Interplay between unconventional superconductivity and heavy-fermion quantum criticality: CeCu2Si2 versus YbRh2Si2

In this paper the low-temperature properties of two isostructural canonical heavy-fermion compounds are contrasted with regards to the interplay between antiferromagnetic (AF) quantum criticality and superconductivity. For CeCu₂Si₂, fully-gapped d-wave superconductivity forms in the vicinity of an itinerant three-dimensional heavy-fermion spin-density-wave (SDW) quantum critical point (QCP). Inelastic neutron scattering results highlight that both quantum critical SDW fluctuations as well as Mott-type fluctuations of local magnetic moments contribute to the formation of Cooper pairs in CeCu₂Si₂. In YbRh₂Si₂, superconductivity appears to be suppressed at T???10?mK by AF order (T_N?=?70?mK). Ultra-low temperature measurements reveal a hybrid order between nuclear and 4f-electronic spins, which is dominated by the Yb-derived nuclear spins, to develop at T_A slightly above 2?mK. The hybrid order turns out to strongly compete with the primary 4f-electronic order and to push the material towards its QCP. Apparently, this paves the way for heavy-fermion superconductivity to form at T_c?=?2?mK. Like the pressure – induced QCP in CeRhIn₅, the magnetic field – induced one in YbRh₂Si₂ is of the local Kondo-destroying variety which corresponds to a Mott-type transition at zero temperature. Therefore, these materials form the link between the large family of about fifty low-T unconventional heavy – fermion superconductors and other families of unconventional superconductors with higher T_cs, notably the doped Mott insulators of the cuprates, organic charge-transfer salts and some of the Fe-based superconductors. Our study suggests that heavy-fermion superconductivity near an AF QCP is a robust phenomenon.     

Borinostats: solid-phase synthesis of carborane-capped histone deacetylase inhibitors with a tailor-made selectivity profile

The elevated expression of histone deacetylases (HDACs) in various tumor types renders their inhibition an attractive strategy for epigenetic therapeutics. One key issue in the development of improved HDAC inhibitors (HDACis) is the selectivity for single HDAC isoforms over unspecific pan inhibition to minimize off-target toxicity. Utilizing the carborane moiety as a fine-tuning pharmacophore, we herein present a robust solid phase synthetic approach towards tailor-made HDACis meeting both ends of the selectivity spectrum, namely pan inhibition and highly selective HDAC6 inhibition.

This work describes a versatile solid phase synthesis of carborane-capped histone deacetylase inhibitors with a tunable selectivity profile and synergistic anticancer activity with bortezomib.     

Observation of a resonancelike structure in the pi +- psi' mass distribution in exclusive B-->Kpi +- psi' decays

A distinct peak is observed in the pi +/- psi' invariant mass distribution near 4.43 GeV in B-->K pi +/- psi' decays. A fit using a Breit-Wigner resonance shape yields a peak mass and width of M=4433+/-4(stat)+/-2(syst) MeV and Gamma=45-13+18(stat)-13+30(syst) MeV. The product branching fraction is determined to be B(B 0-->K -/+Z+/-(4430)) x B(Z+/-(4430)-->pi+/-psi')=(4.1+/-1.0(stat)+/-1.4(syst)) x 10(-5), where Z+/-(4430) is used to denote the observed structure. The statistical significance of the observed peak is 6.5 sigma. These results are obtained from a 605 fb(-1) data sample that contains 657 x 10(6) BB pairs collected near the Upsilon(4S) resonance with the Belle detector at the KEKB asymmetric energy e+ e- collider.     

Measurement of time-dependent CP-violating parameters in B(0)-->K_(S)(0)K_(S)(0) decays

We report a measurement of the CP-violating parameters in B;{0}-->K_{S}{0}K_{S}{0} decays based on a data sample of 657x10{6} BB[over ] pairs collected at the Upsilon(4S) resonance with the Belle detector at the KEKB asymmetric-energy e;{+}e{-} collider. In this Letter, one neutral B meson is fully reconstructed in the B;{0}-->K_{S}{0}K_{S}{0} decay mode, and the flavor of the accompanying B meson is identified by its decay products. The CP-violating parameters are measured from the asymmetry in the distributions of the proper-time interval between the two B decays: S_K_{S}{0}K_{S}{0}}=-0.38_{-0.77}{+0.69}(stat)+/-0.09(syst) and A_{K_{S}{0}K_{S}{0}}=-0.38+/-0.38(stat)+/-0.05(syst).     

Acid-catalysed liquid-to-solid transitioning of arylazoisoxazole photoswitches

Molecular photoswitches play a vital role in the development of responsive materials. These molecular building blocks are particularly attractive when multiple stimuli can be combined to bring about physical changes, sometimes leading to unexpected properties and functions. The arylazoisoxazole molecular switch was recently shown to be capable of efficient photoreversible solid-to-liquid phase transitions with application in photoswitchable surface adhesion. Here, we show that the arylazoisoxazole forms thermally stable and photoisomerisable protonated Z- and E-isomers in an apolar aprotic solvent when the pK_a of the applied acid is sufficiently low. The tuning of isomerisation kinetics from days to seconds by the pK_a of the acid not only opens up new reactivity in solution, but also the solid-state photoswitching of azoisoxazoles can be efficiently reversed with selected acid vapours, enabling acid-gated photoswitchable surface adhesion.

Molecular photoswitches are versatile components for materials with bistable and photoreversible properties. Here, we enrich the functionality of the arylazoisoxazole molecular switch by analyzing its photoresponsive protonated Z- and E-isomers.     

Activation of Metallacyclopropenes,five-membered Metallacyclocumulenes and Metallacyclopentynes of Zirconium with iBu2AlH

The recently described reaction products of zirconacyclopropenes Cp^′₂Zr(η²-Me₃SiC₂SiMe₃) and five-membered zirconacyclocumulenes (zirconacyclopenta-2,3,4-trienes) Cp*₂Zr(η⁴-1,2,3,4-RC₄R), Cp* = η⁵-pentamethylcyclopentadienyl, R = Me, Me₃Si and Ph, with i-Bu₂AlH are active catalysts in the polymerization of ethylene and in the ring opening polymerization of ε-caprolactone. Here we describe the different activity of these complexes after thermal activation or if additional i-Bu₂AlH together with water are added. These results are compared to those which were obtained with the complexes Cp₂Zr(η⁴-1,2,3,4-H₂C₄H₂), rac-(EBTHI)ZrF₂, rac-(EBTHI)ZrCl₂, [rac-(EBTHI)Zr(H)(µ-H)]₂ and rac (EBTHI)Zr(F)CH₂-CH₂(2-Py) after activation with i-Bu₂AlH together with water.     

Concise synthesis of aryl-C-nucleosides by Friedel-Crafts alkylation

A fast and simplified synthesis of 1',2'-dideoxy-1'-pyrenyl-riboside and several other C-nucleosides is shown. Shelf-stable 1-O-methyl-3,5-di-O-toluoyl-2-deoxyribose is demonstrated to serve as a versatile glycosyl donor in Lewis acid promoted Friedel-Crafts alkylations of unsubstituted pyrene and other inexpensive arenes such as fluorene and methylnaphthalene. The reaction conditions favour the formation of beta-configurated C-nucleosides which renders additional epimerisation steps unnecessary. As a result, protected beta-aryl-C-nucleosides are available directly from non-substituted arenes in three steps overall.     

Observation of B(+/-) --> p(-)pK(+/-)

We report the observation of the decay mode B(+/-) --> p(-)pK(+/-)based on an analysis of 29.4 fb(-1) of data collected by the Belle detector at KEKB. This is the first example of a b-->s transition with baryons in the final state. The p(-)p mass spectrum in this decay is inconsistent with phase space and is peaked at low mass. The branching fraction for this decay is measured to be B(B+/--->p(-)pK+/-) = [4.3(+1.1)(-0.9)(stat)+/-0.5(syst)]x 10(-6). We also report upper limits for the decays B(0)-->p(-)pK(S) and B(+/-)-->p(-)p pi(+/-).