Dendrimeric organochalcogen catalysts for the activation of hydrogen peroxide: improved catalytic activity through statistical effects and cooperativity in successive generations

Dendrimeric polyphenylsulfides, -selenides, and -tellurides are prepared in high yield using propyloxy spacers to connect the phenylchalcogeno groups to the dendrimeric core. The selenides and tellurides catalyze the oxidation of bromide with hydrogen peroxide to give positive bromine species that can be captured by cyclohexene in two-phase systems. The corresponding sulfides show no catalytic activity. The increase in the rate of catalysis followed statistical effects for 1, 6, and 12 phenyltelluro groups. However, the increase in the rate of catalysis exceeds statistical contributions for the first few generations with 1, 3, 6, and 12 phenylseleno groups and suggested cooperativity among phenylseleno groups. The increase in catalytic rate was lost upon replacing all but one phenylseleno group with phenoxy groups. On the basis of H2O2 consumed, the dendrimer with 12 phenylseleno groups has a turnover number of >60 000 mol of H2O2 consumed per mole of catalyst.     

A hasse principle for function fields over pac fields

LetK be a perfect pseudo-algebraically closed field and letF be an extension ofK of relative transcendence degree 1. It is shown that the restriction map Res: Br(F)→Π_p Br(F _p ^h ) is injective, where p ranges over all non-trivialK-places ofF, andF _p ^h is the corresponding henselization. Conversely, the validity of this Hasse principle for all such extensionsF implies a weaker version of pseudo-algebraic closedness. As an application we determine the finitely generated pro-p closed subgroups of the absolute Galois group ofK(t).     

Affinity Maturation of Macrocyclic Peptide Modulators of Lys48-Linked Diubiquitin by a Twofold Strategy

Messenger RNA display of peptides containing non-proteinogenic amino acids, referred to as RaPID system, has become one of the leading methods to express libraries consisting of more than trillion-members of macrocyclic peptides, which allows for discovering de novo bioactive ligands. Ideal macrocyclic peptides should have dissociation constants (K_D) as low as single-digit values in the nanomolar range towards a specific target of interest. Here, a twofold strategy to discover optimized macrocyclic peptides within this affinity regime is described. First, benzyl thioether cyclized peptide libraries were explored to identify tight binding hits. To obtain more insights into critical sequence information, sequence alignment was applied to guide rational mutagenesis for the improvement of their binding affinity. Using this twofold strategy, benzyl thioether macrocyclic peptide binders against Lys48-linked ubiquitin dimer (K48-Ub2) were successfully obtained that display K_D values in the range 0.3–1.2 nm , which indicate binding two orders of magnitude stronger than those of macrocyclic peptides recently reported. Most importantly, this macrocyclic peptide also showed an improved cellular inhibition of the K48-Ub2 recognition by deubiquitinating enzymes and the 26S proteasome, resulting in the promotion of apoptosis in cancer cells.     

Synthesis and BK channel-opening activity of novel N-acylhydrazone derivatives from dehydroabietic acid

A series of hydrazone and N-acylhydrazone derivatives of dehydroabietic acid were synthesized and evaluated for BK channel-opening activities in an assay system of CHO-K1 cells expressing hBKa channels.The assay results indicated that the activities of the investigated compounds were influenced by the physicochemical properties of the substituent at hydrazone moiety.     

Hydrothermally etched titanium: a review on a promising mechano-bactericidal surface for implant applications

The growing demand for titanium-based implants and the subsequent rise in implant-associated infections necessitate novel developments in anti-infective technologies. Recent research has drawn inspiration from nature to solve this problem. The nanoscale topography observed on cicada and dragonfly wings serves as a blueprint for synthetic analogs which seek to kill bacteria on contact through mechanical forces. This type of interaction has been dubbed the mechano-bactericidal effect. Various techniques have been utilized to mimic and improve upon these natural bactericidal surfaces. Alkaline hydrothermal etching is a simple and cost-effective technique to fabricate nanoscale protrusions on titanium and its alloys. This review aims to consolidate the current knowledge surrounding how fabrication parameters lead to varying surface topographies on titanium substrates, and subsequently, how surface topography and bacterial characteristics affect bactericidal activity. The bactericidal mechanism of hydrothermally etched titanium is inferred from comparisons with similar mechano-bactericidal biomaterials. The hostility of hydrothermally etched titanium toward bacteria is discussed in contrast to the observed host cell compatibility. Last, suggestions are made for the standardization of terminology in this emerging field.     

The Zassenhaus filtration,Massey products,and representations of profinite groups

We consider the p  -Zassenhaus filtration (_Gn)$(G_n)$ of a profinite group G  . Suppose that G=S/N$G=S/N$ for a free profinite group S and a normal subgroup N of S   contained in _Sn$S_n$. Under a cohomological assumption on the n-fold Massey products (which holds, e.g., if G has p  -cohomological dimension ≤ 1), we prove that _Gn+1$G_{n+1}$ is the intersection of all kernels of upper-triangular unipotent (n+1)$(n+1)$-dimensional representations of G   over _Fp${\mathbb{F}}_p$. This extends earlier results by Miná?, Spira, and the author on the structure of absolute Galois groups of fields.     

Self-accelerating self-trapped optical beams

We present self-accelerating self-trapped beams in nonlinear optical media, exhibiting self-focusing and self-defocusing Kerr and saturable nonlinearities, as well as a quadratic response. In Kerr and saturable media such beams are stable under self-defocusing and weak self-focusing, whereas for strong self-focusing the beams off-shoot solitons while their main lobe continues to accelerate. Self-accelerating self-trapped wave packets are universal, and can also be found in matter waves, plasma, etc.     

Airy beam laser

A method to design lasers that emit an arbitrary beam profile is studied. In these lasers, output-coupling is performed by a diffraction grating that imposes a phase and amplitude distribution onto the diffracted light. A solid-state laser emitting beams with a two-dimensional Airy intensity profile is demonstrated both theoretically and experimentally. In this case, the diffraction grating adds a transverse cubic phase to the diffracted light. An Airy beam is obtained by performing optical Fourier transform of the out-coupled light. The laser beam profile and power characteristics are shown to agree with theory.