Geometrical frustration versus Kitaev interactions in BaCo2(AsO4)2.

Recently, Co-based honeycomb magnets have been proposed as promising candidate materials to host the Kitaev spin liquid (KSL) state. One of the front-runners is BaCo2(AsO4)2 (BCAO), where it was suggested that the exchange processes between Co2+ ions via the surrounding edge-sharing oxygen octahedra could give rise to bond-dependent Kitaev interactions. In this work, we present and analyze a comprehensive inelastic neutron scattering (INS) study of BCAO with fields in the honeycomb plane. Combining the constraints from the magnon excitations in the high-field polarized state and the inelastic spin structure factor measured in zero magnetic field, we examine two leading theoretical models: the Kitaev-type [Formula: see text] model and the XXZ[Formula: see text]model. We show that the existing experimental data can be consistently accounted for by the XXZ[Formula: see text]model but not by the [Formula: see text] model, and we discuss the implications of these results for the realization of a spin liquid phase in BCAO and more generally for the realization of the Kitaev model in cobaltates.

Optically Mediated Hydrogel-Based Ionic Diode.

Ionic diodes with environmentally modulated ion-rectifying characteristics have attracted much attention and show great promise in the construction of smart devices with environmental adaptability. One immediate challenge is to integrate stimuli responsiveness and ion rectification into one single ionic diode, which requires a close cooperation of chemical principles and device technologies. Herein, an ionic diode based on a photoresponsive hydrogel with optically mediated ion-rectifying performances is introduced. Relying on the photoresponsive concentration of proton in the hydrogel, the ionic current rectification can be prominently enhanced upon ultraviolet (UV) irradiation. A maximum ionic current rectification ratio of the optically mediated ionic diode about 4 × 105 is achieved. Furthermore, the hydrogel-based diode can serve as an AND logic gate operated by UV light and voltage bias as two independent inputs. As a proof of concept, to use the optically mediated diode is achieved to modulate the feedback of a robot with logic behaviors. This work provides a novel and valuable strategy for designing functional hydrogel-based devices with the integration of stimuli-responsiveness and logic signal processing through chemical approaches.

The impact of chemical properties of the solid-liquid-adsorbate interfaces on the entropy-enthalpy compensation involved in adsorption.

Despite extensive studies on the thermodynamic mechanism governing molecular adsorption at the solid-water interface, a comprehensive understanding of the crucial role of interface properties in mediating the entropy-enthalpy compensation during adsorption is lacking, particularly at a quantitative level. Herein, we employed two types of surface models (hydroxyapatite and graphene) along with a series of amino acids to successfully elucidate how distinct interfacial features dictate the delicate balance between entropy and enthalpy variations. The adsorption of all amino acids on the hydroxyapatite surface is an enthalpy-dominated process, where the water-induced enthalpic component of the free energy and the surface-adsorbate electrostatic interaction term alternatively act as the driving force for adsorption in different regions of the surface. Although favorable interactions are observed between amino acids and the graphene surface, the entropy-enthalpy compensation exhibits dependence on the molecular size of the adsorbates. For small amino acids, favorable enthalpy changes predominantly determine their adsorption behavior; however, larger amino acids tend to bind more tightly with the graphene surface, which is thermodynamically dominated by the entropy variations despite the structural characteristics of amino acids. This study reveals specific entropy-enthalpy mechanisms underlying amino acid adsorption at the solid-liquid interface, providing guidance for surface design and synthesis of new biomolecules.

Utilizing nanotechnology to boost the reliability and determine the vertical load capacity of pile assemblies.

Because of their high electrocatalytic activity, sensitivity, selectivity, and long-term stability in electrochemical sensors and biosensors, numerous nanomaterials are being used as suitable electrode materials thanks to developments in nanotechnology. Electrochemical sensors and biosensors are two areas where two-dimensional layered materials (2DLMs) are finding increasing utility due to their unusual structure and physicochemical features. Nanosensors, by their unprecedented sensitivity and minute scale, can probe deeper into the structural integrity of piles, capturing intricacies that traditional tools overlook. These advanced devices detect anomalies, voids, and minute defects in the pile structure with unparalleled granularity. Their effectiveness lies in detection and their capacity to provide real-time feedback on pile health, heralding a shift from reactive to proactive maintenance methodologies. Harvesting data from these nanosensors, data was incorporated into a probabilistic model, executing the reliability index calculations through Monte Carlo simulations. Preliminary outcomes show a commendable enhancement in the predictability of vertical bearing capacity, with the coefficient of variation dwindling by up to 12%. The introduction of nanosensors facilitates instantaneous monitoring and fortifies the long-term stability of pile foundations. This study accentuates the transformative potential of nanosensors in geotechnical engineering.

Photosynthesis-Mediated Intracellular Biomineralization of Gold Nanoparticles inside Chlorella Cells towards Hydrogen Boosting under Green Light.

Engineering living microorganisms to enhance green biomanufacturing for the development of sustainable and carbon-neutral energy strategies has attracted the interest of researchers from a wide range of scientific communities. In this study, we develop a method to achieve photosynthesis-mediated biomineralization of gold nanoparticles (AuNPs) inside Chlorella cells, where the photosynthesis-dominated reduction of Au3+ to Au0 allows the formed AuNPs to locate preferentially around the thylakoid membrane domain. In particular, we reveal that the electrons generated by the localized surface plasmon resonance of AuNPs could greatly augment hypoxic photosynthesis, which then promotes the generation and transferring of photoelectrons throughout the photosynthetic chain for augmented hydrogen production under sunlight. We demonstrate that the electrons from AuNPs could be directly transferred to hydrogenase, giving rise to an 8.3-fold enhancement of Chlorella cells hydrogen production independent of the cellular photosynthetic process under monochromatic 560 nm light irradiation. Overall, the photosynthesis-mediated intracellular biomineralization of AuNPs could contribute to a novel paradigm for functionalizing Chlorella cells to augment biomanufacturing.

Physical insight into the entropy-driven ion association.

The ion association is widely believed to be dominated by the favorable entropy change arising from the release of water molecules from ion hydration shells. However, no direct thermodynamic evidence exists to validate the reliability and suitability of this view. Herein, we employ complicated free energy calculations to rigorously split the free energy including its entropic and enthalpic components into the water-induced contributions and ion-ion interaction terms for several ion pairs from monatomic to polyatomic ions, spanning the size range from small kosmotropes to large chaotropes (Na+ , Cs+ , Ca2+ , F- , I- , CO3 2- , and HPO4 2- ). Our results successfully reveal that though ion associations are indeed determined by a delicate balance between the favorable entropy variation and the repulsive enthalpy change, the entropy gain dominated by the solvent occurs only for the monatomic ion pairing. The water-induced entropic contribution significantly goes against the ion pairing between polyatomic anion and cation, which is, alternatively, dominated by the favorable entropy from the ion-ion interaction term, due to the configurational arrangement of polyatomic anions involved in ion association. The structural and dynamic analysis demonstrates that the entropy penalty from the water phase is primarily ascribed to the enhanced stability of water molecules around the cation imposed by the incoming anion. Our study successfully provides a fundamental understanding of water-mediated ion associations and highlights disparate lengthscale dependencies of the dehydration thermodynamics on the specific types of ions.

Two-dimensional overdamped fluctuations of the soft perovskite lattice in CsPbBr3.

Lead halide perovskites exhibit structural instabilities and large atomic fluctuations thought to impact their optical and thermal properties, yet detailed structural and temporal correlations of their atomic motions remain poorly understood. Here, these correlations are resolved in CsPbBr3 crystals using momentum-resolved neutron and X-ray scattering measurements as a function of temperature, complemented with first-principles simulations. We uncover a striking network of diffuse scattering rods, arising from the liquid-like damping of low-energy Br-dominated phonons, reproduced in our simulations of the anharmonic phonon self-energy. These overdamped modes cover a continuum of wave vectors along the edges of the cubic Brillouin zone, corresponding to two-dimensional sheets of correlated rotations in real space, and could represent precursors to proposed two-dimensional polarons. Further, these motions directly impact the electronic gap edge states, linking soft anharmonic lattice dynamics and optoelectronic properties. These results provide insights into the highly unusual atomic dynamics of halide perovskites, relevant to further optimization of their optical and thermal properties.

Electronic properties of the bulk and surface states of Fe1+yTe1-xSex.

The idea of employing non-Abelian statistics for error-free quantum computing ignited interest in reports of topological surface superconductivity and Majorana zero modes (MZMs) in FeTe0.55Se0.45. However, the topological features and superconducting properties are not observed uniformly across the sample surface. The understanding and practical control of these electronic inhomogeneities present a prominent challenge for potential applications. Here, we combine neutron scattering, scanning angle-resolved photoemission spectroscopy, and microprobe composition and resistivity measurements to characterize the electronic state of Fe1+yTe1-xSex. We establish a phase diagram in which the superconductivity is observed only at sufficiently low Fe concentration, in association with distinct antiferromagnetic correlations, whereas the coexisting topological surface state occurs only at sufficiently high Te concentration. We find that FeTe0.55Se0.45 is located very close to both phase boundaries, which explains the inhomogeneity of superconducting and topological states. Our results demonstrate the compositional control required for use of topological MZMs in practical applications.

FAM98A promotes resistance to 5-fluorouracil in colorectal cancer by suppressing ferroptosis.

BACKGROUND: FAM98A is a microtubule-associated protein involved in cell proliferation and migration, and is frequently dysregulated in epithelial cancers. But its role in the development of colorectal cancer (CRC) cancer remains unknown. METHODS: Immunohistochemical analysis was performed to examine the expression of FAM98A in CRC samples. We also investigated the effects of abnormal expression on the biological behavior of colorectal cancer cells both in vitro and in vivo. Immunoblotting and immunoprecipitation were used to screen FAM98A-related signalling pathways and downstream factors. RESULTS: FAM98A was upregulated in CRC tissues and CRC cell lines. Overexpression of FAM98A promoted cell proliferation and recovered 5-FU suppressed CRC cell proliferation both in vitro and in vivo. In addition, the Enhanced expression of FAM98A inhibited ferroptosis in CRC cells by activating the translation of xCT in stress granules (SGs). Furthermore, we identified that metformin could reverse FAM98A-mediated 5-FU resistance in CRC cells. CONCLUSIONS: Our results for the first time indicate that FAM98A plays a critical role in promoting CRC progression, which provides a novel target for clinical drug resistance of colorectal cancer. And metformin may sensitize 5-FU in the treatment of colorectal cancer.

Incomplete genome doubling enables to consistently enhance plant growth for maximum biomass production by altering multiple transcript co-expression networks in potato.

KEY MESSAGE: Cytochimera potato plants, which mixed with diploid and tetraploid cells, could cause the highest and significantly increased biomass yield than the polyploid and diploid potato plants. Polyploidization is an important approach in crop breeding for agronomic trait improvement, especially for biomass production. Cytochimera contains two or more mixed cells with different levels of ploidy, which is considered a failure in whole genome duplication. Using colchicine treatment with diploid (Dip) potato (Solanum chacoense) plantlets, this study generated tetraploid (Tet) and cytochimera (Cyt) lines, which, respectively, contained complete and partial cells with genome duplication. Compared to the Dip potato, we observed remarkably enhanced plant growth and biomass yields in Tet and Cyt lines. Notably, the Cyt potato straw, which was generated from incomplete genome doubling, was of significantly higher biomass yield than that of the Tet with a distinctively altered cell wall composition. Meanwhile, we observed that one layer of the tetraploid cells (about 30%) in Cyt plants was sufficient to trigger a gene expression pattern similar to that of Tet, suggesting that the biomass dominance of Cyt may be related to the proportion of different ploidy cells. Further genome-wide analyses of co-expression networks indicated that down-regulation (against Dip) of spliceosomal-related transcripts might lead to differential alternative splicing for specifically improved agronomic traits such as plant growth, biomass yield, and lignocellulose composition in Tet and Cyt plants. In addition, this work examined that the genome of Cyt line was relatively stable after years of asexual reproduction. Hence, this study has demonstrated that incomplete genome doubling is a promising strategy to maximize biomass production in potatoes and beyond.

Diagnosis of Primary Cutaneous Amyloidosis by Rapid 4,6-Diamidino-2-Phenylindole Staining.

BACKGROUND: Quick and accurate diagnosis of primary cutaneous amyloidosis (PCA) may be difficult because its symptoms are often subtle and nonspecific. OBJECTIVE: We sought to review the literature on the roles of various staining methods in the diagnosis of amyloidosis and demonstrate added benefits of using rapid 4,6-diamidino-2-phenylindole (DAPI) staining in the diagnosis of PCA. METHODS: Three groups of cases, namely, PCA, neurodermatitis, and prurigo nodularis, were retrieved from a computerized pathology database for study, and their paraffin-embedded tissue blocks were cut following standard procedures. The tissue sections were stained with three stains: hematoxylin-eosin (HE), Congo red, and DAPI stains, and examined under the microscope to compare the staining patterns of these three methods. We also performed amyloid keratin and apolipoprotein E (APOE) staining on the sections of PCA in order to further support our conclusion. The PCA sections were read by junior and senior dermatopathologists for comparison. RESULTS: The sensitivity of DAPI staining for PCA was significantly higher than that of Congo red staining and HE staining (p < 0.001). This statement holds true whether the experiment was grouped in one sample or was divided into groups of junior and senior dermatopathologists (p < 0.001). The DAPI-positive staining areas, except for the nuclei, were consistent with the amyloid deposition areas. In this study, DAPI staining had a sensitivity of 98.6% and a specificity of 100%. CONCLUSION: DAPI staining could serve as a useful technique to establish the diagnosis of PCA, and its high efficacy in diagnosing PCA makes it less dependent on the experience levels of the evaluators. Additionally, the binding of DAPI to the A-T-rich sequence of double-stranded DNA suggests that amyloid may contain DNA or a similarly structured nucleic acid.

Cutaneous malakoplakia with verruciform xanthoma in the same lesion.

Cutaneous malakoplakia (CM) is a rare, chronic, granulomatous disease characterized histopathologically by Michaelis-Gutmann bodies (MGB). Verruciform xanthoma (VX) is a rare, benign lesion characterized histopathologically by epithelial papillomatous hyperplasia, local hyperkeratosis with incomplete keratosis, infiltration of foam cells and inflammatory cells in the papillary dermis. We present an elderly Chinese man with CM and coexisting VX with histological confirmation of MGB.

Strong quantum fluctuations in a quantum spin liquid candidate with a Co-based triangular lattice.

Currently under active study in condensed matter physics, both theoretically and experimentally, are quantum spin liquid (QSL) states, in which no long-range magnetic ordering appears at low temperatures due to strong quantum fluctuations of the magnetic moments. The existing QSL candidates all have their intrinsic disadvantages, however, and solid evidence for quantum fluctuations is scarce. Here, we report a previously unreported compound, [Formula: see text], a geometrically frustrated system with effective spin-1/2 local moments for Co2+ ions on an isotropic 2-dimensional (2D) triangular lattice. Magnetic susceptibility and neutron scattering experiments show no magnetic ordering down to 0.05 K. Thermodynamic measurements show that there is a tremendous amount of magnetic entropy present below 1 K in 0-applied magnetic field. The presence of localized low-energy spin fluctuations is revealed by inelastic neutron measurements. At low applied fields, these spin excitations are confined to low energy and contribute to the anomalously large specific heat. In larger applied fields, the system reverts to normal behavior as evident by both neutron and thermodynamic results. Our experimental characterization thus reveals that this material is an excellent candidate for the experimental realization of a QSL state.

Buschke-Ollendorff syndrome with LEMD3 germline stopgain mutation p.R678* presenting as multiple subcutaneous nodules with mucin deposition.

Buschke-Ollendorff syndrome (BOS; OMIM 166700) is a rare autosomal dominant disorder characterized by the existence of connective tissue nevus and/or osteopoikilosis. The skin lesions usually present as firm, yellow, or flesh-colored papules and nodules, which may coalesce into plaques and increase in size and number over time. We present a case of a 26-year-old male with multiple subcutaneous nodules on the waist and thigh for more than 20 years. Being deeply seated, his skin lesions were not visible and could only be appreciated by palpation. Accordingly, pathology showed an increase in thick, crossed, or paralleled, elastic fibers arranged between the collagen bundles in the lower part of the reticular dermis and the subcutaneous fat with mucin deposition. Heterozygous point mutation in exon 8 of the LEMD3 gene was detected, which confirmed the diagnosis of BOS. The deeply situated nature of skin lesions noted in our case has not been reported in the literature of BOS. Our case thus expands the clinical and pathological features of the disease.

Sanger's Reagent Sensitized Photocleavage of Amide Bond for Constructing Photocages and Regulation of Biological Functions.

Photolabile groups offer promising tools to study biological processes with high spatial and temporal control. In the investigation, we designed and prepared several new glycine amide derivatives of Sanger's reagent and demonstrated that they serve as a new class of photocages for Zn2+ and an acetylcholinesterase (AChE) inhibitor. We showed that the mechanism for photocleavage of these substances involves initial light-driven cyclization between the 2,4-dinitrophenyl and glycine methylene groups to form acyl benzimidazole N-oxides, which undergo secondary photoinduced decarboxylation in association with rupture of an amide bond. The cleavage reactions proceed with modest to high quantum yields. We demonstrated that these derivatives can be used in targeted intracellular delivery of Zn2+, fluorescent imaging by light-triggered Zn2+ release, and regulation of biological processes including the enzymatic activity of carbonic anhydrase (CA), negative regulation of N-methyl-d-aspartate receptors (NMDARs), and pulse rate of cardiomyocytes. The successful proof-of-concept examples described above open a new avenue for using Sanger's reagent-based glycine amides as photocages for the exploration of complex cellular functions and signaling pathways.

Topological Singularity Induced Chiral Kohn Anomaly in a Weyl Semimetal.

The electron-phonon interaction (EPI) is instrumental in a wide variety of phenomena in solid-state physics, such as electrical resistivity in metals, carrier mobility, optical transition, and polaron effects in semiconductors, lifetime of hot carriers, transition temperature in BCS superconductors, and even spin relaxation in diamond nitrogen-vacancy centers for quantum information processing. However, due to the weak EPI strength, most phenomena have focused on electronic properties rather than on phonon properties. One prominent exception is the Kohn anomaly, where phonon softening can emerge when the phonon wave vector nests the Fermi surface of metals. Here we report a new class of Kohn anomaly in a topological Weyl semimetal (WSM), predicted by field-theoretical calculations, and experimentally observed through inelastic x-ray and neutron scattering on WSM tantalum phosphide. Compared to the conventional Kohn anomaly, the Fermi surface in a WSM exhibits multiple topological singularities of Weyl nodes, leading to a distinct nesting condition with chiral selection, a power-law divergence, and non-negligible dynamical effects. Our work brings the concept of the Kohn anomaly into WSMs and sheds light on elucidating the EPI mechanism in emergent topological materials.

Entropy-Enthalpy Compensation in Peptide Adsorption on Solid Surfaces: Dependence on Surface Hydration.

Although protein adsorption at the solid-water interface is of immense importance, understanding the crucial role of the water phase in mediating protein-surface interactions is lacking, particularly due to the lack of fundamental thermodynamic data. Herein, we have performed complicated free energy calculations and successfully extracted the entropy and enthalpy changes of molecular adsorption on solids. Using the gold and graphene as the surface models with distinct affinities to the water phase, we successfully unravel the sharply opposite manners of entropy-enthalpy compensation in driving water and tripeptide adsorptions on two surfaces. Though the thermodynamic features of water adsorption on surface are enthalpically dominated based on the positions of free energy barriers and minima, the favorable entropy term significantly decreases the free energy barrier and further stabilizes the adsorbate at the adsorption site on the graphene surface. For the peptide, the shape of the adsorption free energy profile is jointly determined by the enthalpy and entropy changes, which, however, alternatively act the driving force to promote the peptide adsorption on the Au surface and graphene surface. The distinct structural and dynamic properties of solid-liquid interfaces account for the special role of the interfacial water phase in regulating the competitive relationship between the entropy and enthalpy variations.

Strain-Induced Spin-Nematic State and Nematic Susceptibility Arising from 2×2 Fe Clusters in KFe_{0.8}Ag_{1.2}Te_{2}.

Spin nematics break spin-rotational symmetry while maintaining time-reversal symmetry, analogous to liquid crystal nematics that break spatial rotational symmetry while maintaining translational symmetry. Although several candidate spin nematics have been proposed, the identification and characterization of such a state remain challenging because the spin-nematic order parameter does not couple directly to experimental probes. KFe_{0.8}Ag_{1.2}Te_{2} (K_{5}Fe_{4}Ag_{6}Te_{10}, KFAT) is a local-moment magnet consisting of well-separated 2×2 Fe clusters, and in its ground state the clusters order magnetically, breaking both spin-rotational and time-reversal symmetries. Using uniform magnetic susceptibility and neutron scattering measurements, we find a small strain induces sizable spin anisotropy in the paramagnetic state of KFAT, manifestly breaking spin-rotational symmetry while retaining time-reversal symmetry, resulting in a strain-induced spin-nematic state in which the 2×2 clusters act as the spin analog of molecules in a liquid crystal nematic. The strain-induced spin anisotropy in KFAT allows us to probe its nematic susceptibility, revealing a divergentlike increase upon cooling, indicating the ordered ground state is driven by a spin-orbital entangled nematic order parameter.

Physical origin underlying the prenucleation-cluster-mediated nonclassical nucleation pathways for calcium phosphate.

The involvement of prenucleation clusters (PNCs) in crystallization from a supersaturated solution has been recently admitted within the framework of nonclassical nucleation theory; however, little is known about PNCs, at the quantitative level, for their formation mechanism and stability, the new phase formed by them, as well as their impact on nucleation barriers. Herein, using the sophisticated free energy calculations with a cumulative simulation time of over 5 µs, we identify a thermodynamically favored pathway of the PNC-mediated nucleation for calcium phosphate, starting with the ion pair association in solution. We demonstrate that such an ion association occurs not only between cations and anions, but also for the polyatomic species with charges of the same sign, which, in fact, leads to PNC formation via the consecutive coordination of the phosphate ions to calcium. The free energy decomposition calculations illustrate that the water phase is capable to either hinder or promote ion association for the abovementioned processes, and its specific role is intricately related to the characteristics of the hydration shell around calcium ions. The favorable interactions between the highly charged species play a crucial role in stabilizing the PNC complexes and the aggregates formed by PNCs. Furthermore, our present work reveals that the uptake of an extra calcium ion is the first and mandatory step to trigger PNC aggregation into amorphous calcium phosphate (ACP) by eliminating the related free energy barriers. Our theoretical study successfully provides quantitative explanations to a large set of experimental data in the field, which is currently under intense discussions associated with the nonclassical nucleation mechanism. The combination of computational methods developed in our present work offers a feasible and general solution to quantitatively and systematically study ion associations and crystal nucleation/growth in an aqueous solution at the atomic level, which are normally inaccessible to most of the existing experimental acquisitions.

Successful voriconazole treatment of Talaromyces marneffei infection in an HIV-negative patient with osteolytic lesions.

Talaromyces marneffei (T. marneffei) is a dimorphic fungus that causes systemic infection in immunocompromised patients. Here, we present a case of T. marneffei infection in an immunocompetent patient with an osteolytic lesion. Diagnosis was established by fungal culture. The patient responded rapidly to intravenous voriconazole, followed by oral voriconazole. We reviewed 18 reported cases of T. marneffei infection with osteolytic lesions, which suggests a much higher rate of osteolytic lesions in immunocompetent patients than previously thought.