An official website of the United States government
A classical model in the framework of the INTERFACE force field has been developed for treating the LiCoO$$_2$$ (LCO) (001)/water interface. In comparison to {\em ab initio} molecular dynamics (MD) simulations based on density functional theory, MD simulations using the classical model lead to generally reliable descriptions of interfacial properties, such as the density distribution of water molecules. Water molecules in close contact with the LCO surface form a strongly adsorbed layer, which leads to a free energy barrier for the absorption of polar or charged molecules to the LCO surface. Moreover, due to the strong hydrogen bonding interactions with the LCO surface, the first water layer forms an interface that exhibits hydrophobic characters, leading to favorable adsorption of non-polar molecules to the interface. Therefore, despite its highly polar nature, the LCO (001) surface binds not only polar/charged but also non-polar solutes. As an application, the model is used to analyze the adsorption of reduced nicotinamide adenine dinucleotide (NADH) and its molecular components to the LCO (001) surface in water. The results suggests that recently observed redox activity of NADH at the LCO/water interface was due to the co-operativity between the ribose component, which drives binding to the LCO surface, and the nicotinamide moiety, which undergoes oxidation.
more »
« less
Interfacial Yield Stress Response in Synthetic Mucin Solutions
Abstract The solution rheology of a fully synthetic, monodisperse mucin that mimics the glycosylated domains of natural mucins, poly(β‐Gal‐Thr)22, is studied to systematically explore relationships between polymer structure, solution conditions, and rheological properties. Using standard cone‐plate rheometry, shear thinning is observed over a range of concentrations, with an apparent yield stress—typical for gels—evident at the highest concentrations. This is surprising given the dilute, weakly interacting nature of the solutions and the lack of observable structure in cryogenic electron microscopy and particle tracking microrheology. However, interfacial rheometry demonstrates that the gel‐like behavior is attributable to a thin structured layer at the air–water interface, without any bulk gelation. This is attributed to an interfacial layer formed by inter‐mucin H‐bonds that yields when sheared. A computational model using kinetic Monte Carlo (kMC) simulations qualitatively reproduces the yield stress response of such a network through an intermolecular bonding potential. An analytical model of stochastic bond formation and breaking, validated by the kMC simulations, demonstrates that having multiple bonding sites per mucin with a force‐dependent debonding rate aligns with experiments, consistent with intermolecular interactions for other mucin proteins. This suggests that in mucin solutions, gelation may begin at the air–water interface, and emphasizes the need for multitechnique validation when exploring structural cues of mucus gelation through rheometry.
more »
« less
- PAR ID:
- 10571439
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials Interfaces
- Volume:
- 12
- Issue:
- 12
- ISSN:
- 2196-7350
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
The bonding of ceramic to metal has been challenging due to the dissimilar nature of the materials, particularly different surface properties and the coefficients of thermal expansion (CTE). To address the issues, gas phase-processed thin metal films were inserted at the metal/ceramic interface to modify the ceramic surface and, therefore, promote heterogeneous bonding. In addition, an alloy bonder that is mechanically and chemically activated at as low as 220 °C with reactive metal elements was utilized to bond the metal and ceramic. Stainless steel (SS)/Zerodur is selected as the metal/ceramic bonding system where Zerodur is chosen due to the known low CTE. The low-temperature process and the low CTE of Zerodur are critical to minimizing the undesirable stress evolution at the bonded interface. Sputtered Ti, Sn, and Cu (300 nm) were deposited on the Zerodur surface, and then dually activated molten alloy bonders were spread on both surfaces of the coated Zerodur and SS at 220 °C in air. The shear stress of the bonding was tested with a custom-designed fixture in a universal testing machine and was recorded through a strain indicator. The mechanical strength and the bonded surface property were compared as a function of interfacial metal thin film and analyzed through thermodynamic interfacial stability/instability calculations. A maximum shear strength of bonding of 4.36 MPa was obtained with Cu interfacial layers, while that of Sn was 3.53 MPa and that of Ti was 3.42 MPa. These bonding strengths are significantly higher than those (∼0.04 MPa) of contacts without interfacial reactive thin metals.more » « less
-
We present the results of molecular dynamics simulations of a nanoscale electrochemical cell. The simulations include an aqueous electrolyte solution with varying ionic strength (i.e., concentrations ranging from 0-4M) between a pair of metallic electrodes held at constant potential difference. We analyze these simulations by computing the electrostatic potential profile of the electric double-layer region and find it to be nearly independent of ionic concentration, in stark contrast to the predictions of standard continuum-based theories. We attribute this lack of concentration dependence to the molecular influences of water molecules at the electrode-solution interface. These influences include the molecular manifestation of water's dielectric response, which tends to drown out the comparatively weak screening requirement of the ions. To support our analysis, we decompose water's interfacial response into three primary contributions: molecular layering, intrinsic (zero-field) orientational polarization, and the dipolar dielectric response.more » « less
-
Single particle tracking (SPT) of PEG grafted nanoparticles (NPs) was used to examine the gelation of tetra poly(ethylene glycol) (TPEG) succinimidyl glutarate (TPEG-SG) and amine (TPEG-A) terminated 4-armed stars. As concentration was decreased from 40 to 20 mg mL −1 , the onset of network formation, t gel , determined from rheometry increased from less than 2 to 44 minutes. NP mobility increased as polymer concentration decreased in the sol state, but remained diffusive at times past the t gel determined from rheometry. Once in the gel state, NP mobility decreased, became sub-diffusive, and eventually localized in all concentrations. The NP displacement distributions were investigated to gain insight into the nanoscale environment. In these relatively homogeneous gels, the onset of sub-diffusivity was marked by a rapid increase in dynamic heterogeneity followed by a decrease consistent with a homogeneous network. We propose a gelation mechanism in which clusters initially form a heterogeneous structure which fills in to form a fully gelled relatively homogenous network. This work aims to examine the kinetics of TPEG gelation and the homogeneity of these novel gels on the nanometer scale, which will aid in the implementation of these gels in biomedical or filtration applications.more » « less
-
The thinning of a cylinder of a polymer solution in a volatile solvent is argued to be controlled by solvent diffusion through a dense polymer layer at the cylinder surface. This naturally leads to the exponential time dependence of cylinder radius that is observed in experiments using a fast camera, such as capillary breakup extensional rheometry (CaBER). The relaxation time is controlled by the thickness of the dense (and often glassy) polymer layer and the diffusion coefficient of solvent through that layer. If correct, this means that while CaBER is very useful for understanding fiber spinning, the relaxation time does not yield a measure of the extensional viscosity of polymer solutions in volatile solvents.more » « less
