Adsorption-desorption kinetics in nanoscopically confined oligomer films under shear

The method of molecular dynamics computer simulations is employed to study oligomer melts confined in ultra-thin films and subjected to shear. The focus is on the self-diffusion of oligomers near attractive surfaces and on their desorption, together with the effects of increasing energy of adsorption and shear. It is found that the mobility of the oligomers near an attractive surface is strongly decreased. Moreover, although shearing the system forces the chains to stretch parallel to the surfaces and thus increase the energy of adsorption per chain, flow also promotes desorption. The study of chain desorption kinetics reveals the molecular processes responsible for the enhancement of desorption under shear. They involve sequences of conformations starting with a desorbed tail and proceeding in a very fast, correlated, segment-by-segment manner to the desorption of the oligomers from the surfaces.

Motion of a driven tracer particle in a one-dimensional symmetric lattice gas

We study the dynamics of a tracer particle subject to a constant driving force $E$ in a one-dimensional lattice gas of hard-core particles whose transition rates are symmetric. We show that the mean displacement of the driven tracer grows in time, $t$, as $\sqrt{\alpha t}$, rather than the linear time dependence found for driven diffusion in the bath of non-interacting (ghost) particles. The prefactor $\alpha$ is determined implicitly, as the solution of a transcendental equation, for an arbitrary magnitude of the driving force and an arbitrary concentration of the lattice gas particles. In limiting cases the prefactor is obtained explicitly. Analytical predictions are seen to be in a good agreement with the results of numerical simulations.Comment: 21 pages, LaTeX, 4 Postscript fugures, to be published in Phys. Rev. E, (01Sep, 1996

APOBEC Mutagenesis Inhibits Breast Cancer Growth through Induction of T cell-Mediated Antitumor Immune Responses

The APOBEC family of cytidine deaminases is one of the most common endogenous sources of mutations in human cancer. Genomic studies of tumors have found that APOBEC mutational signatures are enriched in theHER2 subtype of breast cancer and are associated with immunotherapy response in diverse cancer types. However, the direct consequences of APOBEC mutagenesis on the tumor immune microenvironment have not been thoroughly investigated. To address this, we developed syngeneic murine mammary tumor models with inducible expression of APOBEC3B. We found that APOBEC activity induced antitumor adaptive immune responses and CD4 T cell-mediated, antigen-specific tumor growth inhibition. Although polyclonal APOBEC tumors had a moderate growth defect, clonal APOBEC tumors were almost completely rejected, suggesting that APOBEC-mediated genetic heterogeneity limits antitumor adaptive immune responses. Consistent with the observed immune infiltration in APOBEC tumors, APOBEC activity sensitized HER2-driven breast tumors to anti- CTLA-4 checkpoint inhibition and led to a complete response to combination anti-CTLA-4 and anti-HER2 therapy. In human breast cancers, the relationship between APOBEC mutagenesis and immunogenicity varied by breast cancer subtype and the frequency of subclonal mutations. This work provides a mechanistic basis for the sensitivity of APOBEC tumors to checkpoint inhibitors and suggests a rationale for using APOBEC mutational signatures and clonality as biomarkers predicting immunotherapy response in HER2-positive (HER2 ) breast cancers

Molecular dynamics for linear polymer melts in bulk and confined systems under shear flow

In this work, we analyzed the individual chain dynamics for linear polymer melts under shear flow for bulk and confined systems using atomistic nonequilibrium molecular dynamics simulations of unentangled (C50H102) and slightly entangled (C178H358) polyethylene melts. While a certain similarity appears for the bulk and confined systems for the dynamic mechanisms of polymer chains in response to the imposed flow field, the interfacial chain dynamics near the boundary solid walls in the confined system are significantly different from the corresponding bulk chain dynamics. Detailed molecular-level analysis of the individual chain motions in a wide range of flow strengths are carried out to characterize the intrinsic molecular mechanisms of the bulk and interfacial chains in three flow regimes (weak, intermediate, and strong). These mechanisms essentially underlie various macroscopic structural and rheological properties of polymer systems, such as the mean-square chain end-to-end distance, probability distribution of the chain end-to-end distance, viscosity, and the first normal stress coefficient. Further analysis based on the mesoscopic Brightness method provides additional structural information about the polymer chains in association with their molecular mechanisms

Evaluation of Chemical Protective Clothing by FT-IR/ATR Spectroscopy

An attenuated total reflectance permeation cell has been used to evaluate the permeation of polymer samples from chemical protective clothing (CPC), mainly gloves, by several chemical types including a solvent, a commercial pesticide mix, and a volatile solid. Good contact between sample and ATR crystal was ensured by the use of low gas pressure. The passage of the chemicals through the CPC sample could be readily followed by analysis of sets of FT-IR spectra measured during permeation experiments. Diffusion coefficients could only be estimated. The ATR method is compared with the traditional two-compartment cell used for evaluation of CPC, and its advantages and disadvantages discussed

TRIBOLOGY STUDIED USING ATOMICALLY SMOOTH SURFACES

An investigation is reported of the boundary layer friction resulting from films of nonpolar liquid lubricants, 1 to 6 layers of molecules thick. The liquids were confined between parallel step-free single crystals of muscovite mica. The apparent dynamic viscosity at 1 Hz (shear rate less than 250 sec???1) was considerably enhanced over that of the isotropic liquids and increased substantially with increasing net normal pressure. A transition to a solid-like response occurred with increasing net normal pressure, without discernible change in thickness. Investigations of the critical shear stress to accomplish sliding showed a buildup of this static friction over times from minutes to hours. For films of hexadecane, the pressure coefficient of the critical shear stress was approximately 2 to 20, depending on the equilibration time allowed at each normal pressure. The tribological behavior of these lubricant films did not appear to reflect material properties of the lubricants as such, but rather to stem, from confinement of the lubricants within the tribological contact, where the freedom of molecules to move was restricted. Potential practical implications are discussed