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1.
ACS Nano ; 18(8): 6690-6701, 2024 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-38345899

RESUMO

In the quest for a sustainable and circular economy, it is essential to explore environmentally friendly alternatives to traditional petroleum-based materials. A promising pathway toward this goal lies in the leveraging of biopolymers derived from food waste, such as proteins and polysaccharides, to develop advanced sustainable materials. Here, we design versatile hybrid materials by hybridizing amyloid nanofibrils derived by self-assembly of whey, a dairy byproduct, with chitin nanofibrils exfoliated from the two distinct allomorphs of α-chitin and ß-chitin, extracted from seafood waste. Various hydrogels and aerogels were developed via the hybridization and reassembly of these biopolymeric nanobuilding blocks, and they were further magnetized upon biomineralization with iron nanoparticles. The pH-phase diagram highlights the significant role of electrostatic interactions in gel formation, between positively charged amyloid fibrils and negatively charged chitin nanofibrils. Hybrid magnetic aerogels exhibit a ferromagnetic response characterized by a low coercivity (<50 Oe) and a high specific magnetization (>40 emu/g) at all temperatures, making them particularly suitable for superparamagnetic applications. Additionally, these aerogels exhibit a distinct magnetic transition, featuring a higher blocking temperature (200 K) compared to previously reported similar nanoparticles (160 K), indicating enhanced magnetic stability at elevated temperatures. Finally, we demonstrate the practical application of these hybrid magnetic materials as catalysts for carbon monoxide oxidation, showcasing their potential in environmental pollution control and highlighting their versatility as catalyst supports.

2.
J Phys Condens Matter ; 36(10)2023 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-37988753

RESUMO

We report a study of the superconducting pairing of the noncentrosymmetric La4Be33Pt16alloy using muon-spin rotation and relaxation (µSR) technique. BelowTc=2.4 K, La4Be33Pt16exhibits bulk superconductivity (SC), here characterized by heat-capacity and magnetic-susceptibility measurements. The temperature dependence of the superfluid densityρsc(T), extracted from the transverse-fieldµSR measurements, reveals a nodeless SC in La4Be33Pt16. The best fit ofρsc(T)using ans-wave model yields a magnetic penetration depthλ0=542 nm and a superconducting gapΔ0=0.37 meV at zero Kelvin. The single-gapped superconducting state is further evidenced by the temperature-dependent electronic specific heatCe(T)/Tand the linear field-dependent electronic specific-heat coefficientγH(H). The zero-fieldµSR spectra collected in the normal- and superconducting states of La4Be33Pt16are almost identical, confirming the absence of an additional field-related relaxation and, thus, of spontaneous magnetic fields belowTc. The nodeless SC combined with a preserved time-reversal symmetry in the superconducting state proves that the spin-singlet pairing is dominant in La4Be33Pt16. This material represents yet another example of a complex system showing only a conventional behavior, in spite of a noncentrosymmetric structure and a sizeable spin-orbit coupling.

3.
Herit Sci ; 11(1): 43, 2023.
Artigo em Inglês | MEDLINE | ID: mdl-36873814

RESUMO

A knob bow fibula (Bügelknopffibel) of the Leutkirch type, which typologically belongs to the second half of the 4th and early 5th century CE, was excavated in 2018 in the Roman city of Augusta Raurica, present-day Kaiseraugst (AG, Switzerland). This was analyzed for the first time for its elemental composition by using the non-destructive technique of Muon Induced X-ray Emission (MIXE) in the continuous muon beam facility at the Paul Scherrer Institute (PSI). In the present work, the detection limit is 0.4 wt% with ∼ 1.5 hours of measurement time. The fibula was measured at six different positions, at a depth of 0.3-0.4 mm inside the material. The experimental results show that the fibula is made of bronze, containing the main elements copper (Cu), zinc (Zn), tin (Sn) and lead (Pb). The compositional similarities/differences between different parts of the fibula reveal that it was manufactured as two "workpieces". One workpiece consists of the knob (13.0±0.6 wt% Pb), bow (11.9±0.4 wt% Pb) and foot (12.5 ± 0.9 wt% Pb). These show a higher Pb content, suggesting a cast bronze. The spiral (3.2 ± 0.2 wt% Pb), which is part of the other workpiece, has a comparatively lower Pb content, suggesting a forged bronze.

4.
Sci Adv ; 8(43): eabq6589, 2022 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-36306356

RESUMO

Crystalline symmetry is a defining factor of the electronic band topology in solids, where many-body interactions often induce a spontaneous breaking of symmetry. Superconductors lacking an inversion center are among the best systems to study such effects or even to achieve topological superconductivity. Here, we demonstrate that TRuSi materials (with T a transition metal) belong to this class. Their bulk normal states behave as three-dimensional Kramers nodal-line semimetals, characterized by large antisymmetric spin-orbit couplings and by hourglass-like dispersions. Our muon-spin spectroscopy measurements show that certain TRuSi compounds spontaneously break the time-reversal symmetry at the superconducting transition, while unexpectedly showing a fully gapped superconductivity. Their unconventional behavior is consistent with a unitary (s + ip) pairing, reflecting a mixture of spin singlets and spin triplets. By combining an intrinsic time-reversal symmetry-breaking superconductivity with nontrivial electronic bands, TRuSi compounds provide an ideal platform for investigating the rich interplay between unconventional superconductivity and the exotic properties of Kramers nodal-line/hourglass fermions.

6.
Proc Natl Acad Sci U S A ; 118(8)2021 Feb 23.
Artigo em Inglês | MEDLINE | ID: mdl-33608457

RESUMO

Nontrivial topology in condensed-matter systems enriches quantum states of matter to go beyond either the classification into metals and insulators in terms of conventional band theory or that of symmetry-broken phases by Landau's order parameter framework. So far, focus has been on weakly interacting systems, and little is known about the limit of strong electron correlations. Heavy fermion systems are a highly versatile platform to explore this regime. Here we report the discovery of a giant spontaneous Hall effect in the Kondo semimetal [Formula: see text] that is noncentrosymmetric but preserves time-reversal symmetry. We attribute this finding to Weyl nodes-singularities of the Berry curvature-that emerge in the immediate vicinity of the Fermi level due to the Kondo interaction. We stress that this phenomenon is distinct from the previously detected anomalous Hall effect in materials with broken time-reversal symmetry; instead, it manifests an extreme topological response that requires a beyond-perturbation-theory description of the previously proposed nonlinear Hall effect. The large magnitude of the effect in even tiny electric and zero magnetic fields as well as its robust bulk nature may aid the exploitation in topological quantum devices.

7.
Sci Rep ; 10(1): 15862, 2020 Sep 28.
Artigo em Inglês | MEDLINE | ID: mdl-32985519

RESUMO

Although the frustrated (zigzag) spin chain is the Drosophila of frustrated magnetism, our understanding of a pair of coupled zigzag chains (frustrated spin ladder) in a magnetic field is still lacking. We address this problem through nuclear magnetic resonance (NMR) experiments on BiCu[Formula: see text]PO[Formula: see text] in magnetic fields up to 45 T, revealing a field-induced spiral magnetic structure. Conjointly, we present advanced numerical calculations showing that even a moderate rung coupling dramatically simplifies the phase diagram below half-saturation magnetization by stabilizing a field-induced chiral phase. Surprisingly for a one-dimensional model, this phase and its response to Dzyaloshinskii-Moriya (DM) interactions adhere to classical expectations. While explaining the behavior at the highest accessible magnetic fields, our results imply a different origin for the solitonic phases occurring at lower fields in BiCu[Formula: see text]PO[Formula: see text]. An exciting possibility is that the known, DM-mediated coupling between chirality and crystal lattice may give rise to a new kind of spin-Peierls instability.

8.
ACS Cent Sci ; 6(7): 1138-1149, 2020 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-32724848

RESUMO

Lead-halide perovskites increasingly mesmerize researchers because they exhibit a high degree of structural defects and dynamics yet nonetheless offer an outstanding (opto)electronic performance on par with the best examples of structurally stable and defect-free semiconductors. This highly unusual feature necessitates the adoption of an experimental and theoretical mindset and the reexamination of techniques that may be uniquely suited to understand these materials. Surprisingly, the suite of methods for the structural characterization of these materials does not commonly include nuclear magnetic resonance (NMR) spectroscopy. The present study showcases both the utility and versatility of halide NMR and NQR (nuclear quadrupole resonance) for probing the structure and structural dynamics of CsPbX3 (X = Cl, Br, I), in both bulk and nanocrystalline forms. The strong quadrupole couplings, which originate from the interaction between the large quadrupole moments of, e.g., the 35Cl, 79Br, and 127I nuclei, and the local electric-field gradients, are highly sensitive to subtle structural variations, both static and dynamic. The quadrupole interaction can resolve structural changes with accuracies commensurate with synchrotron X-ray diffraction and scattering. It is shown that space-averaged site-disorder is greatly enhanced in the nanocrystals compared to the bulk, while the dynamics of nuclear spin relaxation indicates enhanced structural dynamics in the nanocrystals. The findings from NMR and NQR were corroborated by ab initio molecular dynamics, which point to the role of the surface in causing the radial strain distribution and disorder. These findings showcase a great synergy between solid-state NMR or NQR and molecular dynamics simulations in shedding light on the structure of soft lead-halide semiconductors.

9.
J Am Chem Soc ; 132(6): 2064-8, 2010 Feb 17.
Artigo em Inglês | MEDLINE | ID: mdl-20102192

RESUMO

We report here on the preparation and characterization of a fullerenium salt in the solid state, where the fullerene is in the 2+ oxidized state. To succeed in this long-standing challenge, we exploit the oxidizing power of one of the strongest Lewis acids, AsF(5). The weak nucleophilic character of its conjugate base is essential in stabilizing the fullerene dication in a crystal lattice. High-resolution structural analysis of this compound, with the formula C(60)(AsF(6))(2), indicates that the highly reactive C(60)(2+) units are arranged according to a novel 1D "zigzag" polymer structure. The molecules are connected by an alternating sequence of four-membered carbon rings ([2 + 2] cycloaddition) and single C-C bonds. The long awaited high-T(c) superconductivity and magnetism, expected in a hole-doped C(60) compound, are replaced instead by a semiconducting behavior, quite probably originating from the reduced crystal and molecular symmetry upon polymerization. The small value of the energy gap (approximately 70 meV) suggests, nevertheless, the proximity of a metallic phase.

10.
Chemistry ; 11(9): 2856-61, 2005 Apr 22.
Artigo em Inglês | MEDLINE | ID: mdl-15744708

RESUMO

The magnetic behaviour of the even-electron [Ni16Pd16(CO)40]4- cluster, in its [NnBu4]+ salt, has been investigated by magnetometry and muon spin rotation/relaxation (muSR) spectroscopy. The susceptibility measurements show an exceptionally high magnetic moment corresponding to a total spin value J=2. This suggests a Hund filling of a quadruplet ground state, quite unique in carbonyl-metal clusters. SQUID magnetometry shows a departure from the Curie-Weiss law, for T>150 K, and strong deviation from a Brillouin behaviour of the magnetisation curves. muSR spectroscopy in zero applied field shows a temperature independent decay of the muon spin polarisation, similar to that of a purely paramagnetic system. The observed muon spin repolarisation in a moderate external longitudinal field, however, invalidates this simple picture and suggests the presence of a local anisotropy field acting on the cluster's magnetic moment. A consistent interpretation of magnetometry and muSR results implies the occurrence of an additional interaction of the cluster spin with an effective crystalline field. The inclusion of this interaction in a model Hamiltonian allows us to successfully reproduce both the susceptibility and magnetisation data.

11.
J Am Chem Soc ; 126(46): 15032-3, 2004 Nov 24.
Artigo em Inglês | MEDLINE | ID: mdl-15547992

RESUMO

All known fullerene polymers have interfullerene connections via either [2 + 2] cycloaddition or single C-C bonds. The high-resolution synchrotron X-ray powder diffraction technique was employed here to determine the crystal structure of the Li4C60 fulleride. We find that the ground state of Li4C60 is a two-dimensional polymer with monoclinic crystal symmetry and an unprecedented architecture, combining both the [2 + 2] cycloaddition and the single C-C bridging motifs. The small size of the Li+ cations is crucial in stabilizing the resulting tightly packed polymeric structure.

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