Entropic contributions to the stability of electrochemically adsorbed anion layers on Au(111): a microcalorimetric study

We measure the entropy of formation of the interface upon anion adsorption (Cl$^−$, Br$^−$ I$^−$ and SO$_4$$^{2−}$) on Au(111) as an important indicator for the structure, order and composition of the interface. The entropy of formation of the interface exhibits a rather universal behaviour for all anions with a steep decrease upon initial adsorption followed by a shallow minimum at intermediate anion coverages and a strong increase close to the completion of the adsorbate adlayer. The strong variation of the entropy signals significant entropic contributions to the free enthalpy of the adsorption process and thus the stability of the adsorbed phase. At low anion coverages, close to the potential of zero charge, we attribute the entropy variations to the rearrangement of the interfacial water structure. At intermediate and high anion coverages, a comparison with the results of a lattice-gas model, considering pairwise repulsive interactions within the quasi-chemical approximation, shows that the entropy changes upon anion adsorption can be explained by the configurational entropy of the adsorbed phase. Thus, entropic contributions from both the solvent and the adsorbate are important for the stability of surface phases, particularly for disordered systems

Identification of Electrochemically Adsorbed Species via Electrochemical Microcalorimetry: Sulfate Adsorption on Au(111)

We investigate compositional changes of an electrochemical interface upon polarization with electrochemical microcalorimetry. From the heat exchanged at a Au(111) electrode upon sulfate adsorption, we determine the reaction entropy of the adsorption process for both neutral and acidic solutions, where the dominant species in solution changes from SO$_4$$^{2−}$ to HSO$_4$$^{−}$. In neutral solution, the reaction entropy is about 40 J mol$^{−1}$ K$^{−1}$ more positive than that in acidic solution over the complete sulfate adsorption region. This entropy offset is explicable by a deprotonation step of HSO$_4$$^{−}$ preceding sulfate adsorption in acidic solution, which shows that the adsorbing species is SO$_4$* in both solutions. The observed overall variation of the reaction entropy in the sulfate adsorption region of ca. 80 J mol$^{−1}$ K$^{−1}$ indicates significant sulfate-coverage dependent entropic contributions to the Free Enthalpy of the surface system

Nanoscale electrochemical 3D deposition of cobalt with nanosecond voltage pulses in an STM

To explore a minimal feature size of <100 nm with electrochemical additive manufacturing, we use a strategy originally applied to microscale electrochemical machining for the nanoscale deposition of Co on Au. The concept's essence is the localization of electrochemical reactions below a probe during polarization with ns-long voltage pulses. As shown, a confinement that exceeds that predicted by a simple model based on the time constant for one-dimensional double layer charging enables a feature size of <100 nm for 2D patterning. We further indirectly verify the potential for out-of-plane deposition by tracking growth curves of high-aspect-ratio deposits. Importantly, we report a lack of anodic stability of Au tips used for patterning. As an inert probe is the prerequisite for controlled structuring, we experimentally verify an increased resistance of Pt probes against degradation. Consequently, the developed setup and processes show a path towards reproducible direct 2D and 3D patterning of metals at the nanoscale.ISSN:2040-3364ISSN:2040-337

Molecular characterization of breast cancer cell pools with normal or reduced ability to respond to progesterone: a study based on RNA-seq.

BACKGROUND About one-third of patients with estrogen receptor alpha (ERα)-positive breast cancer have tumors which are progesterone receptor (PR) negative. PR is an important prognostic factor in breast cancer. Patients with ERα-positive/PR-negative tumors have shorter disease-free and overall survival than patients with ERα-positive/PR-positive tumors. New evidence has shown that progesterone (P4) has an anti-proliferative effect in ERα-positive breast cancer cells. However, the role of PR in breast cancer is only poorly understood. METHODS We disrupted the PR gene (PGR) in ERα-positive/PR-positive T-47D cells using the CRISPR/Cas9 system. This resulted in cell pools we termed PR-low as P4 mediated effects were inhibited or blocked compared to control T-47D cells. We analyzed the gene expression profiles of PR-low and control T-47D cells in the absence of hormone and upon treatment with P4 alone or P4 together with estradiol (E2). Differentially expressed (DE) genes between experimental groups were characterized based on RNA-seq and Gene Ontology (GO) enrichment analyses. RESULTS The overall gene expression pattern was very similar between untreated PR-low and untreated control T-47D cells. More than 6000 genes were DE in control T-47D cells upon stimulation with P4 or P4 plus E2. When PR-low pools were subjected to the same hormonal treatment, up- or downregulation was either blocked/absent or consistently lower. We identified more than 3000 genes that were DE between hormone-treated PR-low and control T-47D cells. GO analysis revealed seven significantly enriched biological processes affected by PR and associated with G protein-coupled receptor (GPCR) pathways which have been described to support growth, invasiveness, and metastasis in breast cancer cells. CONCLUSIONS The present study provides new insights into the complex role of PR in ERα-positive/PR-positive breast cancer cells. Many of the genes affected by PR are part of central biological processes of tumorigenesis

TassDB: a database of alternative tandem splice sites

Subtle alternative splice events at tandem splice sites are frequent in eukaryotes and substantially increase the complexity of transcriptomes and proteomes. We have developed a relational database, TassDB (TAndem Splice Site DataBase), which stores extensive data about alternative splice events at GYNGYN donors and NAGNAG acceptors. These splice events are of subtle nature since they mostly result in the insertion/deletion of a single amino acid or the substitution of one amino acid by two others. Currently, TassDB contains 114 554 tandem splice sites of eight species, 5209 of which have EST/mRNA evidence for alternative splicing. In addition, human SNPs that affect NAGNAG acceptors are annotated. The database provides a user-friendly interface to search for specific genes or for genes containing tandem splice sites with specific features as well as the possibility to download large datasets. This database should facilitate further experimental studies and large-scale bioinformatics analyses of tandem splice sites. The database is available at