bluuebunny/crossref_metadata_2025 huggingface dataset:
Intratumoral Injectable Redox‐Responsive Immune Niche Improves the Abscopal Effect in Radiotherapy
Authors: Au Kin Man , Swinnea J. Steven , Wang Andrew Z.
Published: November 2024

Radiotherapy (XRT) is often utilized to improve the immune checkpoint blockade response in cancer management. Such combination treatment can enhance the abscopal effect, facilitating a prolonged and durable systemic response. However, despite intense research efforts, only a minority of patients respond to this approach, and novel strategies to increase the abscopal effect are urgently needed. Here, the development of an intratumoral (i.t.) injectable nanofiber (NF)‐based tumor immune niche (TIN) that converts XRT‐treated tumors into an in situ cancer vaccine, eliciting robust systemic antitumor immunity, is reported. This NF‐based immune niche incorporates redox‐degradable anti‐CTLA‐4 (α‐CTLA‐4) nanogels (NGs) and interleukin‐2 (IL‐2) NGs for controlled release in hypoxic irradiated tumors, reversing the immunosuppressive tumor microenvironment into a pro‐inflammatory microenvironment, and expanding the tumor‐infiltrating CD8+ T cell population. Additionally, it is functionalized with polyinosinic‐polycytidylic acid (poly(I:C)) to promote antigen‐presenting cell maturation and prime neoantigen‐specific CD8+ T cells. In vitro studies demonstrate TIN's ability to prime antigen‐specific CD8+ T cells and increase antigen‐specific cell‐killing efficiency under in vitro immunosuppressive conditions. In vivo studies confirm TIN's ability to elicit robust systemic anticancer activity in mouse melanoma and colorectal cancer models without inducing severe immune‐related adverse events.
Advances in Spectro‐Microscopy Methods and their Applications in the Characterization of Perovskite Materials
Authors: Luo Yanqi , Wieghold Sarah , Nienhaus Lea
Published: November 2024

Perovskite materials are promising contenders as the active layer in light‐harvesting and light‐emitting applications if their long‐term stability can be sufficiently increased. Chemical and structural engineering are shown to enhance long‐term stability, but the increased complexity of the material system also leads to inhomogeneous functional properties across various length scales. Thus, scanning probe and high‐resolution microscopy characterization techniques are needed to reveal the role of local defects and the results promise to act as the foundation for future device improvements. A look at the parameter space: technique‐specific sample penetration depth versus probe size highlights a gap in current methods. High spatial resolution combined with a deep penetration depth is not yet achievable. However, multimodal measurement technique may be the key to covering this parameter space. In this perspective, current advanced spectro‐microscopy methods which have been applied to perovskite materials are highlighted.
RAFT Polymerization for Advanced Morphological Control: From Individual Polymer Chains to Bulk Materials
Authors: Hakobyan Karen , Ishizuka Fumi , Corrigan Nathaniel , Xu Jiangtao , Zetterlund Per B. , Prescott Stuart W. , Boyer Cyrille
Published: November 2024

Control of the morphology of polymer systems is achieved through reversible‐deactivation radical polymerization techniques such as Reversible Addition‐Fragmentation chain Transfer (RAFT). Advanced RAFT techniques offer much more than just “living” polymerization — the RAFT toolkit now enables morphological control of polymer systems across many decades of length‐scale. Morphological control is explored at the molecular‐level in the context of syntheses where individual monomer unit insertion provides sequence‐defined polymers (single unit monomer insertion, SUMI). By being able to define polymer architectures, the synthesis of bespoke shapes and sizes of nanostructures becomes possible by leveraging self‐assembly (polymerization induced self‐assembly, PISA). Finally, it is seen that macroscopic materials can be produced with nanoscale detail, based on phase‐separated nanostructures (polymerization induced microphase separation, PIMS) and microscale detail based on 3D‐printing technologies. RAFT control of morphology is seen to cross from molecular level to additive manufacturing length‐scales, with complete morphological control over all length‐scales.
Congruent Glass Composite Scintillator for Efficient High‐Energy Ray Detection
Authors: Wang Dazhao , Li Hongwei , Chen Jingfei , Hou Dianhao , Liu Xunpiao , Yu Zhuoming , Lv Shichao , Qiu Jianrong , Zhou Shifeng
Published: November 2024

The scintillator is the most crucial component in the high‐energy ray detection system. The available scintillators suffer from the insurmountable drawbacks including poor shaping ability for single crystal and ceramic and low efficiency for glass. Here, a glass composite scintillator is proposed from a congruent crystallization system which possesses both excellent processability and high scintillating yield. It can be fabricated into diverse shapes and sizes including the bulk and tiny fiber. Benefitting from the unique compositing combination with a high crystallization ratio, the glass composite exhibits a giant scintillating light yield of ≈26,000 photons per MeV. The practical application for X‐ray imaging is demonstrated and a high spatial resolution of 12 l p mm−1 is achieved. Furthermore, the fiber derived detector is built and the remote and micro‐area detection is realized. These findings not only represent a novel design concept for the development of glass composite but also suggest a great step for expanding the scope of scintillators.
Mathematical Exploration of Malaria Transmission Dynamics: Insights from Fractional Models and Numerical Simulation
Authors: Bounouiga Souad , Basti Bilal , Benhamidouche Noureddine
Published: November 2024

This study presents an innovative mathematical model denoted as the fractional SIP(H)–SI(M) model, which aims to analyze and understand the dynamics of malaria transmission and spread. This model is distinguished by incorporating memory effects through fractional differential equations, allowing for a more accurate and realistic analysis of disease spread compared to traditional models. The proposed model is applied to Algeria by estimating its parameters using recent health data (from 2000). The results revealed that the disease‐free equilibrium is stable only when the basic reproduction number is less than one, indicating that controlling the spread of malaria and possibly eradicating it can be achieved by implementing appropriate preventive measures. Simulations also demonstrated a direct correlation between the rate of infection transmission and an increase in the number of infected individuals, highlighting the need for swift action when signs of an outbreak emerge. Based on these findings, a set of preventive measures is recommended, including insecticide spraying programs, widespread distribution of insecticide‐treated bed nets, and implementation of effective treatment protocols for infected individuals. This study also emphasizes the importance of continuous monitoring of health data and updating model parameters to ensure the effectiveness and sustainability of preventive measures.
Catalytically Active Ti‐Based Nanomaterials for Hydroxyl Radical Mediated Clinical X‐Ray Enhancement
Authors: Gerken Lukas R. H. , Beckers Claire , Brugger Beatrice A. , Kissling Vera M. , Gogos Alexander , Wee Shianlin , Lukatskaya Maria R. , Schiefer Hans , Plasswilm Ludwig , Pruschy Martin , Herrmann Inge K.
Published: November 2024

Nanoparticle radioenhancement offers a promising strategy for augmenting radiotherapy by locally increasing radiation damage to tumor tissue. While past research has predominantly focused on nanomaterials with high atomic numbers, such as Au and HfO2, recent work has revealed that their radioenhancement efficacy decreases considerably when using clinically relevant megavoltage X‐rays as opposed to the orthovoltage X‐rays typically employed in research settings. Here, radiocatalytically active Ti‐based nanomaterials for clinical X‐ray therapy settings are designed. A range of candidate materials, including TiO2 (optionally decorated with Ag or Pt nanoseeds), Ti‐containing metal–organic frameworks (MOFs), and 2D Ti‐based carbides known as Ti3C2Tx MXenes, is investigated. It is demonstrated that these titanium‐based candidates remain consistently performant across a wide energy spectrum, from orthovoltage to megavoltage. This sustained performance is attributed to the catalytic generation of reactive oxygen species, moving beyond the simple physical dose enhancements associated with photoelectric effects. Beyond titania, emergent materials like titanium‐based MOFs and MXenes exhibit encouraging results, achieving dose‐enhancement factors of up to three in human soft tissue sarcoma cells. Notably, these enhancements are absent in healthy human fibroblast cells under similar conditions of particle uptake, underscoring the selective impact of titanium‐based materials in augmenting radiotherapy across the clinically relevant spectral range.
Bone‐Targeted Fluoropeptide Nanoparticle Inhibits NF‐κB Signaling to Treat Osteosarcoma and Tumor‐Induced Bone Destruction
Authors: Li Lin , Rong Guangyu , Gao Xin , Cheng Yiyun , Sun Zhengwang , Cai Xiaopan , Xiao Jianru
Published: November 2024

Osteosarcoma is a malignant bone cancer usually characterized by symptoms of bone loss due to pathologically enhanced osteoclast activity. Activated osteoclasts enhance bone resorption and promote osteosarcoma cell progression by secreting various cytokines. Intercepting the detrimental interplay between osteoclasts and osteosarcoma cells is considered as an option for osteosarcoma treatment. Here, a bone‐targeted fluoropeptide nanoparticle that can inhibit the nuclear factor kappa B (NF‐κB) signaling in both osteoclasts and osteosarcoma to address the above issue is developed. The NF‐κB essential modulator binding domain (NBD) peptide is conjugated with a fluorous tag to improve its proteolytic stability and intracellular penetration. The NBD peptide is efficiently delivered into cells after fluorination to induce apoptosis of osteocarcoma cells, and inhibits osteoclasts differentiation. The fluorous‐tagged NBD peptide is further co‐assembled with an oligo (aspartic acid) terminated fluoropeptide to form bone‐targeted peptide nanoparticles for osteosarcoma treatment. The targeted nanoparticles efficiently inhibited tumor progression and osteosarcoma‐induced bone destruction in vivo. This co‐assembled fluoropeptide nanoplatform proposed in this study offers a promising approach for targeted and intracellular delivery of peptide therapeutics in the treatment of various diseases.
Redox Mediator as Highly Efficient Charge Storage Electrode Additive for All‐Solid‐State Lithium Metal Batteries
Authors: Liu Haixing , Wang Suqing , Kong Wenhan , Liu Yangxi , Ren Wenhao , Wang Haihui
Published: November 2024

All‐solid‐state lithium metal batteries (ASSLBs) have the potential to provide a significant increase in energy density and safety. However, most ASSLBs are still suffering from low cathode loading, poor rate capability, and low attainable energy/power densities, which seriously limit their practical application. Besides developing solid electrolytes with high conductivity, constructing a highly loaded cathode with rapid reaction kinetics is also essential for achieving high‐performance ASSLBs. Herein, the methylamine hydroiodide (CH6NI) is investigated as a functional electrode additive to enable rapid Li+ transport and charge transfer in LiFePO4 (LFP) cathode, whereby the CH6NI serves as a charge storage carrier that facilitates the reaction kinetics during the delithiation and lithiation process of LFP. As a result, the ASSLB assembled with LFP@CH6NI cathode shows excellent cycling stability over 700 cycles at 2 C with a high capacity retention of 87.6%, while the cell with bare LFP cathode shows no capacity at high current rates (≥0.5 C). Moreover, the ASSLB pared with a high active loading cathode (5.6 mg cm−2) still exhibits a high specific capacity of 144.9 mAh g−1 at 0.5 C. This work provides a facile strategy that opens new possibilities for designing high‐loading electrodes for high‐performance ASSLBs.
Herbarium specimens reveal links between leaf shape of Capsella bursa‐pastoris and climate
Authors: Hightower Asia T. , Chitwood Daniel H. , Josephs Emily B.
Published: November 2024

Premise

Studies into the evolution and development of leaf shape have connected variation in plant form, function, and fitness. For species with consistent leaf margin features, patterns in leaf architecture are related to both biotic and abiotic factors. However, for species with inconsistent leaf shapes, quantifying variation in leaf shape and the effects of environmental factors on leaf shape has proven challenging.

Methods

To investigate leaf shape variation in a species with inconsistently shaped leaves, we used geometric morphometric modeling and deterministic techniques to analyze approximately 500 digitized specimens of Capsella bursa‐pastoris collected throughout the continental United States over 100 years. We generated a morphospace of the leaf shapes and modeled leaf shape as a function of environment and time.

Results

Leaf shape variation of C. bursa‐pastoris was strongly associated with temperature over its growing season, with lobing decreasing as temperature increased. While we expected to see changes in variation over time, our results show that the level of leaf shape variation was consistent over the 100 years.

Conclusions

Our findings showed that species with inconsistent leaf shape variation can be quantified using geometric morphometric modeling techniques and that temperature is the main environmental factor influencing leaf shape variation.
Should Zoo Food Be Chopped for Ruffed Lemurs? It's Not so Black and White
Authors: Davison Jenna Mae , Hammond Amy , Abernethy‐Palmer Georgia , Brereton James Edward
Published: November 2024

Whole food diets in zoos have the potential to reduce microbial contamination and keeper preparation time, whilst also reducing food nutrient breakdown. Given these benefits, it is important to determine whether there is any value in chopping up food. Lemurs (Family Lemuridae) are common in zoos, with over 7500 individuals housed globally. Given their regular occurrence in collections, plus the high incidence of frugivory, lemurs are an excellent taxon to investigate food presentation effects on behavior. A study was undertaken at Beale Wildlife Park on a group of four black‐and‐white ruffed lemurs (Varecia variegata) to investigate food presentation and preference. Animal behavior was recorded using instantaneous focal sampling at 60 s intervals to record state behaviors and continuous focal sampling to record event behaviors in 1‐h sessions. Food preference was done by recording the first three food items consumed by individual lemurs. Overall, food manipulation was significantly increased during whole food presentation allowing the lemurs to display species‐specific behaviors. Feeding and foraging were highest during very chopped food condition and inactivity was lowest in very chopped food presentation. When looking at aggressive interactions, there was an increase in stealing and locomotion with food during whole food presentation, whereas biting and startle were lower. Proving high‐value food items chopped and low‐value food items whole could reduce aggression while reduce aggression seen over high‐value food items. For food preference, sweet potato was consistently in the top three food items for all lemurs, with beetroot being the second most‐picked food item. This suggests that these individuals have a strong preference for food items high in carbohydrates. Keeper preparation time was significantly reduced during whole food preparation. Further research assessing a wider range of zoo‐housed species would be beneficial to assess the effects of food presentation on behavior.
The Scientific and Therapeutic Rationale for Off‐Label Treatments in Amyotrophic Lateral Sclerosis
Authors: Bedlack Richard , Li Xiaoyan , Evangelista Baggio Angelo , Panzetta Maria E. , Kwan Justin , Gittings Lauren M. , Sattler Rita
Published: November 2024

There are no dramatically effective pharmacological treatments for most patients with amyotrophic lateral sclerosis, a complex disease with multiple underlying mechanisms, such as neuroinflammation, oxidative stress, mitochondrial dysfunction, microbiome alteration, and antiretroviral activity. We sifted through 15 years of reviews by a group called ALSUntangled to identify 8 alternative and off‐label treatments that target ≥1 of these mechanisms, and have ≥1 human trial suggesting meaningful benefits. Given the overlapping pathological mechanisms of the highlighted products, we suggest that combinations of these treatments targeting diverse mechanisms might be worthwhile for future amyotrophic lateral sclerosis therapy development. ANN NEUROL 2025;97:15–27
Studies of Parity Violation in Atoms
Authors: Nanos Stefanos , Papigkiotis Iraklis , Antypas Dionysios
Published: November 2024

Studies of the effects of the weak interaction in atomic systems provide tests of the Standard Model of particle physics, and explore physics scenarios beyond the Standard Model. In addition, these studies can offer valuable insights into low‐energy nuclear physics. An overview of the field of atomic parity violation is provided, and implications to nuclear and particle physics and ongoing experimental efforts are discussed. Furthermore, the plans for precision measurements of the signatures of the weak interaction in atomic ytterbium are discussed.
High‐Entropy Electrolyte Driven by Multi‐Solvation Structures for Long‐Lifespan Aqueous Zinc Metal Pouch Cells
Authors: Wang Ziqing , Diao Jiefeng , Vaidyula Rinish R. , Henkelman Graeme , Mullins C. Buddie
Published: November 2024

Aqueous zinc metal batteries (AZMBs) are promising candidates for grid‐scale energy storage due to their low cost and high safety. However, the poor stability and the unfavorable freezing point of aqueous electrolytes hinder their actual application. Herein, a ternary salts‐based high‐entropy electrolyte (HEE) composed of Zn0.2Na0.4Li0.4(ClO4)1.2 ⋅ 7H2O is proposed to address the above issues. The addition of perchlorate salts with different cations reduces the size of ion clusters, significantly increases the solvation structure species, and promotes the anion‐rich Zn2+ solvation structures, resulting in an enlarged electrochemical stability window, favorable viscosity and ionic conductivity, and low freezing point. Furthermore, advanced characterization and theoretical calculations confirm that multiple types of solvation structures effectively increase the entropy of the electrolyte. As a consequence, the Zn/Zn symmetric cells in HEE can sustainably cycle for at least 1000 hours and 1500 hours under room and subzero temperatures, respectively. The Na0.33V2O5/Zn and polyaniline/Zn full cells can even last for 30000 and 20000 cycles without capacity decay at −20 °C, respectively. The pouch cells employing HEE deliver promising capacity and stability, even at high mass loading of active materials. This strategy of introducing multiple salts with different cations to construct a high‐entropy environment provides a facile approach for high‐performance and long‐lifespan AZMBs across a wide temperature range.
Regulating Interface Dipole Interaction between Ethers and Active Species Toward Highly Stable Li‐SPAN Batteries
Authors: Liu Xinyi , Wu Shuang , Hao Zhimeng , Shang Long , Guo Mao , Hou Jinze , Shao Siyuan , Li Haixia , Li Yixin , Lu Yong , Zhang Kai , Yan Zhenhua , Chen Jun
Published: November 2024

Sulfurized polyacrylonitrile (SPAN) is recognized as a promising organic cathode for long‐lifespan lithium metal batteries. Nevertheless, the irreversible cleavage/formation of multiple sulfur‐sulfur (S−S) bonds of SPAN within conventional ether‐based electrolytes results in loss of active S species, severe capacity fading and shuttle effects. Herein, we propose a new electrolyte based on dipropyl ether (PE) solvent for Li‐SPAN batteries. Benefiting from the particular chain‐coordination structure and weak dipole interactions with Li+ and active species, the resulting electrolyte not only achieves low desolvation energy barrier and high Li+ transference number, but also displays stable electrolyte‐electrode interface (EEI). Consequently, the full cells utilizing this electrolyte exhibit good cyclability, outstanding capacity retention and superior extreme‐temperature (−50 °C to 50 °C) performance. Furthermore, the Ah‐scale pouch cell with lean electrolyte (2.5 g Ah−1) achieves record cycle stability with 96.5 % capacity retention after 75 cycles, which deliver an initial specific energy density of 150 Wh kg−1 (based on the weight of the entire cell). Impressively, this strategy demonstrates universality in a series of organic electrodes employing with PE‐based electrolytes. This work highlights the strategy for modulating the dipole interaction at EEI for long‐lifespan Li‐organic batteries at extreme conditions.
Vertically Expanded Covalent Organic Frameworks for Photocatalytic Water Oxidation into Oxygen
Authors: Xie Shuailei , Liu Ruoyang , Liu Nengyi , Xu Hetao , Chen Xiong , Wang Xinchen , Jiang Donglin
Published: November 2024

Covalent organic frameworks with unique π architectures and pores could be developed as photocatalysts for transformations. However, they usually form π‐stacking layers, so that only surface layers function in photocatalysis. Here we report a strategy for developing vertically expanded frameworks to expose originally inaccessible active sites hidden in layers to catalysis. We designed covalently linked two‐dimensional cobalt(II) porphyrin layers and explored coordination bonds to connect the cobalt(II) porphyrin layers with bidentate ligands via a three‐component one‐pot polymerization. The resultant frameworks expand the interlayer space greatly, where both the up and down faces of each cobalt(II) porphyrin layer are exposed to reactants. Unexpectedly, the vertically expanded frameworks increase skeleton oxidation potentials, decrease exciton dissociation energy, improve pore hydrophilicity and affinity to water, and facilitate water delivery. Remarkably, these positive effects work collectively in the photocatalysis of water oxidation into oxygen, with an oxygen production rate of 1155 μmol g−1 h−1, a quantum efficiency of 1.24 % at 450 nm, and a turnover frequency of 1.39 h−1, which is even 5.1‐fold as high as that of the π‐stacked frameworks and ranks them the most effective photocatalysts. This strategy offers a new platform for designing layer frameworks to build various catalytic systems for chemical transformations.
Palladium Single Atom‐supported Covalent Organic Frameworks for Aqueous‐phase Hydrogenative Hydrogenolysis of Aromatic Aldehydes via Hydrogen Heterolysis
Authors: Ouyang Zhihao , Sheng Guan , Zhong Yao , Wang Jun , Cai Jianxin , Deng Shuguang , Deng Qiang
Published: November 2024

Developing a method for the tandem hydrogenative hydrogenolysis of bio‐based furfuryl aldehydes to methylfurans is crucial for synthesizing sustainable biofuels and chemicals; however, it poses a challenge due to the easy hydrogenation of the C=C bond and difficult cleavage of the C−O bond. Herein, a palladium (Pd) single‐atom‐supported covalent organic framework was fabricated and showed a unique 2,5‐dimethylfuran yield of up to 98.2 % when reacted with 5‐methyl furfuryl aldehyde in an unprecedented water solvent at 30 °C. Furthermore, it exhibited excellent catalytic universality while converting various furfuryl‐, benzyl‐, and heterocyclic aldehydes at room temperature. The analysis of the catalytic mechanism confirmed that H2 was heterolytically activated on the Pd−N pair and triggered the keto‐enol tautomerism of the covalent organic frameworks (COFs) host, resulting in H−−Pd⋅⋅⋅O−H+ sites. These sites served as novel asymmetric hydrogenation sites for the C=O group and hydrogenolysis sites for the C−OH group through a scarce SN2 mechanism. This study demonstrated remarkable bifunctional catalysis through the H2‐induced keto‐enol tautomerism of COF catalysts for the atypical preparation of methyl aromatics in a water solvent at room temperature.
Enhancing the Cumulene Character of One‐Dimensional Acetylene‐Based Systems by Stimuli‐Induced Planarization of Their Two Pro‐diradicaloid Cyclopenta[h,i]aceanthrylene Units
Authors: Fernández Álvaro Corrochano , Rivero Samara Medina , Chaurasia Sumit , Torres Tomás , Casado Juan , Bottari Giovanni
Published: November 2024

Acetylene/polyynes −(C≡C−)n and cumulenes =(C=)n are connectors widely used for the realization of one‐dimensional (1D) π‐conjugates. Although both π‐moieties are constituted by sp carbon atoms, their different bond connectivity confers distinct physicochemical properties to the resulting systems. In this context, while many acetylene/polyyne‐ and cumulene‐based derivatives have been prepared and studied, no reports have tackled the possibility to reversibly alter the acetylene/polyyne‐cumulene electronic character of these derivatives using mild conditions. Herein, we present a novel approach to enhance the cumulene character of 1D acetylene‐based conjugates consisting in the preparation of derivatives featuring an acetylene moiety connecting two pro‐diradicaloid species, namely cyclopenta[h,i]aceanthrylene (CPA), at their pro‐radical positions. A thoughtful spectroscopic study of the prepared dimers, complemented by theoretical calculations, suggest a high π‐electronic delocalization of the pro‐diradicaloid CPAs through the central acetylene spacer upon the dimers’ planarization which, in turn, increases the cumulenic character of the acetylenic π‐bridge, a feature enhanced for one of the two dimers at low temperature and in methylcyclohexane due to an aggregation‐induced planarization process. We reckon that the proposed approach offers an interesting avenue towards the realization of 1D systems which cumulenic character of the acetylenic π‐connector could be altered in response to external stimuli.
Supramolecular Spring‐Like Fe(II) Spin‐Crossover Complexes Experiencing Giant and Anisotropic Thermal Expansion Across Two Distinct Temperature Regimes
Authors: Zhao Xin‐Hua , Deng Yi‐Fei , Xi Jing , Huang Jia‐Quan , Zhang Yuan‐Zhu
Published: November 2024

Dynamic molecules with tunable chemical and physical properties in response to external stimuli hold great potential for applications in various fields such as information storage, smart molecular machines, and biomimetics. Among them, supramolecular springs and spin‐crossover (SCO) complexes can both undergo visible macroscopic changes under heat or light stimulation. In this study, we synthesized a unique trinuclear Fe(II)‐SCO complex, [(R−L)FeII{Au(CN)2}2] (R 1), using a chiral chelating ligand decorated with rotatable benzyl rings. The [FeAu2] trinuclear molecules form a 21‐helical supramolecular chain via elastic Au
Au contacts. Interestingly, the synergy between the multiple dynamic factors (SCO event, rotation of the rings, and flexibility in Au
Au distance) endows the complex with multiple switchings in both magnetism and structure, as well as the most intriguing characteristic of giant and anisotropic “breathing” feature in thermal expansion within two distinct temperature regimes. Specifically, complex R 1 undergoes two hysteretic magnetic transitions: a non‐spin transition between 360 and 380 K and an unsymmetric SCO transition in the region of 160–280 K, associated with a symmetry‐breaking event between the non‐polar and polar space groups (P212121↔P21). Both transitions are triggered/accompanied by the rotation (inward vs. outward) of the benzyl rings. Correspondingly, reversible spring‐like motions of the helical chains with the helical pitches varying from 11.345140 K to 12.509280 K then back to 11.630380 K Å are observed in the two distinct temperature regimes. This work demonstrates a significant success in incorporating both SCO and spring‐like motion in one system, paving the way for designing multifunctional dynamic materials for future devices.
Reversible Redox Probes to Determine Band‐Edge Locations and Dopant Concentrations of Nano‐TiO2 Thin‐Films: Settling the Mott‐Schottky Conundrum
Authors: Khurana Divyansh Anil , Plankensteiner Nina , Vermang Bart , Vereecken Philippe M.
Published: November 2024

Knowing the exact location of the semiconductor band‐edges is key for mechanistic insights into their use for water and CO2 photo/electrocatalysis. In this regard, a reliable strategy for nano‐semiconductors did not exist yet. We demonstrate the use of reversible redox probes on nano‐semiconductor electrodes to determine their band‐edge locations in aqueous solutions. Rectifying current‐potential (i‐U) characteristics with the high work function (i.e. more positive formal potential) Fe(CN)63−/Fe(CN)64− redox couple yielded the exact flatband potential at various pH whereas the reversible i‐U characteristics with the low work function (i.e. more negative formal potential) Ru(NH3)63+/Ru(NH3)62+ redox couple provided the conduction band‐edge location and dopant concentration for a 30 nm thin‐film n‐TiO2. The methodology can be extended to other nano‐semiconductors and serves as an alternative to and goes beyond the capabilities of the Mott‐Schottky procedure for bulk semiconductor electrodes.
Core–Shell–Satellite Au@CeO2–Pd Plasmonical Photocatalysts for Suzuki–Miyaura Coupling Reaction
Authors: Zhao Xiaohua , Liu Xiaoxiao , Liu Xiang , Li Weiyi , Wang Ping
Published: November 2024

Integration of localized surface plasmon resonance (LSPR) metallic nanocrystals into photocatalysis is an intriguing approach for light‐driven organic transformations. However, uncertain direction of hot carriers is a grand challenge, which fails to take full advantage of the LSPR excitation. In this work, core–shell gold@ceria nanosphere–supported segregated palladium species (Au@CeO2–Pd) have developed to steer the light absorption capability and charge carrier migration. Under simulated solar light irradiation, the core–shell–satellite Au@CeO2–Pd exhibited efficient light harvesting and colossal activity in the Suzuki coupling reaction. The plasmon‐induced hot electrons overpassed the Schottky barrier at the Au@CeO2 interfaces and migrated from Au core to CeO2 shell accordingly. Subsequently, the photogenerated electrons and hot electrons migrated from Au@CeO2 core–shells to Pd, which acted as an electron acceptor. Detailed photocatalytic mechanism studies revealed that both photoexcited electrons and holes were the main active species involved in the photocatalytic Suzuki coupling reaction process. In particular, the diphenyl yield over Au@CeO2–Pd catalyst was ~1.7 times higher than that of core–shell–satellite Au@SiO2–Pd, where a 19‐nm‐thick SiO2 shell was introduced to prevent the migration of hot electrons. This distinctly certified that the hot electrons transfer in the core–shell–satellite Au@CeO2–Pd under illumination played an important role to drive Suzuki reaction. Overall, this design of core–shell–satellite Au@CeO2–Pd plasmonic photocatalyst has the potential in the field of photo‐driven organic transformations.
Fabrication and Evaluation of Polyacrylate Nanocomposites Embedded With Metal Oxides as Enhanced Multipurpose Nanocarriers for Long‐Term Anti‐Inflammatory and Amazing Antimicrobial Properties
Authors: Sobh Rokaya A. , Magar Hend S. , Fahim Asmaa M. , El‐Masry Hossam M. , Hashem M. S.
Published: November 2024

The design of super‐antimicrobially active multipurpose nanocarriers as polymeric nanocomposites embedded with metal oxides with sustained drug release is beneficial in medical treatment for controlling inflammation and targeting a wide range of pathogenic microorganisms. Brilliant metal oxide nanoparticles (MOx) involving selenium dioxide, titanium dioxide, and vanadium pentoxide were well prepared in good yields, and their morphologies and structures were specified. Then they were embedded in copolymeric nanocomposites through in situ microemulsion polymerization of (E)‐2‐cyano‐N‐cyclohexyl‐3‐(dimethylamino)acrylamide (CHAA) with methyl methacrylate (MMA), dimethylaminoethyl methacrylate (DMAEMA), and acrylic acid (AA). In addition, ibuprofen was then loaded into the synthesized polymers and their nanocomposites to achieve high drug entrapment efficiency EE%, and its release behavior was studied in various simulated fluids. The produced drug‐loaded polymers and their nanocomposites were characterized using Fourier‐transform infrared spectroscopy (FT‐IR), transmission electron microscope (TEM), X‐ray diffraction (XRD), and thermogravimetric analysis (TG). Well‐defined nanospheres of polymeric‐metal oxide nanocomposites were generated in a size range of 50 nm, with ibuprofen loaded at a high encapsulation efficiency of approximately 97%. In vitro drug release was inspected for the polymer and its nanocomposites revealing that the presence of metal oxide nanoparticles resulted in prolonged and sustained release behavior for wound dressing. The antimicrobial study based on the zone of inhibition against various pathogenic microorganisms showed excellent activity against Bacillus cereus, Staphylococcus aureus, Escherichia coli, Helicobacter pylori, and Candida albicans. These findings validate the potential of these nanocomposites to serve as a viable upcoming antimicrobial agent for the treatment of human ailments.
FeBTC MOF‐Derived Fe3O4@C Nanocomposite: Controlled Synthesis and Application as Potential Adsorbent for Rhodamine Dye Elimination From Wastewater
Authors: Said Mohamed I. , Abd EL‐Wahab Mohamed M. , Sadek Alshimaa M.
Published: November 2024

This study explores the controlled synthesis of a novel Fe3O4@C magnetic nanocomposite derived from FeBTC metal–organic framework (MOF) and its application as an efficient adsorbent for the removal of rhodamine dye from wastewater. The FeBTC MOF was first synthesized and then thermally decomposed in a controlled oxygen atmosphere at 375°C (1 h) to form the Fe3O4@C nanocomposite with a magnetic Fe3O4 core embedded in a porous carbon matrix. A comprehensive characterization of the nanocomposite was performed using x‐ray diffraction (XRD), transmission electron microscopy (TEM), and x‐ray photoelectron spectroscopy (XPS) to confirm the successful formation and to evaluate its structural and morphological properties. The morphological investigation revealed that the particles of Fe3O4 had a spherical shape with diameter of 10–15 nm. The carbon coating appeared as a thin amorphous layer surrounding the Fe3O4 nanoparticles. The adsorption capacity of Fe3O4@C for rhodamine B (RhB) dye was assessed under various conditions, including different pH values, contact times, initial dye concentrations, and temperatures. Complete dye removal was attained in 45 min using 50 mg of the nanocomposite and 50 mL of 5.0 ppm RhB at the optimum pH of 9.1. Under the same experimental conditions, the highest adsorption capacity of 13.0 mg/g was obtained, but using 15.0 mg of the nanocomposite. Fe3O4@C nanocomposite exhibits high adsorption efficiency, with a maximum removal capacity of 100%, which is clearly superior to many conventional adsorbents. This performance can be attributed to the synergistic effects of the magnetic Fe3O4 and the large surface area of the carbon matrix. Kinetic models were employed to understand the adsorption mechanism. The adsorption kinetics followed a pseudo‐second‐order model. The reusability of the adsorbent was tested over multiple cycles and showed a minimal loss of performance (drops to 93.0% after five removal cycles). The study demonstrates that the Fe3O4@C nanocomposite is a promising candidate for the effective removal of organic dyes from wastewater, offering potential benefits for environmental remediation and sustainable water management.
Linear parameter varying μ synthesis robust control of CDC semi‐active suspension system for nonlinearity and uncertainty
Authors: Kou Farong , Li Shenglin , Yang Xudong
Published: November 2024

Because the continuous damping control (CDC) semi‐active suspension system has complex nonlinear and uncertain characteristics that can significantly affect the performance of the system. And in the controller design process, achieving a balance of multiple performance objectives is often difficult. Therefore, this paper designs a linear parameter varying (LPV) μ synthesis robust controller for the vibration suppression and multi‐objective control of a 7‐degree‐of‐freedom (7‐DOF) vehicle suspension system equipped with CDC dampers. Firstly, the nonlinear force model of the solenoid valve CDC damper is developed based on the actual damping variation. Considering the nonlinear forces of the coil springs, the nonlinear model of the 7‐DOF suspension system is expressed as LPV form. Further, the linear fractional transformation (LFT) method is used to analyze and reconstruct the system model for multiple parameter uncertainties of the suspension. The actuator time delays are also simulated through a frequency domain transfer function, which is considered to be an unmodeled dynamic at the input of the system. Finally, an LPV‐μ synthesis robust controller based on nonlinearity and mixed uncertainty is designed to improve car ride comfort and achieve the best relationship between comfort and handling stability. Simulation and experimental results under random disturbance conditions show that the LPV‐μ synthesis controller has better anti‐jamming performance and controllability compared to the H∞ controller and μ synthesis controller.
Combined inhibition of histone methyltransferases EZH2 and DOT1L is an effective therapy for neuroblastoma
Authors: Seneviratne Janith A. , Ravindrarajah Daenikka , Carter Daniel R. , Zhai Vicki , Lalwani Amit , Krishan Sukriti , Balachandran Anushree , Ng Ernest , Pandher Ruby , Wong Matthew , Nero Tracy L. , Wang Shudong , Norris Murray D. , Haber Michelle , Liu Tao , Parker Michael W. , Cheung Belamy B. , Marshall Glenn M.
Published: November 2024

Background

The child cancer, neuroblastoma (NB), is characterised by a low incidence of mutations and strong oncogenic embryonal driver signals. Many new targeted epigenetic modifier drugs have failed in human trials as monotherapy.

Methods

We performed a high‐throughput, combination chromatin‐modifier drug screen against NB cells. We screened 13 drug candidates in 78 unique combinations.

Results

We found that the combination of two histone methyltransferase (HMT) inhibitors: GSK343, targeting EZH2, and SGC0946, targeting DOT1L, demonstrated the strongest synergy across 8 NB cell lines, with low normal fibroblast toxicity. High mRNA expression of both EZH2 and DOT1L in NB tumour samples correlated with the poorest patient survival. Combination HMT inhibitor treatment caused activation of ATF4‐mediated endoplasmic reticulum (ER) stress responses. In addition, glutathione and several amino acids were depleted by HMT inhibitor combination on mass spectrometry analysis. The combination of SGC0946 and GSK343 reduced tumour growth in comparison to single agents.

Conclusion

Our results support further investigation of HMT inhibitor combinations as a therapeutic approach in NB.
Nanoparticles for Delivering Micro and Macromolecules for the Management of Diabetic Wounds
Authors: Sanapalli Vidyasrilekha , Haque Md Azizul , Sanapalli Bharat Kumar Reddy , Karri Veera Venkata Satyanarayana Reddy , Mondal Tonmoy Kumar , Barai Paritosh , Islam Md. Rabiul , Farahim Farha , Ali Talat , Barai Hasi Rani , Roy Madhusudan
Published: November 2024

Diabetes mellitus (DM) is a chronic metabolic disorder that affects most vital organs in the body. Approximately 463 million people were diagnosed with DM worldwide in 2019. The incidence of DM is estimated to increase by 700 million by 2045. Diabetic wounds (DWs) are among the most severe complications in people suffering from DM. Although diverse standard care treatment strategies are available for DWs, they are unsatisfactory because of the multifactorial pathophysiology of DWs. Cutting‐edge nanoparticles are increasingly being used in treating DWs. In particular, few nanoparticles naturally act as ROS scavengers, promote angiogenesis, exhibit antimicrobial activity, and form the extracellular matrix, which is considered beneficial for DW healing. The current review focused on the pivotal potential of the present nanoparticles for DW healing, emphasizing and highlighting the use of the nanoparticles in delivering micro and macromolecules in tissue regeneration for DW healing and future perspectives.
Reprogramming of Glucose Metabolism for Revisiting Hepatocellular Carcinoma Resistance to Transcatheter Hepatic Arterial Chemoembolization
Authors: Zhang Ruijie , Dai Fan , Deng Songhan , Zeng Yun , Wang Jinyang , Liu Gang
Published: November 2024

Hepatocellular carcinoma (HCC) is recognized globally as one of the most lethal tumors, presenting a significant menace to patients’ lives owing to its exceptional aggressiveness and tendency to recur. Transcatheter hepatic arterial chemoembolization (TACE) therapy, as a first‐line treatment option for patients with advanced HCC, has been proven effective. However, it is disheartening that nearly 40 % of patients exhibit resistance to this therapy. Consequently, this review delves into the metabolic aspects of glucose metabolism to explore the underlying mechanisms behind TACE treatment resistance and to propose potentially fruitful therapeutic strategies. The ultimate objective is to present novel insights for the development of personalized treatment methods targeting HCC.
Changes in starch properties during malting and their correlations with the malting quality of multiple barley cultivars
Authors: Fan Xiangyun , Zhu Juan , Dong Wenbin , Hong Yi , Lv Chao , Zhang Peng , Xu Rugen
Published: November 2024

Background and Objective

There is still a lack of information about detailed dynamic changes in starch properties during malting among multiple barley varieties and correlations of starch properties with malting qualities. In this work, compositional, physicochemical, morphological, and structural properties of starches from four barley varieties at six time points across the malting process were first investigated to better understand the starch modification of barley malting. Furthermore, a total of 30 barley varieties were used to investigate the relationship between malting qualities and starch properties. The results provide a reference for breeding high‐malting quality barley based on starch properties.

Findings

Significant decreases in starch contents, paste viscosities, relative crystallinity, as well as the ratio of 1045/1022 cm−1 of starch, were exhibited, while comparatively small changes were found in the thermal parameters during malting. Amylose and amylopectin polymers were both hydrolyzed in malting. After malting, pits and holes were discovered on the surface of some starch granules. Four parameters of peak viscosity (PV), breakdown, peak time (PeT), and pasting temperature (PT) had significant correlations with diastatic power (DP), while the above four indicators together with amylose content, total starch content, onset temperature, peak temperature, and swelling power had significant correlations with malt extract (ME).

Conclusions

The trend of changes in starch properties among all four genotypes was similar. However, the variety with better malting quality showed a greater degree of measurements in some starch characters. Starch properties are mainly related to the two malting quality indicators of DP and ME.

Significance and Novelty

PV, breakdown, PeT, and PT had significant correlations with malting qualities.
Benign paroxysmal positional vertigo: A case report in which four wrongs made a right
Authors: Young Lisa , Badihian Shervin , Zee David S. , Newman‐Toker David E. , Kerber Kevin A. , Bhandari Anita , Bhandari Rajneesh
Published: November 2024

Key Clinical Message

Repositioning maneuvers for benign paroxysmal positional vertigo (BPPV) designed to induce otoconial movement in one canal can trigger and sometimes unwittingly treat BPPV in other canals. Patients with BPPV are best managed by precisely diagnosing the canal variant and using correctly performed, standardized testing and treatment maneuvers.
Tuning Electron‐Transfer Driving Force in Photosynthetic Special Pair Models
Authors: Ramírez‐Wierzbicki Ivana , Sanchez Merlinsky Luciano , Pieslinger German E. , Domínguez Sofía , Slep Leonardo D. , Baraldo Luis M. , Cadranel Alejandro
Published: November 2024

Visible‐light excitation of a family of bimetallic ruthenium polypyridines with the formula [RuII(tpy)(bpy)(‐CN)RuII(py)4L]n+ (RuRuLn+), where L=Cl−, NCS−, DMAP and ACN, was used to prepare photoinduced mixed‐valence (PI‐MV) MLCT states as models of the photosynthetic reaction center. Ultrafast transient absorption spectroscopy allowed to monitor photoinduced IVCT bands between 6000 and 11000 cm−1. Mulliken spin densities resulting from DFT and (TD)DFT computations revealed the modulation of the charge density distribution depending on the ligand substitution pattern. Results are consistent with PI‐MV systems ranging from non‐degenerate Class II to degenerate Class III or II/III, with electronic couplings between 1000 and 3500 cm−1. These findings guide the control electron localization‐delocalization in charge‐transfer/charge‐separated excited states, like those involved in the photosynthetic reaction center.
Construction and Comparative Research of Two MOFs Proton Conducting Materials Containing Nitro Groups
Authors: Guo Yuan‐Yuan , Wang Rui‐Dong , Zhao Xu‐Hui , Lv Hong‐Bo , Wei Wei‐Ming , Wang Lei , Zhang Suo‐Shu , Du Lin , Zhao Qi‐Hua
Published: November 2024

In field of electrochemistry, there has been a growing interest in the potential applications of proton‐conducting metal‐organic frameworks (MOFs). Therefore, how to design and synthesize MOFs with high proton conductivity is considered crucial. In this study, two examples of nitro‐containing Cd‐based MOFs, MOF‐1 {[Cd3(TIPE)1.5(NO3)5Cl(H2O)2] ⋅ 17H2O}n and MOF‐2 {[Cd(TIPE)0.5(nip)] ⋅ 10H2O}n (TIPE=1,1,2,2‐tetrakis(4‐(1H‐imidazole‐1‐yl)phenyl)ethene, H2nip=5‐Nitroisophthalic Acid), had been successfully designed and synthesized, and their proton‐conducting properties were thoroughly investigated. Notably, both materials displayed peak proton conductivity at 98 % RH and 90 °C, exhibiting values of 9.13×10−3 and 3.00×10−3 S cm−1 for MOF‐1 and MOF‐2, respectively. The plausible proton conduction pathways and mechanisms were elucidated through structural analyses, water vapor adsorption studies, and the determination of activation energy (Ea) values. It was found that the difference in proton conductivity between MOF‐1 and MOF‐2 was mainly associated with the different water absorption rates of the samples. The uniqueness of this study was that for the first time conducted an in‐depth study of the role of nitrate in proton conduction, providing new ideas for designing materials with excellent proton conductivity.