Search results for "Hydrophobic effect"
showing 10 items of 74 documents
Differential interactions of the broad spectrum drugs artemisinin, dihydroartemisinin and artesunate with serum albumin
2013
Artemisinin is a drug, widely used in malaria treatment. As the binding affinity of artemisinin and its derivatives dihydroartemisinin and artesunate to blood serum proteins might influence the effectiveness of the drug, binding of artemisinin and derivatives to serum albumin was studied under near physiological conditions. Binding kinetics indicate a simple, single-step association process for all artemisinin derivatives. The determined changes in enthalpy and entropy upon drug binding clearly indicate that hydrophobic forces are most important for artemisinin and dihydroartemisinin binding, whereas binding of artesunate is governed by both hydrophilic and hydrophobic forces. Key residues,…
“Dumb” pH-Independent and Biocompatible Hydrogels Formed by Copolymers of Long-Chain Alkyl Glycidyl Ethers and Ethylene Oxide
2020
The formation and rheological properties of hydrogels based on amphiphilic ABA triblock polyether copolymers are described, relying solely on the hydrophobic interaction of long-chain alkyl glycidyl ether (AlkGE)- based A-blocks that are combined with a hydrophilic poly(ethylene glycol) (PEG) midblock. Via anionic ring-opening copolymerization (AROP), ethylene oxide (EO) and long-chain alkyl glycidyl ethers (AlkGEs) were copolymerized, using deprotonated poly(ethylene glycol) (PEG) macroinitiators (Mn of 10, 20 kg mol-1). The polymerization afforded amphiphilic ABA triblock copolymers with molar masses in the range of 21-32 kg mol-1 and dispersities (Đ) of Đ = 1.07-1.17. Kinetic studies rev…
Enhanced [4+2] cycloadditions by solvophobic effects and gravity-induced mixing in core-shell droplets
2017
A new way to perform reactions in core—shell double emulsions is reported herein. The phase boundaries of the threephase droplet flow were used to pressurize the reactants in the shell liquid, enhancing the reaction rate of a cycloaddition greatly in comparison to known methods. As key parameters, solvophobic effects and precise control over the droplet sizes were used to exploit a reaction with a negative volume of activation. The internal pressure of the reaction solution was regulated purely by the thickness of the shell liquid without adding additional reagents. Additionally, the reaction performed better when the core droplet was used to stir the shell droplet, considerably improving t…
Physics and biophysics of solvent induced forces: hydrophobic interactions and context-dependent hydration
1998
Solvent induced forces (SIFs) among solutes derive from solvent structural modification due to solutes, and consequent thermodynamic drive towards minimization of related free energy costs. The role of SIFs in biomolecular conformation and function is appreciated by observing that typical SIF values fall within the 20–200 pN interval, and that proteins are stable by only a few kcal mol–1 (1 kcal mol–1 corresponds to 70 pN A). Here we study SIFs, in systems of increasing complexity, using Molecular Dynamics (MD) simulations which give time- and space-resolved details on the biologically significant scale of single protein residues and sidechains. Of particular biological relevance among our …
Crystallography of encapsulated molecules.
2017
The crystallography of supramolecular host–guest complexes is reviewed and discussed as a part of small molecule crystallography. In these complexes, the host binds the guests through weak supramolecular interactions, such as hydrogen and halogen bonding, cation–π, anion–π, C–H–π, π–π, C–H–anion interactions and the hydrophobic effect. As the guest often shows severe disorder, large thermal motion and low occupancies, the reliable crystallographic determination of the guest can be very demanding. The analysis of host–guest interactions using tools such as Hirshfeld and cavity volume surface analysis will help to look closely at the most important host–guest interactions. The jewel in the cr…
Inclusion complexes of triphenylphosphine derivatives and peracetylated-β-cyclodextrin in supercritical carbon dioxide
2008
The supramolecular chemistry of peracetylated-β-CD (perAc-β-CD) as a host for triphenyphosphine derivatives has been studied in supercritical (scCO2) using UV absorption spectroscopy. It was found that the association constant in scCO2 at 40°C and 300 bar is 10 to 1000 times smaller compared to analogous systems in aqueous solvent. Studies of the thermodynamics of the inclusion process found an enthalpy of association of -30 kJ/mole and an entropy of -55 J/moleK. This difference with respect to water is attributed to the absence of the hydrophobic effect in scCO2 due to the much smaller polarity of scCO2 versus water. To further explore the effect of the solvent on the association constant,…
Hydrophobic interactions and stacking forces: A convenient model system
1980
Abstract We consider solvent–biomolecule interactions and the role of solvent structural and isotopic alterations on the thermodynamic stability of biomolecular structures. Approaches to this problem range from the study of biomolecular functional stability, to that of the stability of small structural entities suitable of being taken as model systems for (parts of) larger molecules. We shall focus on this latter case and shall consider the dimerization process of small planar molecules (Methylene Blue). These are a convenient model system for the study of interactions responsible e.g. for base stacking in DNA. As an additional advantage, they do not form hydrogen bonds. The experimental st…
Capturing Hydrophobic Trifluoroiodomethane in Water into an M 4 L 6 Cage
2016
Synthetically important trifluoroiodomethane (CF3I) was trapped in water by using a metal–organic supramolecular anionic cage. Under ambient conditions, nearly 1:1 encapsulation of the hydrophobic, gaseous CF3I substrate with the cage was observed, and its binding constant was calculated by relative comparison with benzene encapsulation.
Slippage of water over hydrophobic surfaces
1999
When water is confined between hydrophobic surfaces, its flow properties are significantly different from those in bulk, or between hydrophilic surfaces. These changes (that are usually ignored) may be interpreted in terms of hydrophobic slippage. This chapter reviews recent developments in the hydrodynamics of water confined between solid hydrophobic surfaces, emphasizing the main experimental facts, theoretical models suggested, and different aspects of thin film drainage. The relevance of slippage in hydrophobic surface force measurements and on the coagulation rate of hydrophobic particles is discussed.
Selectivity in the direction of photoisomerization reactions in liquid-crystalline guest-host systems
1995
E ⇄ Z photoisomerization reactions of stilbenes la-c were studied in liquid-crystalline (LC) phases and in the corresponding isotropic melts. Whereas viscosity has a moderate influence on the photostationary states, a strong effect caused by the regular incorporation of the stilbene molecules in the LC phases was observed. The direction of the isomerization can be reversed, up to the case of a one-way isomerization Z E for the tailored guest-host system 1b/BS. Such an LC-matrix effect is of typical highly ordered (smectic) phases with free volumina which are strictly limited by hydrophobic interactions; it could not be detected in a much more mobile nematic phase. Textures based on the bire…