Hidden magnetism uncovered in a charge ordered bilayer kagome material ScV6Sn6.

Charge ordered kagome lattices have been demonstrated to be intriguing platforms for studying the intertwining of topology, correlation, and magnetism. The recently discovered charge ordered kagome material ScV6Sn6 does not feature a magnetic groundstate or excitations, thus it is often regarded as a conventional paramagnet. Here, using advanced muon-spin rotation spectroscopy, we uncover an unexpected hidden magnetism of the charge order. We observe an enhancement of the internal field width sensed by the muon ensemble, which takes place within the charge ordered state. More importantly, the muon spin relaxation rate below the charge ordering temperature is substantially enhanced by applying an external magnetic field. Taken together with the hidden magnetism found in AV3Sb5 (A = K, Rb, Cs) and FeGe kagome systems, our results suggest ubiqitous time-reversal symmetry-breaking in charge ordered kagome lattices.

Local spectroscopic evidence for a nodeless magnetic kagome superconductor CeRu2.

We report muon spin rotation (µSR) experiments on the microscopic properties of superconductivity and magnetism in the kagome superconductor CeRu2withTc≃5 K. From the measurements of the temperature-dependent magnetic penetration depthλ, the superconducting order parameter exhibits nodeless pairing, which fits best to an anisotropics-wave gap symmetry. We further show that theTc/λ-2ratio is comparable to that of unconventional superconductors. Furthermore, the powerful combination of zero-field (ZF)-µSR and high-fieldµSR has been used to uncover magnetic responses across three characteristic temperatures, identified asT1∗≃110 K,T2∗≃65 K, andT3∗≃40 K. Our experiments classify CeRu2as an exceedingly rare nodeless magnetic kagome superconductor.

Time-reversal symmetry-breaking charge order in a kagome superconductor.

The kagome lattice1, which is the most prominent structural motif in quantum physics, benefits from inherent non-trivial geometry so that it can host diverse quantum phases, ranging from spin-liquid phases, to topological matter, to intertwined orders2-8 and, most rarely, to unconventional superconductivity6,9. Recently, charge sensitive probes have indicated that the kagome superconductors AV3Sb5 (A = K, Rb, Cs)9-11 exhibit unconventional chiral charge order12-19, which is analogous to the long-sought-after quantum order in the Haldane model20 or Varma model21. However, direct evidence for the time-reversal symmetry breaking of the charge order remains elusive. Here we use muon spin relaxation to probe the kagome charge order and superconductivity in KV3Sb5. We observe a noticeable enhancement of the internal field width sensed by the muon ensemble, which takes place just below the charge ordering temperature and persists into the superconducting state. Notably, the muon spin relaxation rate below the charge ordering temperature is substantially enhanced by applying an external magnetic field. We further show the multigap nature of superconductivity in KV3Sb5 and that the [Formula: see text] ratio (where Tc is the superconducting transition temperature and λab is the magnetic penetration depth in the kagome plane) is comparable to those of unconventional high-temperature superconductors. Our results point to time-reversal symmetry-breaking charge order intertwining with unconventional superconductivity in the correlated kagome lattice.

Unconventional Transverse Transport above and below the Magnetic Transition Temperature in Weyl Semimetal EuCd_{2}As_{2}.

As exemplified by the growing interest in the quantum anomalous Hall effect, the research on topology as an organizing principle of quantum matter is greatly enriched from the interplay with magnetism. In this vein, we present a combined electrical and thermoelectrical transport study on the magnetic Weyl semimetal EuCd_{2}As_{2}. Unconventional contribution to the anomalous Hall and anomalous Nernst effects were observed both above and below the magnetic transition temperature of EuCd_{2}As_{2}, indicating the existence of significant Berry curvature. EuCd_{2}As_{2} represents a rare case in which this unconventional transverse transport emerges both above and below the magnetic transition temperature in the same material. The transport properties evolve with temperature and field in the antiferromagnetic phase in a different manner than in the paramagnetic phase, suggesting different mechanisms to their origin. Our results indicate EuCd_{2}As_{2} is a fertile playground for investigating the interplay between magnetism and topology, and potentially a plethora of topologically nontrivial phases rooted in this interplay.

Simultaneous Nodal Superconductivity and Time-Reversal Symmetry Breaking in the Noncentrosymmetric Superconductor CaPtAs.

By employing a series of experimental techniques, we provide clear evidence that CaPtAs represents a rare example of a noncentrosymmetric superconductor which simultaneously exhibits nodes in the superconducting gap and broken time-reversal symmetry (TRS) in its superconducting state (below T_{c}≈1.5 K). Unlike in fully gapped superconductors, the magnetic penetration depth λ(T) does not saturate at low temperatures, but instead it shows a T^{2} dependence, characteristic of gap nodes. Both the superfluid density and the electronic specific heat are best described by a two-gap model comprising of a nodeless gap and a gap with nodes, rather than by single-band models. At the same time, zero-field muon-spin relaxation spectra exhibit increased relaxation rates below the onset of superconductivity, implying that TRS is broken in the superconducting state of CaPtAs, hence indicating its unconventional nature. Our observations suggest CaPtAs to be a new remarkable material that links two apparently disparate classes, that of TRS-breaking correlated magnetic superconductors with nodal gaps and the weakly correlated noncentrosymmetric superconductors with broken TRS, normally exhibiting only a fully gapped behavior.

Spin fluctuation induced Weyl semimetal state in the paramagnetic phase of EuCd2As2.

Weyl fermions as emergent quasiparticles can arise in Weyl semimetals (WSMs) in which the energy bands are nondegenerate, resulting from inversion or time-reversal symmetry breaking. Nevertheless, experimental evidence for magnetically induced WSMs is scarce. Here, using photoemission spectroscopy, we observe that the degeneracy of Bloch bands is already lifted in the paramagnetic phase of EuCd2As2. We attribute this effect to the itinerant electrons experiencing quasi-static and quasi-long-range ferromagnetic fluctuations. Moreover, the spin-nondegenerate band structure harbors a pair of ideal Weyl nodes near the Fermi level. Hence, we show that long-range magnetic order and the spontaneous breaking of time-reversal symmetry are not essential requirements for WSM states in centrosymmetric systems and that WSM states can emerge in a wider range of condensed matter systems than previously thought.

Dipolar Spin Ice States with a Fast Monopole Hopping Rate in CdEr_{2}X_{4} (X=Se, S).

Excitations in a spin ice behave as magnetic monopoles, and their population and mobility control the dynamics of a spin ice at low temperature. CdEr_{2}Se_{4} is reported to have the Pauling entropy characteristic of a spin ice, but its dynamics are three orders of magnitude faster than the canonical spin ice Dy_{2}Ti_{2}O_{7}. In this Letter we use diffuse neutron scattering to show that both CdEr_{2}Se_{4} and CdEr_{2}S_{4} support a dipolar spin ice state-the host phase for a Coulomb gas of emergent magnetic monopoles. These Coulomb gases have similar parameters to those in Dy_{2}Ti_{2}O_{7}, i.e., dilute and uncorrelated, and so cannot provide three orders faster dynamics through a larger monopole population alone. We investigate the monopole dynamics using ac susceptometry and neutron spin echo spectroscopy, and verify the crystal electric field Hamiltonian of the Er^{3+} ions using inelastic neutron scattering. A quantitative calculation of the monopole hopping rate using our Coulomb gas and crystal electric field parameters shows that the fast dynamics in CdEr_{2}X_{4} (X=Se, S) are primarily due to much faster monopole hopping. Our work suggests that CdEr_{2}X_{4} offer the possibility to study alternative spin ice ground states and dynamics, with equilibration possible at much lower temperatures than the rare earth pyrochlore examples.

Time-Reversal Symmetry Breaking in Re-Based Superconductors.

To trace the origin of time-reversal symmetry breaking (TRSB) in Re-based superconductors, we performed comparative muon-spin rotation and relaxation (µSR) studies of superconducting noncentrosymmetric Re_{0.82}Nb_{0.18} (T_{c}=8.8 K) and centrosymmetric Re (T_{c}=2.7 K). In Re_{0.82}Nb_{0.18}, the low-temperature superfluid density and the electronic specific heat evidence a fully gapped superconducting state, whose enhanced gap magnitude and specific-heat discontinuity suggest a moderately strong electron-phonon coupling. In both Re_{0.82}Nb_{0.18} and pure Re, the spontaneous magnetic fields revealed by zero-field µSR below T_{c} indicate time-reversal symmetry breaking and thus unconventional superconductivity. The concomitant occurrence of TRSB in centrosymmetric Re and noncentrosymmetric ReT (T=transition metal), yet its preservation in the isostructural noncentrosymmetric superconductors Mg_{10}Ir_{19}B_{16} and Nb_{0.5}Os_{0.5}, strongly suggests that the local electronic structure of Re is crucial for understanding the TRSB superconducting state in Re and ReT. We discuss the superconducting order parameter symmetries that are compatible with the experimental observations.

Pyridine Based Antitumour Compounds Acting at the Colchicine Site.

Antimitotics binding at the colchicine site of tubulin are important antitumour and vascular disrupting agents. Pyridines and azines are privileged scaffolds in medicinal chemistry and in recent years many colchicine site ligands (CSL) have incorporated them into their structures with the aim of improving their pharmacokinetic and pharmacodynamics properties. CSL have been classified according to their chemical structures and the chemical structures of the pyridine and azine containing antimitotic compounds are described. The designed principles behind the structural modifications and the achieved effect on the biological activity upon inclusion of these heterocycles are also discussed. Lessons from the achievements and failures have been extracted and future perspectives delineated.

1D to 2D Na+ ion diffusion inherently linked to structural transitions in Na0.7CoO2.

We report the observation of a stepwise "melting" of the low-temperature Na-vacancy order in the layered transition-metal oxide Na0.7CoO2. High-resolution neutron powder diffraction analysis indicates the existence of two first-order structural transitions, one at T1≈290 K followed by a second at T2≈400 K. Detailed analysis strongly suggests that both transitions are linked to changes in the Na mobility. Our data are consistent with a two-step disappearance of Na-vacancy order through the successive opening of first quasi-1D (T1>T>T2) and then 2D (T>T2) Na diffusion paths. These results shed new light on previous, seemingly incompatible, experimental interpretations regarding the relationship between Na-vacancy order and Na dynamics in this material. They also represent an important step towards the tuning of physical properties and the design of tailored functional materials through an improved control and understanding of ionic diffusion.

Tunable conductivity threshold at polar oxide interfaces.

The physical mechanisms responsible for the formation of a two-dimensional electron gas at the interface between insulating SrTiO(3) and LaAlO(3) have remained a contentious subject since its discovery in 2004. Opinion is divided between an intrinsic mechanism involving the build-up of an internal electric potential due to the polar discontinuity at the interface between SrTiO(3) and LaAlO(3), and extrinsic mechanisms attributed to structural imperfections. Here we show that interface conductivity is also exhibited when the LaAlO(3) layer is diluted with SrTiO(3), and that the threshold thickness required to show conductivity scales inversely with the fraction of LaAlO(3) in this solid solution, and thereby also with the layer's formal polarization. These results can be best described in terms of the intrinsic polar-catastrophe model, hence providing the most compelling evidence, to date, in favour of this mechanism.

LaBaNiO(4): a Fermi glass.

Polycrystalline samples of LaSr(1-x)Ba(x)NiO(4) show a crossover from a state with metallic transport properties for x = 0 to an insulating state as [Formula: see text]. The end member LaBaNiO(4) with a nominal nickel Ni 3d(7) configuration might therefore be regarded as a candidate for an antiferromagnetic insulator. However, we do not observe any magnetic ordering in LaBaNiO(4) down to 1.5 K, and despite its insulating transport properties several other physical properties of LaBaNiO(4) resemble those of metallic LaSrNiO(4). Based on an analysis of electrical and thermal-conductivity data as well as magnetic-susceptibility and low-temperature specific-heat measurements, we suggest that LaBaNiO(4) is a Fermi glass with a finite electron density of states at the Fermi level but these states are localized.

Spin-state transition in LaCoO3: direct neutron spectroscopic evidence of excited magnetic states.

A gradual spin-state transition occurs in LaCoO3 around T approximately 80-120 K, whose detailed nature remains controversial. We studied this transition by means of inelastic neutron scattering and found that with increasing temperature an excitation at approximately 0.6 meV appears, whose intensity increases with temperature, following the bulk magnetization. Within a model including crystal-field interaction and spin-orbit coupling, we interpret this excitation as originating from a transition between thermally excited states located about 120 K above the ground state. We further discuss the nature of the magnetic excited state in terms of intermediate-spin (t(2g)(5)e(g)(1), S=1) versus high-spin (t(2g)(4)e(g)(2), S=2) states. Since the g factor obtained from the field dependence of the inelastic neutron scattering is g approximately 3, the second interpretation is definitely favored.

A fast and simple GC MS method for lignan profiling in Anthriscus sylvestris and biosynthetically related Plant species.

A new GC-MS method for monitoring lignans was developed to study the variation in plants and elucidate the biosynthetic steps. A simple and fast extraction procedure for lyophilised plant material was developed, giving a lignan-rich extract. A GC-MS method was set up using an apolar WCOT fused silica column using a high temperature programme (150 degrees C to 320 degrees C at 15 degrees C min(-1)). This new GC-MS method gave a clear lignan profile of plant material. It was possible to show the large variation in the concentrations of deoxypodophyllotoxin (DOP), yatein and anhydropodorhizol (AHP) in Anthriscus sylvestris (L.) Hoffm. plants growing on different locations using cinchonidin as an internal standard. In contrast with existing GC methods for lignan analysis no derivatisation is needed. It is also possible to use this method for the detection of different classes of lignans in biosynthetically related plant species.

Trypanosoma cruzi: inhibition of parasite growth and respiration by oxazolo(thiazolo)pyridine derivatives and its relationship to redox potential and lipophilicity.

Chagas' disease constitutes a therapeutic challenge because presently available drugs have wide toxicity to the host and are generally ineffective in the chronic stages of the disease. A series of oxazolo(thiazolo)pyridene derivatives were studied on Trypanosoma cruzi epimastigote growth and oxygen consumption and their electrochemical (redox) potentials and lipophilicity. The derivatives produced different degrees of parasite growth and respiration inhibition on CL Brener, LQ, and Tulahuen strains of T. cruzi epimastigotes. Respiratory chain inhibition appears to be a determinant of the trypanosomicidal activity of these compounds, since a significant correlation between respiration and culture growth inhibition was found. A similar correlation was found, within the different structural subfamilies, between toxic effects and the ability of the compounds to be oxidized in aqueous media. The inhibition of respiration and of parasite growth in culture increases with the lipophilicity of the substituents on the oxazolopyridine nucleus. No difference in the action of these derivatives was found among the different parasite strains. It is concluded that these compounds may have a potential usefulness in the treatment of Chagas' disease.

Synthesis of imidazo[4,5-d]oxazolo[3,4-a]pyridines. New heterocyclic analogues of lignans.

The preparation of new analogues of lignans carrying an imidazole ring has been achieved. Starting from L-histidinol, cis and trans stereoisomers have been obtained. The synthesized products lack the cytotoxicity displayed by related podophyllotoxins and azatoxin.

Structural characterization and cytostatic activity of chlorobischolylglycinatogold(III).

Based on the ability of bile acids for vectorializing the cytostatic activity of other agents, we have designed and synthesized a new bile acid cholylglycinato Au(III) complex, named Bamet-A1. It has been characterized by means of EA (elemental analysis), FT-IR, NMR, FAB-MS (fast atom bombardment-mass spectrometry) and Vis-UV techniques. This characterization allowed us to propose a structure of the type [Au CG(O) CG(N,O) Cl] for the neutral complex, which has the composition C522H84N2O12AuCl and is very soluble in water, methanol, ethanol and DMSO (dimethylsulfoxide). The study in aqueous solution suggested a redox process for its transformation, which is accompanied by the appearance of colloidal gold phase. The behavior in 4 mM NaCl water (in order to mimic the cytoplasmatic fluid) was similar to that observed in water, while in a 150 mM NaCl (similar to extracellular fluid and serum), the apparition of a dark blue precipitate was observed. This complex displays fluorescence, which does not change when incubated with DNA obtained from E. coli. Bamet-A1 was found to inhibit the growth of a variety of cell lines. The cytostatic effect was mild against human hepatoma HepG2, mouse hepatoma Hepa 1-6, rat hepatoma McA RH-7777 and human colon adenocarcinoma LS-174T, and stronger against mouse sarcoma S180-II and mouse leukemia L-1210 cells. The appearance of colloidal Au during the process of hydrolysis under physiological conditions may explains the low cytostatic activity.

Cardenolides and diterpenes as a source of and model for positive ionotropic agents.

Taking the natural cardenolides as a model for new inotropic agents, pimaranic, cyclohexanic and hydroindenic derivatives have been synthesized and tested. Several of these derivatives are positive inotropics and two of the D3a-unsaturated bis(amidinohydrazono)hydroinenes also are selective Na(+), K(+)-ATPase inhibitors.

Design, synthesis and cytotoxic activities of naphthyl analogues of combretastatin A-4.

The 3,4,5-trimethoxyphenyl and 3-hydroxy-4-methoxyphenyl rings of combretastatin A-4 are deemed optimal for its activity as antimitotic agent. The replacement of either one by a naphthalene ring results in compounds with a potency comparable to that of the parent compound. These results show that the naphthalene ring is a good surrogate for the 3,4,5-trimethoxyphenyl or the 3-hydroxy-4-methoxyphenyl rings of combretastatin A-4 and that neither of them is essential for the antitumor activity.

Open analogues of arcyriaflavin A. Synthesis through Diels-Alder reaction between maleimides and 1-aryl-3-tert-butyldimethylsiloxy-1, 3-butadienes.

The preparation of a range of open analogues of arcyriaflavin A is described. The synthetic approach is based on the use of perhydroisoindole-1,3,5-triones as key intermediates, which were obtained via Diels-Alder methodology using 1-aryl-3-siloxy-1, 3-butadienes as starting materials. Fischer indolization and aromatization processes afforded different methoxy-substituted arylpyrrolocarbazoles. The stereochemistry and conformation of the Diels-Alder products and the regiochemistry of the indolization reactions are supported by NMR and molecular modeling studies.