Objetivo: Determinar la tasa de recurrencia regional en pacientes diagnosticados con melanoma maligno cutáneo localizado en tronco y extre-midades, con una biopsia de ganglio centinela negativa. Métodos: Serie de casos. Se revisaron los registros de pacientes estadio clínico IB, IIA, IIB, IIIC tratados con biopsia de ganglio centinela entre enero de 2000 y diciembre de 2007. Se realizaron análisis descriptivos y se analizó la super-vivencia mediante el método de Kaplan-Meier. Resultados: Se incluyó a 170 pacientes. La mediana de seguimiento fue de 21,5 meses, con una tasa de recurrencia regional del 11,76%. La supervivencia global a 24 meses en ganglio centinela negativo fue del 100%. Conclusiones: La tasa de recurrencia regional en la serie analizada de pacientes con melanoma y ganglio linfático centinela negativo se halla dentro de lo reportado en la literatura, aunque el tiempo de seguimiento es relativamente corto.

The Supplementary material contains additional theory (derivation of CP-SCF equations, additional contributions which arise from ECPs and point charges), figures and tables supporting conclusions drawn in the main text.

The bending fatigue resistance of superelastic shape memory alloys (SMAs) is a key determinant for their reliable function in cyclic applications such as biomedical implants, adaptive actuators, and elastocaloric devices. However, conventional NiTi alloys exhibit limited fatigue life due to premature crack initiation and propagation under cyclic tensile loading. Here, we report a surface engineering strategy that overcomes this limitation by inducing a hierarchical surface architecture via pre-strain warm laser shock peening (pw-LSP). This architecture integrates a high-strength titanium nitride-enriched top layer, an ultrafine-grained layer with an inverse grain size gradient and a B19′–R–B2 phase gradient, and a substantial compressive residual stress exceeding 1 GPa. These features act synergistically to suppress crack nucleation and arrest propagation through a crack-tip shielding mechanism. As a result, the treated NiTi demonstrates a bending fatigue life exceeding 5 million cycles at a maximum surface tensile strain of 1.94%—representing a more than 3000-fold enhancement over untreated nanocrystalline NiTi. This work presents a robust and scalable approach for designing fatigue-resistant SMAs with broad implications for high-cycle, high-reliability applications. Laser-based surface treatment creates a hierarchical architecture in superelastic NiTi, integrating hard nitrides, graded grains and phases, and high compressive stress. This synergy suppresses cracking and extends bending fatigue life beyond 5 million cycles.

ABSTRACT Intelligent thermal management is essential for battery safety in sustainable development. Herein, we incorporate the “intelligence” property into aqueous zinc‐ion batteries (AZIBs) by introducing a thermo‐responsive graphene oxide/hydroxypropyl cellulose (GO/HPC) composite membrane as a smart thermal protection component. The as‐prepared membrane demonstrates exceptional flexibility and mechanical robustness, with a Young's modulus of 3.3 GPa. Taking advantage of the reversible lower critical solution temperature (LCST)‐driven phase transition of HPC, the membrane undergoes autonomous shrinkage and ionic shutdown when the ambient temperature reaches 65°C‐triggering an immediate self‐protective state to suppress thermal runaway in AZIBs. Mechanistically, the conformational transition of HPC (from hydrophilic extended chains to hydrophobic globules) upon heating simultaneously blocks Zn 2+ transport and water permeation across the membrane, while the amphiphilic GO surface guides the ordering of liquid crystalline HPC domains to optimize this dual‐functional switching behavior. Notably, AZIBs integrated with this intelligent membrane retain 92% and 80% of their initial capacity after a single thermal shutdown‐cooling cycle and after 15 repeated shutdown‐recovery cycles, respectively, confirming the reversibility of the membrane's thermo‐responsive behavior. This work provides a rational material design paradigm for the safety of AZIBs, facilitating their use in practical applications from consumer electronics to large‐scale grid energy storage.

Spin-adapted configuration state functions (CSFs) provide a compact many-electron basis for open-shell molecules. This basis is employed in one flavor of the recently introduced iterative configuration expansion (ICE) selected CI method. In this work, we implemented spin-dependent operators like spin-orbit coupling and direct spin-spin coupling for use in quasidegenerate perturbation theory on top of nonrelativistic/scalar-relativistic ICE wave functions. At the core of the new implementation are matrix elements of spin tensor excitation operators between CSFs, which are evaluated as products of orbital-specific factors. Two applications, the electron paramagnetic resonance g-factors of a Mo^III-based catalytic intermediate and the zero-field splitting in dioxygen, illustrate the capabilities of the new method.

Metabolic reprogramming controls protective and pathogenic T helper 17 (T H 17) cell responses. When naïve T cells are differentiated into T H 17 cells in vitro, the presence of the cytokine activin A promotes their maturation into a nonpathogenic state. Here, we found that nonpathogenic T H 17 cells induced by activin A displayed reduced aerobic glycolysis and increased oxidative phosphorylation (OXPHOS). In response to activin A, signaling through the adenosine A 2A receptor (A 2A R) and AMP-activated protein kinase (AMPK) enhanced OXPHOS and reprogrammed pathogenic T H 17 cells toward nonpathogenic states that did not induce central nervous system autoimmunity in a mouse model of multiple sclerosis. In pathogenic T H 17 cells, the transcriptional coactivator p300/CBP-associated factor (PCAF) increased acetylation at histone 3 Lys 9 (H3K9ac) of genes involved in aerobic glycolysis and T H 17 pathogenic programs. In contrast, in nonpathogenic activin A–treated T H 17 cells, AMPK signaling suppressed PCAF-mediated H3K9ac modification of genes involved in aerobic metabolism and enhanced H3K9ac modification of genes involved in OXPHOS and nonpathogenic T H 17 programs. Together, our findings uncover A 2A R-AMPK signaling as a central metabolic checkpoint that suppresses T H 17 cell pathogenicity.

Here, we report a one‐spot, temperature‐controlled AC electropolymerization strategy for converting graphene oxide and aniline into a crystalline, processable reduced graphene oxide (rGO)/polyaniline (PANI) composite for wearable ionic transistor textiles. By tuning the electropolymerization temperature from 4°C to 55°C under a low‐frequency triangular AC waveform, followed by mild postreduction, conformal polycrystalline PANI nanodomains are grown directly on rGO sheets. Low‐temperature synthesis yields the highest structural ordering and the lowest fraction of protonated imine species, directly linking growth conditions to mixed ionic–electronic transport behavior. The resulting rGO/PANI composite functions as an electrolyte‐gated transistor with stable operation and amplified gate response. Furthermore, the composite can be stencil printed onto cotton textiles to realize ratiometric Na + /K + sensing at constant ionic strength, highlighting its potential for scalable, wearable ion‐sensing architectures.

The advent of van der Waals (vdW) heterostructures has enabled formation of bespoke materials with atomic precision, where numerous quantum and topological phenomena have already been discovered. This atomic-layer tunability, however, comes at a cost: individual 2D layers must be picked up, moved, and placed in a deterministic manner while keeping their interfaces atomically clean. Recent advances in machine learning and robotics place even stronger emphasis on the deterministic aspect of vdW assembly. Current polymer-based transfer methods satisfy neither the determinism nor cleanliness requirements. To this end, solutions are needed where adhesion can be dynamically and deterministically controlled without leaving organic contamination. Here, we present a polymer-free transfer technique employing thin muscovite (mica) crystals. Temperature control over mica adhesion enables deterministic pick-up, stacking, and release of 2D materials, while their crystalline, inorganic nature ensures pristine interfaces and suppresses strain. Fully compatible with existing fabrication workflows, this approach enables the assembly of demanding vdW heterostructures, including those with exposed conductive layers, moiré superlattices and suspended membranes. Our method represents a promising strategy for vdW heterostructure fabrication toward its automatisation.

Carboxylate-bridged Mn(II)–Ca(II) complexes are potentially relevant for mimicking the first stages of the Oxygen-Evolving Complex (OEC) assembly process. Here, we report on new homonuclear Ca(II) and heteronuclear Mn(II)–Ca(II) complexes with carboxylate-functionalized tripodal tris(2-pyridylmethyl)amine ligands, the heptadentate H<sub>3</sub>tpaa, previously reported, and the new hexadentate H<sub>2</sub>tpada, containing respectively three and two carboxylate units. The mononuclear [Ca(Htpaa)(OH<sub>2</sub>)] (Ca<sub>1</sub>) and dinuclear [Ca(tpada)(OH<sub>2</sub>)<sub>2</sub>]<sub>2</sub> (Ca<sub>2</sub>) calcium complexes, as well as the tetranuclear [{Mn(tpaa)}<sub>2</sub>{Ca(OH<sub>2</sub>)<sub>5</sub>(μ-OH<sub>2</sub>)}<sub>2</sub>][Mn(tpaa)]<sub>2</sub> (Mn<sub>2</sub>Ca<sub>2</sub>·2Mn) and dinuclear [Mn(tpada)ClCa(OH<sub>2</sub>)<sub>2.67</sub>(MeOH)<sub>2.33</sub>]Cl (MnCa) heterometallic species have been structurally characterized; the syntheses of Ca<sub>1</sub> and Mn<sub>2</sub>Ca<sub>2</sub>·2Mn being previously reported by us (Inorg. Chem., 2015, 54, 1283). The Mn(II) and Ca(II) are linked by two μ<sub>1,1</sub>-bridging carboxylates in MnCa, while only one μ<sub>1,3</sub>-carboxylate bridge connects each Ca<sup>2+</sup> ion to each Mn(II) in Mn<sub>2</sub>Ca<sub>2</sub>. A variable number of water molecules (n = 1 to 7) are coordinated to Ca in all complexes, most of them being involved in hydrogen-bond networks, in analogy to what occurs in the photosystem II. All donor atoms of the tpaa<sup>3−</sup> and tpada<sup>2−</sup> ligands are coordinated to the Mn<sup>2+</sup> ions, despite the unusually long distance between the Mn<sup>2+</sup> ion and the tertiary amine imposed by the constraining nature of the ligands, as supported by theoretical calculations. Solid state EPR spectroscopy, in combination with DFT calculations, has also shown that the Ca<sup>2+</sup> ion has an effect on the electronic parameters (zero field splitting) of the linked Mn(II) in the case of MnCa (μ<sub>1,1</sub>-carboxylate bridges). In Mn<sub>2</sub>Ca<sub>2</sub> (μ<sub>1,3</sub>-carboxylate bridge) the Ca<sup>2+</sup> ion induces only slight structural changes in the Mn coordination sphere.

Graphene is an ideal sample support for electron microscopy experiments. Its crystalline nature and single atomic thickness make it easy for any objects placed on graphene to be identified and studied. At the same time, these advantages can easily be negated by contamination of the graphene surface, which often occurs during growth and transfer procedures. In this study, we present a new polymer-free transfer method by direct adhesion, which produces contamination-free graphene for sample support in transmission electron microscopy studies. High-angle annular dark-field scanning transmission electron microscopy and convergent beam electron diffraction images of the samples obtained using the new graphene transfer protocol show the absence of any contamination originating from the transfer procedure, and only soft contamination due to hydrocarbons is observed. These observations are supported by simulations of graphene with hydrocarbons. We also compare the new dry transfer method against two other procedures known from the previous literature. The samples prepared using the new direct polymer-free adhesion method demonstrate superior quality when compared to the samples prepared by the two other procedures.

In this study, we consider the extended Brinkman's-Darcy model for a triple diffusive convection system which consists of some parameters such as Taylor number (Ta), Solutal Rayleigh numbers (RC1 , RC2 ), and Prandtl number (Pr). To investigate the range of these parameters, a dynamical system of the Ginzburg-Landau equation is developed. The parametric analysis and comparative study of the model for the three Rayleigh numbers which leads to the clear fluid layer, sparsely packed porous layer, and densely packed porous layer is done with the help of bifurcation maps and the Lyapunov exponents. It is found that for a certain range of parameters, the system exhibits a chaotic behaviour.