System Water ◽  
Orientation Of Molecules

The validity of the Fowkes theory for the interaction of dispersion forces at interfaces was inspected for the system water-aliphatic hydrocarbons with 5 to 16 C atoms. The obtained results lead to the conclusion that the hydrocarbon molecules cannot lie in a parallel position or be randomly arranged on the surface but that orientation of molecules increases there the ration of CH3 to CH2 groups with respect to that in the bulk. This ratio is changed at the interface with water so that the surface free energy of the hydrocarbon, γH, rises to a higher value, γ’H, which is effective in the interaction with water molecules. Not only the orientation of molecules depends on the adjoining phase and on the temperature but also the density of hydrocarbons on the surface of the liquid phase changes. It is lower than in the bulk and at the interface with water. Moreover, the volume occupied by the CH3 group increases on the surface more than that of the CH2 group. The dispersion component of the surface free energy of water, γdW = 19.09 mJ/m2, the non-dispersion component, γnW = 53.66 mJ/m2, and the surface free energies of the CH2 and CH3 groups, γ(CH2) = 32.94 mJ/m2 and γ(CH3) = 15.87 mJ/m2, were determined at 20 °C. The dependence of these values on the temperature in the range 15-40 °C was also evaluated.

scholarly journals Investigation of the functional network modifier loading on the stoichiometric ratio of epoxy resins and their dielectric properties

2021 ◽  
Author(s):  
Istebreq A. Saeedi ◽  
Sunny Chaudhary ◽  
Thomas Andritsch ◽  
Alun S. Vaughan
Keyword(s):  
Glass Transition ◽  
Dielectric Properties ◽  
Electrical Properties ◽  
Epoxy Resins ◽  
Functional Network ◽  
Cross Linking ◽  
Network Modifier ◽  
Epoxy Resin System ◽  
The Cross ◽  
The Impact

AbstractReactive molecular additives have often been employed to tailor the mechanical properties of epoxy resins. In addition, several studies have reported improved electrical properties in such systems, where the network architecture and included function groups have been modified through the use of so-called functional network modifier (FNM) molecules. The study reported here set out to investigate the effect of a glycidyl polyhedral oligomeric silsesquioxane (GPOSS) FNM on the cross-linking reactions, glass transition, breakdown strength and dielectric properties of an amine-cured epoxy resin system. Since many previous studies have considered POSS to act as an inorganic filler, a key aim was to consider the impact of GPOSS addition on the stoichiometry of curing. Fourier transform infrared spectroscopy revealed significant changes in the cross-linking reactions that occur if appropriate stoichiometric compensation is not made for the additional epoxide groups present on the GPOSS. These changes, in concert with the direct effect of the GPOSS itself, influence the glass transition temperature, dielectric breakdown behaviour and dielectric response of the system. Specifically, the work shows that the inclusion of GPOSS can result in beneficial changes in electrical properties, but that these gains are easily lost if consequential changes in the matrix polymer are not appropriately counteracted. Nevertheless, if the system is appropriately optimized, materials with pronounced improvements in technologically important characteristics can be designed.

scholarly journals The Effect of Surfactant-Modified Montmorillonite on the Cross-Linking Efficiency of Polysiloxanes

Materials ◽  
2021 ◽  
Vol 14 (10) ◽  
pp. 2623
Author(s):  
Monika Wójcik-Bania ◽  
Jakub Matusik
Keyword(s):  
Total Pore Volume ◽  
Cross Linking ◽  
X Ray Diffraction ◽  
X Ray ◽  
Transmission Electron ◽  
The Cross ◽  
Chain Lengths ◽  
First Time ◽  
Substituent Influence ◽  
Benzyl Substituent

Polymer–clay mineral composites are an important class of materials with various applications in the industry. Despite interesting properties of polysiloxanes, such matrices were rarely used in combination with clay minerals. Thus, for the first time, a systematic study was designed to investigate the cross-linking efficiency of polysiloxane networks in the presence of 2 wt % of organo-montmorillonite. Montmorillonite (Mt) was intercalated with six quaternary ammonium salts of the cation structure [(CH3)2R’NR]+, where R = C12, C14, C16, and R’ = methyl or benzyl substituent. The intercalation efficiency was examined by X-ray diffraction, CHN elemental analysis, and Fourier transform infrared (FTIR) spectroscopy. Textural studies have shown that the application of freezing in liquid nitrogen and freeze-drying after the intercalation increases the specific surface area and the total pore volume of organo-Mt. The polymer matrix was a poly(methylhydrosiloxane) cross-linked with two linear vinylsiloxanes of different siloxane chain lengths between end functional groups. X-ray diffraction and transmission electron microscopy studies have shown that the increase in d-spacing of organo-Mt and the benzyl substituent influence the degree of nanofillers’ exfoliation in the nanocomposites. The increase in the degree of organo-Mt exfoliation reduces the efficiency of hydrosilylation reaction monitored by FTIR. This was due to physical hindrance induced by exfoliated Mt particles.

Effects of a crosslinking agent on a supramolecular gel to control lost circulation

2021 ◽  
Vol 45 (16) ◽  
pp. 7089-7095
Author(s):  
Bo Wang ◽  
Jinsheng Sun ◽  
Kaihe Lv ◽  
Feng Shen ◽  
Yingrui Bai
Keyword(s):  
Crosslinking Agent ◽  
Network Density ◽  
Cross Linking ◽  
Supramolecular Gel ◽  
Lost Circulation ◽  
The Cross

The Cr3+ can improve the cross-linking degree and network density of the GP-A gel, and enhance its strength and plugging ability to control lost circulation.

scholarly journals Accounting for Cooperativity in the Thermotropic Volume Phase Transition of Smart Microgels

Gels ◽  
2021 ◽  
Vol 7 (2) ◽  
pp. 42
Author(s):  
Simon Friesen ◽  
Yvonne Hannappel ◽  
Sergej Kakorin ◽  
Thomas Hellweg
Keyword(s):  
Phase Transition ◽  
Interaction Parameter ◽  
Quantitative Description ◽  
Water Molecules ◽  
Volume Phase Transition ◽  
Network Chain ◽  
Solvent Interaction ◽  
Volume Phase ◽  
The Cross ◽  
Interaction Parameter Χ

A full quantitative description of the swelling of smart microgels is still problematic in many cases. The original approach of Flory and Huggins for the monomer–solvent interaction parameter χ cannot be applied to some microgels. The reason for this obviously is that the cross-linking enhances the cooperativity of the volume phase transitions, since all meshes of the network are mechanically coupled. This was ignored in previous approaches, arguing with distinct transition temperatures for different meshes to describe the continuous character of the transition of microgels. Here, we adjust the swelling curves of a series of smart microgels using the Flory–Rehner description, where the polymer–solvent interaction parameter χ is modeled by a Hill-like equation for a cooperative thermotropic transition. This leads to a very good description of all measured microgel swelling curves and yields the physically meaningful Hill parameter ν. A linear decrease of ν is found with increasing concentration of the cross-linker N,N′-methylenebisacrylamide in the microgel particles p(NIPAM), p(NNPAM), and p(NIPMAM). The linearity suggests that the Hill parameter ν corresponds to the number of water molecules per network chain that cooperatively leave the chain at the volume phase transition. Driven by entropy, ν water molecules of the solvate become cooperatively “free” and leave the polymer network.

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