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At least 955 records · Page 53

Calcium-Ion Binding Mediates the Reversible Interconversion of Cis and Trans Peroxido Dicopper Cores

Coupled dinuclear copper oxygen cores (Cu 2 O 2 ) featured in type III copper proteins (hemocyanin, tyrosinase, catechol oxidase) are vital for O 2 transport and substrate oxidation in many organisms. μ-1,2-cis peroxido dicopper cores ( C P) have been proposed as key structures in the early stages of O 2 binding in these proteins; their reversible isomerization to other Cu 2 O 2 cores are directly relevant to enzyme function. Furthermore, despite the relevance of such species to type III copper proteins and the broader interest in the properties and reactivity of bimetallic C P cores in biological and synthetic systems, the properties and reactivity of C P Cu 2 O 2 species remain largely unexplored. Herein, we report the reversible interconversion of μ-1,2-trans peroxido ( T P) and C P dicopper cores. Ca II mediates this process by reversible binding at the Cu 2 O 2 core, highlighting the unique capability for metal-ion binding events to stabilize novel reactive fragments and control O 2 activation in biomimetic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Calcium‐Ion Binding Mediates the Reversible Interconversion of Cis and Trans Peroxido Dicopper Cores

Abstract Coupled dinuclear copper oxygen cores (Cu 2 O 2 ) featured in type III copper proteins (hemocyanin, tyrosinase, catechol oxidase) are vital for O 2 transport and substrate oxidation in many organisms. μ ‐1,2‐ cis peroxido dicopper cores ( C P ) have been proposed as key structures in the early stages of O 2 binding in these proteins; their reversible isomerization to other Cu 2 O 2 cores are directly relevant to enzyme function. Despite the relevance of such species to type III copper proteins and the broader interest in the properties and reactivity of bimetallic C P cores in biological and synthetic systems, the properties and reactivity of C P Cu 2 O 2 species remain largely unexplored. Herein, we report the reversible interconversion of μ ‐1,2‐ trans peroxido ( T P ) and C P dicopper cores. Ca II mediates this process by reversible binding at the Cu 2 O 2 core, highlighting the unique capability for metal‐ion binding events to stabilize novel reactive fragments and control O 2 activation in biomimetic systems.

Vargo, Natasha P.↗

Micron-size Silicon Monoxide Asymmetric Membranes for Highly Stable Lithium Ion Battery Anode

To meet the increasing demand for high energy density lithium ion batteries for electric vehicles and mobile electronics, it is mandatory to make revolutionary changes in electrode materials and chemistry. In this report, micron-size silicon monoxide powders are utilized to fabricate asymmetric membranes via a phase inversion method. We investigate the effects of carbonization temperature, silicon monoxide concentration and glues on membrane microstructure and electrochemical performance. It is also observed that silicon monoxide powders in the membranes consist of silicon with multiple oxidation states. All silicon monoxide asymmetric membrane electrodes are characteristic of significantly improved cycling stability as compared to the control silicon monoxide electrode. The best cycling performance is achieved from the asymmetric membrane with lower silicon monoxide content and using carboxymethyl cellulose as the glue. 95% initial capacity can be retained after 110 cycles at 400 mA g -1 for the membrane with ~33 wt.% silicon monoxide. Its initial capacity loss is only 23.1% with an average coulombic efficiency of 99.82% over 110 cycles.

25 ENERGY STORAGE↗

Enhancing the Multifunctional Photocatalytic Activity of Sustainable Magnetic Nanoparticles

The development of efficient photocatalytic materials has intensified in response to increasing emphasis on sustainable energy conversion and environmental restoration. However, the excessive use and indiscriminate release of heavy metals from photocatalytic nanoparticles pose potential environmental risks. This study provides insights into optimizing visible-light-active photocatalysts to enhance their photocatalytic properties and stability. Specifically, cobalt doping and controlled pH modulation are employed on the modified Fe 3 O 4 , forming two distinct samples: Co@Fe 3 O 4 -B (base-treated) and Co@Fe 3 O 4 -A (acid-treated) nanoparticles. Microscopic characterization reveals that Co@Fe 3 O 4 -A undergoes a phase transition to hematite, whereas Co@Fe 3 O 4 -B retains its mixed-phase configuration. Spectroscopic analyses confirm that the cobalt dopants decorate the outskirts of each nanoparticle, forming a core–shell structure. However, Co@Fe 3 O 4 -B exhibit Co 2+ states with a high oxygen vacancy content, whereas Co@Fe 3 O 4 -A contain mixed Co 2+/3+ states. The high density of defect states in the Co@Fe 3 O 4 -B results in superior photocatalytic efficiency, achieving near-complete oxidation of furfuraldehyde (97% conversion) and 5-hydroxymethylfurfural (94% conversion), as well as effective degradation of toluene (78% conversion). This study demonstrates that the combined approach of doping and pH treatment is promising for the surface-defect engineering of photocatalysts, enhancing their multifunctional performance and reusability for sustainable energy conversion.

Fe3 O4 nanoparticles↗

Rapid Solidification of Sn-Cu-Al Alloys for High-Reliability, Lead-Free Solder: Part II. Intermetallic Coarsening Behavior of Rapidly Solidified Solders After Multiple Reflows

Controlling the size, dispersion, and stability of intermetallic compounds in lead-free solder alloys is vital to creating reliable solder joints regardless of how many times the solder joints are melted and resolidified (reflowed) during circuit board assembly. In this article, the coarsening behavior of Cu x Al y and Cu 6 Sn 5 in two Sn-Cu-Al alloys, a Sn-2.59Cu-0.43Al at. pct alloy produced via drip atomization and a Sn-5.39Cu-1.69Al at. pct alloy produced via melt spinning at a 5-m/s wheel speed, was characterized after multiple (1-5) reflow cycles via differential scanning calorimetry between the temperatures of 293 K and 523 K (20 °C and 250 °C). Little-to-no coarsening of the Cu x Al y particles was observed for either composition; however, clustering of Cu x Al y particles was observed. For Cu 6 Sn 5 particle growth, a bimodal size distribution was observed for the drip atomized alloy, with large, faceted growth of Cu 6 Sn 5 observed, while in the melt spun alloy, Cu 6 Sn 5 particles displayed no significant increase in the average particle size, with irregularly shaped, nonfaceted Cu 6 Sn 5 particles observed after reflow, which is consistent with shapes observed in the as-solidified alloys. The link between original alloy composition, reflow undercooling, and subsequent intermetallic coarsening behavior was discussed by using calculated solidification paths. As a result, the reflowed microstructures suggested that the heteroepitaxial relationship previously observed between the Cu x Al y and the Cu 6 Sn 5 was maintained for both alloys.

36 MATERIALS SCIENCE↗

Dystonia-4 (DYT4)-associated TUBB4A mutants exhibit disorganized microtubule networks and inhibit neuronal process growth

Highlights: • Dystonia-4-associated TUBB4A mutants (R2G) exhibit disorganized tubulin networks. • Dystonia-4-associated TUBB4A mutants (A271T) exhibit disorganized tubulin networks. • Dystonia-4-associated mutants have diminished ability to interact with alpha-type tubulins. • Dystonia-4-associated mutants show inhibited neurite growth in a neuronal cell line. Dystonia-1 (DYT1) is an autosomal dominant early-onset torsion form of dystonia, a neurological disease affecting movement. DYT1 is the prototypic hereditary dystonia and is caused by the mutation of the tor1a gene. The gene product has chaperone functions important for the control of protein folding and stability. Dystonia-4 (DYT4) is another autosomal dominant dystonia that is characterized by onset in the second to third decade of progressive laryngeal dysphonia. DYT4 is associated with the mutation of the tubb4a gene, although it remains to be understood how disease-associated mutation affects biochemical as well as cell biological properties of the gene product as the microtubule component (a tubulin beta subunit). Herein we demonstrate that DYT4-associated TUBB4A missense mutants (Arg2-to-Gly or Ala271-to-Thr) form disorganized tubulin networks in cells. Transfected mutants are indeed expressed in cytoplasmic regions, as observed in wild-type transfectants. However, mutant proteins do not exhibit typical radial tubulin networks. Rather, they have diminished ability to interact with tubulin alpha subunits. Processes do not form in sufficient amounts in cells of the N1E-115 neuronal cell line expressing each of these mutants as compared to parental cells. Together, DYT4-associated TUBB4A mutants themselves form aberrant tubulin networks and inhibit neuronal process growth, possibly explaining progress through the pathological states at cellular levels.

60 APPLIED LIFE SCIENCES↗

Magnetic and mechanical properties of grain-refined Dy-free Nd-Fe-B sintered magnets

In this work, the effects of grain size on magnetic and mechanical properties of Dy-free Nd-Fe-B sintered magnets were studied. The grain size of the sintered magnets was varied by using different sized Dy-free Nd-Fe-B alloy feedstock powders which were ball milled to different extents. Increasing the ball milling time from 7 to 11 h caused the average particle size of the powders to decrease from 3.6 to 2.1 µm, while the average grain size of the corresponding sintered magnets decreased from 5.0 to 4.0 µm. The intrinsic coercivity Hcj and maximum energy product (BH) max of these magnets increased from 11.6 to 13.7 kOe and 41.6 to 43.6 MGOe, respectively. The finer grain magnets exhibited better thermal stability, as indicated by a smaller temperature coefficient of H cj (-0.71%/°C). With extending ball milling time to 15 h, the magnetic properties of the magnets deteriorate, while the flexural strengths first decrease and then increase. The flexural strength improvement is attributed to the increased Oxygen content in the magnets due to finer grains. The coercivity enhancement by reduction of grain size is a promising approach to develop Dy-free Nd-Fe-B sintered magnets with better thermal stability. It is important to control the Oxygen contents in the magnets to compromise both magnetic and mechanical properties.

36 MATERIALS SCIENCE↗

In situ high-temperature Raman spectroscopy for online EAF slag analysis

Real-time monitoring of slag chemistry is critical for optimizing Electric Arc Furnace (EAF) steelmaking operations, where dynamic variations in slag composition directly influence slag foaming, refractory degradation, and thermal efficiency. Conventional techniques such as X-ray fluorescence (XRF), Fourier-transform infrared (FTIR), and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDS) are commonly used to analyze slag composition, but their offline nature and equipment constraints limit their applicability for online monitoring in harsh industrial environments. To address this challenge, we present an in situ, high-temperature analytical approach that integrates Raman spectroscopy with a custom designed fiber-optic probe for real-time slag characterization at 1550 °C. The system enables non destructive spectral acquisition from molten slags, providing molecular-level insights into silicate polymerization and iron oxidation states. Eight synthetic slag samples were evaluated, and key Raman features—such as Q n silicate units and FeO₄/FeO₆ coordination environments—were identified and quantitatively correlated with slag basicity and Fe₂O₃ content. The results demonstrate agreement between Raman spectral ratios and bulk slag chemistry, validating the method’s capability to track compositional and structural changes under molten temperature. This work establishes the feasibility of deploying fiber-optic Raman probe for online EAF slag monitoring and highlights their potential to support closed-loop control strategies, thereby enhancing process stability, refractory protection, and steel quality in industrial steelmaking applications.

47 OTHER INSTRUMENTATION↗

Drug delivery system for an anticancer agent, chlorogenate-Zn/Al-layered double hydroxide nanohybrid synthesised using direct co-precipitation and ion exchange methods

A nano-structured drug-inorganic clay hybrid involving an active anticancer compound, which is chlorogenic acid (CA) intercalated into Zn/Al-layered double hydroxide, has been assembled via ion-exchange and co-precipitation methods to form a nanohybrid CZAE (a chlorogenic acid-Zn/Al nanohybrid synthesised using an ion-exchange method) and CZAC (a chlorogenic acid-Zn/Al nanohybrid synthesised using a direct method), respectively. The X-ray diffraction (XRD) results confirmed that the CA-LDH had a hybrid structure in which the anionic chlorogenate is arranged between the interlayers as a horizontal monolayer at 90 and 20° angles from the x axis for CZAE and CZAC, respectively. Both nanohybrids have the properties of mesoporous materials. The high loading percentage of chlorogenic acid (approximately 43.2% for CZAE and 45.3% for CZAC) with basal spacings of 11.7 and 12.6 Å for CZAE and CZAC, respectively, corroborates the successful intercalation of chlorogenic acid into the interlayer gallery of layered double hydroxides. Free chlorogenic acid and the synthesised nanocomposites (CZAE, CZAC) were assessed for their cytotoxicity against various cancer cells. The Fourier transform infrared data supported the formation of both nanohybrids, and a thermal analysis showed that the nanohybrids are more thermally stable than their counterparts. The chlorogenate shows a sustained release, and the release rate of chlorogenate from CZAE and CZAC nanohybrids at pH 7.4 is remarkably lower than that at pH 4.8 due to their different release mechanisms. The release rate of chlorogenate from both nanohybrids can be described as pseudo-second order. The present investigation revealed the potential of the nanohybrids to enhance the in vitro anti-tumour effect of chlorogenic acid in liver and lung cancer cells in vitro. - Highlights: • We intercalated chlorogenic into Zn/Al-layered double hydroxide by ion-exchange and coprecipitation methods. • The two methods gave nanocomposites with slightly different physico-chemical properties. • Chlorogenate-zinc aluminium layered double hydroxide nanohybrids have the potential to be used as a controlled release formulation. • The thermal stability of chlorogenic acid is markedly enhanced upon the intercalation process. • The inhibition of cancer cell growth is higher for nanohybrids than for free chlorogenic acid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The cytoskeletal inhibitors latrunculin A and blebbistatin exert antitumorigenic properties in human hepatocellular carcinoma cells by interfering with intracellular HuR trafficking

The impact of the RNA-binding protein HuR for the post-transcriptional deregulation of tumor-relevant genes is well established. Despite of elevations in HuR expression levels, an increase in cytoplasmic HuR abundance in many cases correlates with a high grade of malignancy. Here, we demonstrated that administration of the actin-depolymerizing macrolide latrunculin A, or blebbistatin, an inhibitor of myosin II ATPase activity, caused a dose- and time-dependent reduction in the high cytoplasmic HuR content of HepG2 and Huh7 hepatocellular carcinoma (HCC) cells. Subcellular fractionation revealed that in addition, both inhibitors strongly attenuated cytoskeletal and membrane-bound HuR abundance and conversely increased the HuR amount in nuclear cell fractions. Concomitant with changes in intracellular HuR localization, both cytoskeletal inhibitors markedly decreased the half-lives of cyclooxygenase-2 (COX-2), cyclin A and cyclin D{sub 1} encoding mRNAs resulting in a significant reduction in their expression levels in HepG2 cells. Importantly, a similar reduction in the expression of these HuR targets was achieved by a RNA interference (RNAi)-mediated knockdown of either HuR or nonmuscle myoin IIA. Using polysomal fractionation, we further demonstrate that the decrease in cytoplasmic HuR by latrunculin A or blebbistatin is accompanied by a marked change in the allocation of HuR and its mRNA cargo from polysomes to ribonucleoprotein (RNP) particles. Functionally, the basal migration and prostaglandin E{sub 2} synthesis are similarly impaired in inhibitor-treated and stable HuR-knockdown HepG2 cells. Our data demonstrate that interfering with the actomyosin-dependent HuR trafficking may comprise a valid therapeutic option for antagonizing pathologic posttranscriptional gene expression by HuR and furthermore emphasize the potential benefit of HuR inhibitory strategies for treatment of HCC. - Highlights: • We tested the effects of latrunculin A and blebbistatin on different HuR activities. • Both cytoskeletal inhibitors disturbed the RNP-polysome HuR allocation in HepG2 cells. • Accordingly, both inhibitors reduced the stability and levels of HuR controlled mRNAs. • Functionally, important HuR-triggered cell functions were impaired by both compounds. • Targeting of HuR trafficking implies a useful approach for novel antitumor therapy.

60 APPLIED LIFE SCIENCES↗

Tuning the Performance of Single-Atom Electrocatalysts: Support-Induced Structural Reconstruction

We present that creating active and stable electrocatalysts remains a highly desirable and critical goal in the fields of catalysis and clean energy conversion. Single-atom catalyst (SAC), as a new research frontier in heterogeneous catalysis, has demonstrated emerging prospects for many electrocatalytic reactions. Support assisted pyrolysis approaches are widely used in the synthesis of single-atom electrocatalysts. While extensive efforts have been devoted to increase the loading of the atomically dispersed metal sites, the role of the support in creating these active metal sites remains largely unexplored. Herein, we compare catalysts created by support-free and support-assisted pyrolysis of vitamin B12 and cobalt tetramethoxyphenylporphyrin, respectively, and demonstrate an important effect of support-induced structural reconstruction that directly controls the activation of SAC. Electrochemical studies show support-free catalysts are inactive for oxygen reduction reaction whereas the support-assisted pyrolysis yields highly active catalysts using the same molecular precursors. X-ray absorption spectroscopy experiments reveal that both the metal-nitrogen coordination and the type of nitrogen species are different in these two types of samples, which leads to a difference in the d-band of the cobalt metal center and ultimately controls the catalytic activity and stability. In conclusion, this new insight provides a unique perspective on how to tune the electrocatalytic performances of SAC at the molecular level.

30 DIRECT ENERGY CONVERSION↗

Controlling the Reduction of Chelated Uranyl to Stable Tetravalent Uranium Coordination Complexes in Aqueous Solution

The solution-state interactions between octadentate hydroxypyridinone (HOPO) and catecholamide (CAM) chelating ligands and uranium were investigated and characterized by UV-visible spectrophotometry and X-ray absorption spectroscopy (XAS), as well as electrochemically via spectroelectrochemistry (SEC) and cyclic voltammetry (CV) measurements. Depending on the selected chelator, we demonstrate the controlled ability to bind and stabilize U IV , generating with 3,4,3-LI(1,2-HOPO), a tetravalent uranium complex that is practically inert toward oxidation or hydrolysis in acidic, aqueous solution. At physiological pH values, we are also able to bind and stabilize U IV to a lesser extent, as evidenced by the mix of U IV and U VI complexes observed via XAS. Finally, CV and SEC measurements confirmed that the U IV complex formed with 3,4,3-LI(1,2-HOPO) is redox inert in acidic media, and U VI ions can be reduced, likely proceeding via a two-electron reduction process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

In-situ liquid cell transmission electron microscopy investigation on oriented attachment of gold nanoparticles

Inside a liquid solution, oriented attachment (OA) is now recognized to be as important a pathway to crystal growth as other, more conventional growth mechanisms. However, the driving force that controls the occurrence of OA is still poorly understood. Here, using in-situ liquid cell transmission electron microscopy, we demonstrate the ligand-controlled OA of citrate-stabilized gold nanoparticles at atomic resolution. Our data reveal that particle pairs rotate randomly at a separation distance greater than twice the layer thickness of adsorbed ligands. In contrast, when the particles get closer, their ligands overlap and guide the rotation into a directional mode until they share a common {111} orientation, when a sudden contact occurs accompanied by the simultaneous expulsion of the ligands on this surface. Firstprinciple calculations confirm that the lower ligand binding energy on {111} surfaces is the intrinsic reason for the preferential attachment at this facet, rather than on other low-index facets.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

β-Barrel proteins tether the outer membrane in many Gram-negative bacteria

Gram-negative bacteria have a cell envelope that comprises an outer membrane (OM), a peptidoglycan (PG) layer and an inner membrane (IM). The OM and PG are load-bearing, selectively permeable structures that are stabilized by cooperative interactions between IM and OM proteins. In Escherichia coli , Braun’s lipoprotein (Lpp) forms the only covalent tether between the OM and PG and is crucial for cell envelope stability; however, most other Gram-negative bacteria lack Lpp so it has been assumed that alternative mechanisms of OM stabilization are present. In this work we used a glycoproteomic analysis of PG to show that β-barrel OM proteins are covalently attached to PG in several Gram-negative species, including Coxiella burnetii, Agrobacterium tumefaciens and Legionella pneumophila . In C. burnetii , we found that four different types of covalent attachments occur between OM proteins and PG, with tethering of the β-barrel OM protein BbpA becoming most abundant in the stationary phase and tethering of the lipoprotein LimB similar throughout the cell cycle. Using a genetic approach, we demonstrate that the cell cycle-dependent tethering of BbpA is partly dependent on a developmentally regulated L,D-transpeptidase (Ldt). We use our findings to propose a model of Gram-negative cell envelope stabilization that includes cell cycle control and an expanded role for Ldts in covalently attaching surface proteins to PG.

59 BASIC BIOLOGICAL SCIENCES↗

Continuous symmetry breaking in a two-dimensional Rydberg array

Spontaneous symmetry breaking underlies much of our classification of phases of matter and their associated transitions. The nature of the underlying symmetry being broken determines many of the qualitative properties of the phase; this is illustrated by the case of discrete versus continuous symmetry breaking. Indeed, in contrast to the discrete case, the breaking of a continuous symmetry leads to the emergence of gapless Goldstone modes controlling, for instance, the thermodynamic stability of the ordered phase. Here, we realize a two-dimensional dipolar XY model that shows a continuous spin-rotational symmetry using a programmable Rydberg quantum simulator. We demonstrate the adiabatic preparation of correlated low-temperature states of both the XY ferromagnet and the XY antiferromagnet. In the ferromagnetic case, we characterize the presence of a long-range XY order, a feature prohibited in the absence of long-range dipolar interaction. In conclusion, our exploration of the many-body physics of XY interactions complements recent works using the Rydberg-blockade mechanism to realize Ising-type interactions showing discrete spin rotation symmetry.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Gate-tunable gigantic lattice deformation in VO{sub 2}

We examined the impact of electric field on crystal lattice of vanadium dioxide (VO{sub 2}) in a field-effect transistor geometry by in-situ synchrotron x-ray diffraction measurements. Whereas the c-axis lattice parameter of VO{sub 2} decreases through the thermally induced insulator-to-metal phase transition, the gate-induced metallization was found to result in a significant increase of the c-axis length by almost 1% from that of the thermally stabilized insulating state. We also found that this gate-induced gigantic lattice deformation occurs even at the thermally stabilized metallic state, enabling dynamic control of c-axis lattice parameter by more than 1% at room temperature.

36 MATERIALS SCIENCE↗

Control voltage and power fluctuations when connecting wind farms

Voltage, frequency, active power and reactive power are very important parameters in terms of power quality. These parameters are followed when connecting any power plant, the more the connection of wind farms. Connecting wind farms to the electricity system must not cause interference outside the limits set by regulations. Modern solutions for fast and automatic voltage control and power fluctuations using electronic control systems of reactive power flows. FACTS (Flexible Alternating Current Transmision System) systems, established on the basis of power electronic circuits ensure control of electrical status quantities to achieve the necessary transfer of power to the power grid. FACTS devices can quickly control parameters and sizes of state power lines, such as impedance line voltages and phase angles of the voltages of the two ends of the line. Their use can lead to improvement in power system operation by increasing the transmission capacity of power lines, power flow control lines, improved static and transient stability reserve.

24 POWER TRANSMISSION AND DISTRIBUTION↗