ABSTRACT
A coarse-grained Brownian dynamics model was used to simulate two proteins of similar sizes inside model membrane pores of varying size and hydrophobicity. The two proteins, which have radii of gyration of approximately 9.5 Å in their native states, are a 36-residue hydrophilic villin head piece (HP-36) and a 40-residue hydrophobic amyloid beta (Aß-40). From calculations of the separation factor, it is found that the two proteins are best separated using a pore radius of 15 Å and that hydrophobic pores select Aß-40 while the hydrophilic pores preferentially pass through HP-36. In addition, it is found that a simple model based on the net hydropathy of a protein is capable of estimating the separation factor trends of other protein pairs. Together, the coarse-grained Brownian dynamics model and the simple model are fast methodologies to guide experimental membrane design and to provide insights on protein structure variations. Graphical Abstract Simulation setup and snapshots of protein in various pore sizes.
Subject(s)
Amyloid beta-Peptides/chemistry , Models, Molecular , Molecular Dynamics Simulation , Neurofilament Proteins/chemistry , Peptide Fragments/chemistry , Humans , Hydrophobic and Hydrophilic Interactions , Protein Conformation , Protein FoldingABSTRACT
The reaction kinetics between CO2 and trihexyl(tetradecyl)phosphonium ([P66614])-based ionic liquids (ILs) with prolinate ([Pro]), 2-cyanopyrrolide ([2-CNpyr]), and 3-(trifluoromethyl)pyrazolide ([3-CF3pyra]) anions are studied at temperatures from 22-60 °C. The absorption of CO2 is carried out in a stirred reactor under pseudo first order conditions. ILs are diluted to concentrations of 0.05, 0.1 and 0.15 M with tetraglyme--a nonreactive, low volatility solvent with much lower viscosity than the ILs. Physical solubility of CO2 in the mixtures is calculated using correlations developed from CO2 solubility measurements in tetraglyme and the N2O-analogy for ILs and dilute IL solutions. The diffusivity of CO2 is estimated from viscosity-dependent correlations chosen after a thorough literature review. The results indicate partial first order reaction kinetics with respect to IL with values ranging from 19,500 L mol(-1) s(-1) ([P66614][Pro]) to 3200 L mol(-1) s(-1) ([P66614][3-CF3pyra]) at 22 °C. The second order reaction rate constants follow Arrhenius behavior with the highest activation energy of 43 kJ mol(-1) measured for [P66614][Pro]. ILs with aprotic heterocylic anions (AHA), on the other hand, show small activation energies of 18 and 11 kJ mol(-1) for [P66614][3-CF3pyra] and [P66614][2-CNpyr], respectively. The ILs studied in this work exhibit reactivity comparable to or higher than common aqueous amines. High reaction rates and tunable capacity make ILs, and AHA ILs in particular, attractive solvents for CO2 separations.
Subject(s)
Carbon Dioxide/chemistry , Ionic Liquids/chemistry , Organophosphorus Compounds/chemistry , Absorption , Anions/chemistry , Kinetics , Molecular Structure , Surface PropertiesABSTRACT
The influence of calcium phosphate nanoshell materials on the uptake, viability, and mineralization of human fetal osteoblast cultures was evaluated. Proliferation rates and alkaline phosphatase activity of the cultures were unaffected by the addition of nanoshells to the growth media, but mineralization levels were enhanced by nearly 40%, in contrast to media prepared without nanoshells, or with other calcium phosphate nanomaterials. Nanoshells were internalized by macropinocytosis, and migrated toward the cell nucleus at a rate of 0.34 microm hr(-1). Dye-loaded nanoshells maintained high light emission intensity for over five days while inside the cells, where they could be used as intracellular markers for in vitro microscopic imaging. From these results, it appears that the CaP nanoshells could be developed into a safe sensor and delivery vehicle for osteoblast cell culture studies, whereas the carrier itself has intrinsic bioactivity and may itself upregulate the formation of new bone.
Subject(s)
Biocompatible Materials/metabolism , Calcium Phosphates , Cell Differentiation/physiology , Nanoparticles/chemistry , Osteoblasts/physiology , Alkaline Phosphatase/metabolism , Biocompatible Materials/chemistry , Biological Transport/physiology , Calcium Phosphates/chemistry , Calcium Phosphates/metabolism , Cell Line , Fetus/cytology , Humans , Materials Testing , Osteoblasts/cytologyABSTRACT
The consequences of an oscillatory fluid shear mechanism on nutrient transport in bone during physical activity and ultrasonic therapy are discussed. During movement, periodic stress on bone creates transient pressure gradients that circulate interstitial fluid through calcified bone. A transport model derived from oscillatory Taylor-Aris dispersion phenomena was used to predict a ratio of effective-to-molecular diffusivity, K/D, for solutes of varying sizes up to 50 nm in diameter, in pores filled with interstitial fluid and pericellular matrix. The magnitude of the estimated transport enhancement depended on the molecular size, pore dimension, applied frequency and the displacement of the fluid during pressurization. For oscillation frequencies and amplitudes corresponding to those experienced during normal human activity, transport enhancements of up to 100 fold are expected for molecules larger than 5 nm in diameter. Enhancements of up to one order of magnitude, due to ultrasound stimulations in the MHz frequency range, are also expected for 7-nm-sized solutes. No effects are anticipated for ions, whose molecular diffusion time is too fast relative to the oscillation frequency. This model is expected to be useful for understanding differences in bone growth as a function of type of movement or to develop new physical therapies.
