Why is Superlubricity of Diamond-Like Carbon Rare at Nanoscale?

Hydrogenated diamond-like carbon (HDLC) is a promising solid lubricant for its superlubricity which can benefit various industrial applications. While HDLC exhibits notable friction reduction in macroscale tests in inert or reducing environmental conditions, ultralow friction is rarely observed at the nanoscale. This study investigates this rather peculiar dependence of HDLC superlubricity on the contact scale. To attain superlubricity, HDLC requires i) removal of ≈2 nm-thick air-oxidized surface layer and ii) shear-induced transformation of amorphous carbon to highly graphitic and hydrogenated structure. The nanoscale wear depth exceeds the typical thickness of the air-oxidized layer, ruling out the possibility of incomplete removal of the air-oxidized layer. Raman analysis of transfer films indicates that shear-induced graphitization readily occurs at shear stresses lower than or comparable to those in the nanoscale test. Thus, the same is expected to occur at the nanoscale test. However, the graphitic transfer films are not detected in ex-situ analyses after nanoscale friction tests, indicating that the graphitic transfer films are pushed out of the nanoscale contact area due to the instability of transfer films within a small contact area. Combining all these observations, this study concludes the retention of highly graphitic transfer films is crucial to achieving HDLC superlubricity.

Estrogen Effects Differ Between Medium Maintenance and Replacement from Transcriptional and Clinical Perspectives in T47D Breast Cancer Cells.

BACKGROUND/AIM: Our most recent study revealed that the responsiveness of hormone receptor-positive breast cancer (HR+ BC) cells to estrogen or endocrine therapy can be altered by certain cell culture or ambient environmental conditions. Nevertheless, we were unable to investigate the relevant molecular mechanism and clinical relevance. Therefore, this study was planned as a follow-up. MATERIALS AND METHODS: RNA sequencing was mainly used with T47D cells treated with or without 17ß-estradiol (E2) under medium maintenance (MTN; conventional culture method) and medium exchange (EXC; daily replacing the existing medium with fresh medium). RESULTS: The role of E2 in transcription differed between MTN and EXC, and E2 played more important roles in transcription in terms of cancer development under EXC than under MTN, consistent with the previous functional effects of EXC. The novel concept of the "estrogen-responsive and proliferation-related gene (ERPG)" was introduced. The expression of ERPGs, which were distinguished from typical estrogen-responsive genes, was correlated with that of prognostic and predictive factors for HR+ BC. The transcriptional induction of ERPGs and typical estrogen-responsive genes regardless of E2 treatment under MTN was reminiscent of constitutive estrogen receptor (ER) activation. Additionally, phosphatidylinositol 3-kinase (PI3K)/protein kinase B (AKT)/mammalian target of rapamycin (mTOR) inhibitors were more effective under EXC than under MTN. CONCLUSION: This study, demonstrating the more important roles of estrogen in terms of cancer development under EXC than under MTN, supports the use of our research model in future studies to overcome endocrine resistance in HR+ BC.

Tribochemistry of Diamond-like Carbon: Interplay between Hydrogen Content in the Film and Oxidative Gas in the Environment.

The lubricity of hydrogenated diamond-like carbon (HDLC) films is highly sensitive to the hydrogen (H) content in the film and the oxidizing gas in the environment. The tribochemical knowledge of HDLC films with two different H-contents (mildly hydrogenated vs highly hydrogenated) was deduced from the analysis of the transfer layers formed on the counter-surface during friction tests in O2 and H2O using Raman spectroscopic imaging and X-ray photoelectron spectroscopy (XPS). The results showed that, regardless of H-content in the film, shear-induced graphitization and oxidation take place readily. By analyzing the O2 and H2O partial pressure dependence of friction of HDLC with a Langmuir-type reaction kinetics model, the oxidation probability of the HDLC surface exposed by friction as well as the removal probability of the oxidized species by friction were determined. The HDLC film with more H-content exhibited a lower oxidation probability than the film with less H-content. The atomistic origin of this H-content dependence was investigated using reactive molecular dynamics simulations, which showed that the fraction of undercoordinated carbon species decreased as the H-content in the film increased, corroborating the lower oxidation probability of the highly-hydrogenated film. The H-content in the HDLC film influenced the probabilities of oxidation and material removal, both of which vary with the environmental condition.

A New Culture Model for Enhancing Estrogen Responsiveness in HR+ Breast Cancer Cells through Medium Replacement: Presumed Involvement of Autocrine Factors in Estrogen Resistance.

Hormone receptor-positive breast cancer (HR+ BC) cells depend on estrogen and its receptor, ER. Due to this dependence, endocrine therapy (ET) such as aromatase inhibitor (AI) treatment is now possible. However, ET resistance (ET-R) occurs frequently and is a priority in HR+ BC research. The effects of estrogen have typically been determined under a special culture condition, i.e., phenol red-free media supplemented with dextran-coated charcoal-stripped fetal bovine serum (CS-FBS). However, CS-FBS has some limitations, such as not being fully defined or ordinary. Therefore, we attempted to find new experimental conditions and related mechanisms to improve cellular estrogen responsiveness based on the standard culture medium supplemented with normal FBS and phenol red. The hypothesis of pleiotropic estrogen effects led to the discovery that T47D cells respond well to estrogen under low cell density and medium replacement. These conditions made ET less effective there. The fact that several BC cell culture supernatants reversed these findings implies that housekeeping autocrine factors regulate estrogen and ET responsiveness. Results reproduced in T47D subclone and MCF-7 cells highlight that these phenomena are general among HR+ BC cells. Our findings offer not only new insights into ET-R but also a new experimental model for future ET-R studies.

Understanding and Preventing Lubrication Failure at the Carbon Atomic Steps.

Two-dimensional (2D) lamellar materials are normally capable of rendering super-low friction, wear protection, and adhesion reduction in nanoscale due to their ultralow shear strength between two basal plane surfaces. However, high friction at step edges prevents the 2D materials from achieving super-low friction in macroscale applications and eventually leads to failure of lubrication performance. Here, taking graphene as an example, the authors report that not all step edges are detrimental. The armchair (AC) step edges are found to have only a minor topographic effect on friction, while the zigzag (ZZ) edges cause friction two orders of magnitude larger than the basal plane. The AC step edge is less reactive and thus more durable. However, the ZZ structure prevails when step edges are produced mechanically, for example, through mechanical exfoliation or grinding of graphite. The authors found a way to make the high-friction ZZ edge superlubricious by reconstructing the (6,6) hexagon structure to the (5,7) azulene-like structure through thermal annealing in an inert gas environment. This will facilitate the realization of graphene-based superlubricity over a wide range of industrial applications in which avoiding the involvement of step edges is difficult.

Gas-Induced Ion-Free Stable Radical Anion Formation of Organic Semiconducting Solids as Highly Gas-Selective Probes.

The formation of stabilized radical anions on organic materials in the solid state is an important issue in radical-based fundamental research and various applications. Herein, for the first time, we report on gas-induced ion-free stable radical anion formation (SRAF) of organic semiconducting solids with high gas selectivities through the use of organic field-effect transistor (OFET) gas sensors and electron spin resonance spectroscopy. In contrast to the previously reported SRAF, which requires either anionic analytes in solution and/or cationic substituents on π-electron-deficient aromatic cores, NDI-EWGs consist of an n-type semiconducting naphthalene diimide (NDI) and various electron-withdrawing groups (EWGs) that exhibit non-ion-involved, gas-selective SRAF in the solid state. In the presence of hard Lewis base gases, NDI-EWG-based OFETs exhibit enhanced conductivity (Current-ON mode) through the formation of an SRAF NDI/gas complex, while in the presence of borderline and soft Lewis base gases, NDI-EWG-based OFETs show decreased conductivity (Current-OFF mode) by the formation of a resistive NDI/gas complex. Organic semiconducting solids with EWGs exhibiting highly gas-selective solid-SRAF constitute a very promising platform for radical-based chemistry and can be used in various applications, such as highly gas-selective probes.

High performance organic photosensitizers for dye-sensitized solar cells.

We report highly efficient organic photosensitizers containing pi-conjugated alkoxy-substituted oligophenylenevinylene linkers with electron donor-acceptor units for dye-sensitized solar cells. TA-DM-CA showed an overall solar-to-energy conversion efficiency of 9.67% at AM 1.5 illumination (100 mW cm(-2)).