High-Speed Atomic Force Microscopy Reveals the Nucleosome Sliding and DNA Unwrapping/Wrapping Dynamics of Tail-less Nucleosomes.

Each nucleosome contains four types of histone proteins, each with a histone tail. These tails are essential for the epigenetic regulation of gene expression through post-translational modifications (PTMs). However, their influence on nucleosome dynamics at the single-molecule level remains undetermined. Here, we employed high-speed atomic force microscopy to visualize nucleosome dynamics in the absence of the N-terminal tail of each histone or all of the N-terminal tails. Loss of all tails stripped 6.7 base pairs of the nucleosome from the histone core, and the DNA entry-exit angle expanded by 18° from that of wild-type nucleosomes. Tail-less nucleosomes, particularly those without H2B and H3 tails, showed a 10-fold increase in dynamics, such as nucleosome sliding and DNA unwrapping/wrapping, within 0.3 s, emphasizing their role in histone-DNA interactions. Our findings illustrate that N-terminal histone tails stabilize the nucleosome structure, suggesting that histone tail PTMs modulate nucleosome dynamics.

Contributions of histone tail clipping and acetylation in nucleosome transcription by RNA polymerase II.

The N-terminal tails of histones protrude from the nucleosome core and are target sites for histone modifications, such as acetylation and methylation. Histone acetylation is considered to enhance transcription in chromatin. However, the contribution of the histone N-terminal tail to the nucleosome transcription by RNA polymerase II (RNAPII) has not been clarified. In the present study, we reconstituted nucleosomes lacking the N-terminal tail of each histone, H2A, H2B, H3 or H4, and performed RNAPII transcription assays. We found that the N-terminal tail of H3, but not H2A, H2B and H4, functions in RNAPII pausing at the SHL(-5) position of the nucleosome. Consistently, the RNAPII transcription assay also revealed that the nucleosome containing N-terminally acetylated H3 drastically alleviates RNAPII pausing at the SHL(-5) position. In addition, the H3 acetylated nucleosome produced increased amounts of the run-off transcript. These results provide important evidence that the H3 N-terminal tail plays a role in RNAPII pausing at the SHL(-5) position of the nucleosome, and its acetylation directly alleviates this nucleosome barrier.

Proton to hydride umpolung at a phosphonium center via electron relay: a new strategy for main-group based water reduction.

Generation of dihydrogen from water splitting, also known as water reduction, is a key process to access a sustainable hydrogen economy for energy production and usage. The key step is the selective reduction of a protic hydrogen to an accessible and reactive hydride, which has proven difficult at a p-block element. Although frustrated Lewis pair (FLP) chemistry is well known for water activation by heterolytic H-OH bond cleavage, to the best of our knowledge, there has been only one case showing water reduction by metal-free FLP systems to date, in which silylene (SiII) was used as the Lewis base. This work reports the molecular design and synthesis of an ortho-phenylene linked bisborane-functionalized phosphine, which reacts with water stoichiometrically to generate H2 and phosphine oxide quantitatively under ambient conditions. Computational investigations revealed an unprecedented multi-centered electron relay mechanism offered by the molecular framework, shuttling a pair of electrons from hydroxide (OH-) in water to the separated proton through a borane-phosphonium-borane path. This simple molecular design and its water reduction mechanism opens new avenues for this main-group chemistry in their growing roles in chemical transformations.

Catalytic Dehydrogenation of Ammonia Borane Mediated by a Pt(0)/Borane Frustrated Lewis Pair: Theoretical Design.

A new efficient metal-based frustrated Lewis pair constructed by (Pt Bu3 )2 Pt and B(C6 F5 )3 was designed through density functional theory calculations for the catalytic dehydrogenation of ammonia borane (AB). The reaction was composed by the successive dehydrogenation of AB and H2 liberation, which occurs through the cooperative functions of the Pt(0) center and the B(C6 F5 )3 moiety. Two equivalents of H2 were predicted to be liberated from each AB molecule. The generation of the second H2 is the rate-determining step, with a Gibbs energy barrier and reaction energy of 27.4 and 12.8 kcal/mol, respectively.

Influence of handpiece maintenance sprays on resin bonding to dentin.

OBJECTIVE: To investigate the influence of maintenance spray on resin bonding to dentin. MATERIALS AND METHODS: The crown of extracted, caries-free human molars was transversally sectioned with a model trimmer to prepare the dentin surfaces from mid-coronal sound dentin, and then uniformly abraded with #600 silicon carbide paper. The dentin surfaces were randomly divided into three groups: oil-free spray group where maintenance cleaner for air bearing handpieces was sprayed onto the dentin surface for 1 s and rinsed with water spray for 30 s; oil-containing spray group where maintenance cleaner for micro motor handpieces was sprayed onto the dentin surface for 1 s and rinsed with water spray for 30 s; and control group where the surface was rinsed with water spray for 30 s and then air-dried. These surfaces were then bonded with Clearfil SE Bond (Kuraray Medical), and resin composite (Clearfil AP-X, Kuraray Medical) build-up crowns were incrementally constructed on the bonded surfaces. After storage for 24 h in 37°C water, the bonded teeth were sectioned into hour-glass shaped slices (0.7-mm thick) perpendicular to the bonded surfaces. The specimens were then subjected to microtensile bond strength (µTBS) testing at a crosshead speed of 1.0 mm/min. Data were analyzed with one-way ANOVA and the Tukey-Kramer test. RESULTS: Maintenance spray-contaminated specimens (oil-free and oil-containing spray groups) showed significantly lower µTBS than control specimens (P < 0.05). However, there was no significant difference between the spray-contaminated groups (P > 0.05). CONCLUSION: Maintenance spray significantly reduces the bond strength of Clearfil SE Bond to dentin.

Microtensile bond strength of indirect resin composite to resin-coated dentin: interaction between diamond bur roughness and coating material.

This aim of this study was to determine the effect of type of bur and resin-coating material on microtensile bond strength (microTBS) of indirect composite to dentin. Dentin surfaces were first ground with two types of diamond bur and resin-coated using UniFil Bond (UB) or Adper Single Bond (SB), and then bonded to a resin composite disc for indirect restoration with adhesive resin cement. After storage for 24 hr in distilled water at 37 degrees C, microTBS was measured (crosshead speed 1 mm/min). When UB was applied to dentin prepared using the regular-grit diamond bur, microTBS was significantly lower than that in dentin prepared using the superfine-grit bur. In contrast, no significant difference was found between regular-grit and superfine-grit bur with SB. However, more than half of the superfine-grit specimens failed before microTBS testing. These results indicate that selection of bur type is important in improving the bond strength of adhesive resin cement between indirect resin composite and resin-coated dentin.