bluuebunny/crossref_metadata_2025 huggingface dataset:
Tumor Microenvironment‐Activatable Metal‐Phenolic Nanoformulations for Ultrasound‐Boosted Ferroptosis through Triple Regulatory Pathways
Authors: Liu Zhendong , Liu Sainan , Liu Bin , Meng Qi , Yuan Meng , Ma Xinyu , Wang Jiwei , Ma Ping'an , Lin Jun
Published: July 2024

Despite its effectiveness in exterminating tumor cells, ferroptosis is seriously hampered by the high expression of antioxidant glutathione (GSH) and the inadequacy of endogenous H2O2 in tumors. Herein, metal‐phenolic nanoformulations (FNCP NFs) composed of sonosensitizer Chlorin e6 (Ce6), the phenolic GSH consumer naphthazarin, and Fe3+, followed by the modification of PEG2000, are strategically designed and fabricated for ultrasound‐boosted ferroptosis in tumor cells through triple regulatory pathways. The carrier‐free FNCP NFs can rapidly dissociate under tumor microenvironment response with the assistance of ultrasound, releasing Fe2+, Ce6, and naphthazarin. Ce6 and Fe2+ are capable of producing singlet oxygen (1O2) and hydroxyl radicals (·OH) by ultrasound‐activated sonodynamic therapy and Fenton reaction‐mediated chemodynamic therapy (CDT), respectively, which not only induce apoptotic cell death but also lead to the effective accumulation of lipid peroxidation (LPO), resulting in ferroptosis. Meanwhile, the released naphthazarin and the self‐cycling valence alternations of Fe3+/Fe2+ promote the significant decrease of intracellular GSH contents, further inducing the inactivation of glutathione peroxidase 4 (GPX4) and the up‐regulation of LPO levels, eventually realizing the synergistically enhanced ferroptosis. This facile and feasible design for versatile metal‐phenolic nanoformulations offers a new strategy for effectively improving ferroptosis efficiency and multimodal cancer therapies.
Reversible Crystalline‐Crystalline Transitions in Chalcogenide Phase‐Change Materials
Authors: Liu Bin , Li Kaiqi , Zhou Jian , Sun Zhimei
Published: July 2024

Phase‐change random access memory (PCRAM) is one of the most technologically mature candidates for next‐generation non‐volatile memory and is currently at the forefront of artificial intelligence and neuromorphic computing. Traditional PCRAM exploits the typical phase transition and electrical/optical contrast between non‐crystalline and crystalline states of chalcogenide phase‐change materials (PCMs). Currently, traditional PCRAM faces challenges that vastly hinder further memory optimization, for example, the high‐power consumption, significant resistance drift, and the contradictory nature between crystallization speed and thermal stability, nearly all of them are related to the non‐crystalline state of PCMs. In this respect, a reversible crystalline‐to‐crystalline phase transition can solve the above problems. This review delves into the atomic structures and switching mechanisms of the emerging atypical crystalline‐to‐crystalline transitions, and the understanding of the thermodynamic and kinetic features. Ultimately, an outlook is provided on the future opportunities that atypical all‐crystalline phase transitions offer for the development of a novel PCRAM, along with the key challenges that remain to be addressed.
Optimizing Blade‐Coated Tin–lead Perovskite Solar Cells and Tandems with Multi‐Carboxyl and Amino Group Integration
Authors: Shen Weicheng , Fang Hongyi , Pu Dexin , Zheng Wenwen , Zhang Xuhao , Li Guang , Huang Lishuai , Zhou Shun , Chen Weiqing , Zhou Yuan , Feng Zhuo , Liang Jiwei , Zhou Jin , Qin Pingli , Fang Guojia , Ke Weijun
Published: July 2024

Mixed tin–lead (Sn–Pb) perovskites often face a daunting challenge: rapid and uncontrollable crystallization, leading to a plethora of defects and significant stress. This issue is particularly exacerbated during the blade‐coating preparation of scalable Sn–Pb perovskite films. In this study, a facile strategy involving the addition of ammonium citrate (AC) to narrow‐bandgap mixed Sn–Pb perovskite precursors is introduced. AC, armed with its arsenal of multiple carboxyl and amino groups, acts as a virtuoso conductor, orchestrating controlled crystal growth by harmonizing with Pb2+ and Sn2+ ions. This addition significantly boosts the crystallinity of the perovskite films, alleviates interface stress, inhibits Sn2+ oxidation, and mitigates interfacial defects. Consequently, The blade‐coated AC‐incorporated mixed Sn–Pb perovskite solar cells achieve a high photovoltaic conversion efficiency of nearly 21%. Furthermore, extending this strategy to two‐terminal all‐perovskite tandem solar cells yielded a remarkable maximum efficiency of 27.20%. This work presents an effective strategy for producing efficient blade‐coated mixed Sn–Pb perovskite solar cells, heralding a pathway toward scalable fabrication of all‐perovskite tandem solar cells.
Rapid Synthesis of Functions‐Integrated Hydrogel as a Self‐Powered Wound Dressing for Real‐Time Drug Release and Health Monitoring
Authors: Li Haiyu , Zhang Hui , Peng Yangrui , Liu Xinxin , Du Jie , Liao Jianhe
Published: July 2024

A bio‐hydrogel is prepared via a low‐cost and time‐saving strategy and is studied as a self‐powered wound dressing for precision medicine and health monitoring. Promoted by a dual self‐catalytic pair composed of Fe3+ and catechol, gelation time is dramatically accelerated to 15 s and the hydrogel can be freely modeled at −18 °C without losing flexibility. As smart wound dressing, the required properties such as self‐healing, self‐adhesion, antibacterial, and sensing stability, are integrated into one hydrogel. TA@CNC offers abundant hydrogen bond and metal‐ligand coordination which facilitate the hydrogel with a self‐healing efficiency of 91.6%. Owing to the catechol in TA@CNC, hydrogel can adhere to multiple substrates including skin, and show good antibacterial activity. Inspired by a fruit battery, a self‐powered wound dressing is fabricated, which exhibits excellent correlation and efficiency in real‐time monitoring of body activity and drug release. In vivo experiments prove that efficient drug release of hydrogel dressing significantly accelerate wound healing. Additionally, the dressing exhibits excellent biocompatibility and has no negative impacts on organs. Herein, a smart wound dressing that is different from the traditional way is proposed. As a self‐powered device, it can be integrated with wireless devices and is expected to participate in promising applications.
Long‐Term Culture of Human Pluripotent Stem Cells in Xeno‐Free Condition Using Functional Polymer Films
Authors: Cho Younghak , Lee Hana , Jeong Wonji , Jung Kwang Bo , Lee Sun Young , Park Seonghyeon , Yeun Jemin , Kwon Ohman , Son Jin Gyeong , Lee Tae Geol , Son Mi‐Young , Im Sung Gap
Published: July 2024

Human pluripotent stem cells (hPSCs), encompassing human embryonic stem cells (hESCs) and human induced pluripotent stem cells (hiPSCs), hold immense potential in regenerative medicine, offering new opportunities for personalized cell therapies. However, their clinical translation is hindered by the inevitable reliance on xenogeneic components in culture environments. This study addresses this challenge by engineering a fully synthetic, xeno‐free culture substrate, whose surface composition is tailored systematically for xeno‐free culture of hPSCs. A functional polymer surface, pGC2 (poly(glycidyl methacrylate‐grafting‐guanidine‐co‐carboxylic acrylate)), offers excellent cell‐adhesive properties as well as non‐cytotoxicity, enabling robust hESCs and hiPSCs growth while presenting cost‐competitiveness and scalability over Matrigel. This investigation includes comprehensive evaluations of pGC2 across diverse experimental conditions, demonstrating its wide adaptability with various pluripotent stem cell lines, culture media, and substrates. Crucially, pGC2 supports long‐term hESCs and hiPSCs expansion, up to ten passages without compromising their stemness and pluripotency. Notably, this study is the first to confirm an identical proteomic profile after ten passages of xeno‐free cultivation of hiPSCs on a polymeric substrate compared to Matrigel. The innovative substrate bridges the gap between laboratory research and clinical translation, offering a new promising avenue for advancing stem cell‐based therapies.
Algorithm for Reproducible Analysis of Semiconducting 2D Nanomaterials Based on UV‐VIS Spectroscopy
Authors: Kubetschek Nico , Backes Claudia , Goldie Stuart
Published: July 2024

Rapid and reliable analysis of liquid dispersions of 2D materials is essential for fully harnessing their potential, allowing size and quality validation before subsequent processing or device fabrication. Existing UV‐VIS extinction spectroscopy‐based metrics, particularly those related to thickness, have shown promise but rely on manual data processing, which can introduce irreproducibility and user errors. To address this challenge and enable uniform analysis across laboratories, a freely available program is developed for the reproducible analysis of nanosheet dispersions. Specifically, a smoothing routine is applied to the spectral data, takes the second derivative, and use integral areas to find the wavelength of exciton transitions. This program enables rapid measurement of nanosheet concentration, length, and thickness by UV‐VIS spectroscopy and thickness metrics are refined for eight common 2D nanomaterials. The program and methodology are freely available for use and allow metrics for new materials to be implemented easily in the future.
A Stable High‐Performance Zn‐Ion Batteries Enabled by Highly Compatible Polar Co‐Solvent
Authors: Yang Shuo , Wu Guangpeng , Zhang Jing , Guo Yuning , Xue Kui , Zhang Yongqi , Zhu Yuanmin , Li Tao , Zhang Xiaofeng , Zhou Liujiang
Published: July 2024

Uncontrollable growth of Zn dendrites, irreversible dissolution of cathode material and solidification of aqueous electrolyte at low temperatures severely restrict the development of aqueous Zn‐ion batteries. In this work, 2,2,2‐trifluoroethanol (TFEA) with a volume fraction of 50% as a highly compatible polar‐solvent is introduced to 1.3 M Zn(CF3SO3)2 aqueous electrolyte, achieving stable high‐performance Zn‐ion batteries. Massive theoretical calculations and characterization analysis demonstrate that TFEA weakens the tip effect of Zn anode and restrains the growth of Zn dendrites due to electrostatic adsorption and coordinate with H2O to disrupt the hydrogen bonding network in water. Furthermore, TFEA increases the wettability of the cathode and alleviates the dissolution of V2O5, thus improving the capacity of the full battery. Based on those positive effects of TFEA on Zn anode, V2O5 cathode, and aqueous electrolyte, the Zn//Zn symmetric cell delivers a long cycle‐life of 782 h at 5 mA cm−2 and 2 mA h cm−2. The full battery still declares an initial capacity of 116.78 mA h g−1, and persists 87.73% capacity in 2000 cycles at −25 °C. This work presents an effective strategy for fully compatible co‐solvent to promote the stability of Zn anode, V2O5 cathode and aqueous electrolyte for high‐performance Zn‐ion batteries.
Minimally invasive surgery versus open gastrectomy for older patients with gastric cancer: A propensity score‐matching analysis
Authors: Yamamoto Masaaki , Omori Takeshi , Masuike Yasunori , Shinno Naoki , Hara Hisashi , Sugase Takahito , Kanemura Takashi , Takeno Atsushi , Hirao Motohiro , Miyata Hiroshi
Published: July 2024

Aim

To compare minimally invasive and open surgery for older patients with gastric cancer.

Methods

This study included 464 consecutive patients with gastric cancer aged ≥75 years who underwent open or laparoscopic gastrectomy at our institution from January 2004 to December 2018. We performed propensity score‐matching and compared short‐ and long‐term outcomes between the two groups.

Results

After matching, 332 patients were included in the study (166 in each group). The laparoscopy group had a longer operative time, lesser blood loss, and shorter hospital stays than the open surgery group (all p < 0.020). The laparoscopy group had a lower complication rate than the open surgery group (p = 0.002). No significant differences were noted in the 3‐y overall, recurrence‐free, and disease‐free survival between the groups (all p > 0.200).

Conclusion

Minimally invasive surgery for older patients with gastric cancer may be more beneficial than open gastrectomy in terms of blood loss and hospital stay.
Salt tolerance in a neotropical orchid in the absence of local adaptation to salt spray
Authors: de Lima Thales M. , Silva Simone F. , Ribeiro Rafael V. , Sánchez‐Vilas Julia , Pinheiro Fabio
Published: July 2024

Premise

Salt tolerance has rarely been investigated regionally in the neotropics and even more rarely in Orchidaceae, one of the largest families. Therefore, investigating local adaptation to salt spray and its physiological basis in Epidendrum fulgens, a neotropical orchid species, brings important new insights.

Methods

We assessed the degree of salt tolerance in E. fulgens by testing whether coastal populations are more tolerant to salt, which could point to local adaptation. To understand the physiological basis of such salt tolerance, we exposed wild‐collected individuals to salt spray for 60 days, then measured leaf expansion, osmotic potential, sodium leaf concentration, chlorophyll leaf index, chlorophyll fluorescence, relative growth rate, and pressure–volume curves.

Results

There is no local adaptation to salt spray since both inland and coastal plants have a high tolerance to salt stress. This tolerance is explained by the ability to tolerate high concentrations of salt in leaf tissues, which is related to the high succulence displayed by this species.

Conclusions

We showed an unprecedented salt tolerance level for an orchid species, highlighting our limited knowledge of that trait beyond the traditional studied groups. Another interesting finding is that salt tolerance in E. fulgens is linked to succulence, is widespread, and is not the result of local adaptation. We suggest that E. fulgens and its allied species could be an interesting group to explore the evolution of important traits related to tolerance to salt stress, like succulence.
Benign and Selective Amination of Lignins towards Aromatic Biobased Building Blocks with Primary Amines
Authors: Wybo Nathan , Duval Antoine , Avérous Luc
Published: July 2024

Lignin is a widely available second‐generation biopolymer and the main potential source of renewable aromatic building blocks. Lignin‐based polyamines offer great potential in applications based on chemical and materials sciences. However, common aminations techniques for lignin usually involve toxic chemicals and generate hindered and low reactivity amines.

In this study, we developed two new, simple, and benign 2‐step methodologies for the elaboration of lignin‐based polyamines from different technical lignins (kraft, soda and organosolv) with a selectivity towards reactive primary amines. These methods involve grafting amide groups onto lignin followed by a hydrolysis step. Non‐toxic heterocyclic compounds N‐acetyl‐2‐oxazolidinone and 2‐methyl‐2‐oxazoline were used as amidation agents. Hydrolysis was performed in acetone‐water mixtures. Reactions were studied on model compounds and optimized on lignins. Aminated lignins were fully characterized and primary amines were quantified using quantitative 19F NMR.

Our methods generated aminated lignins with low apparent molar masses and high solubility in water and solvents. Nitrogen contents of the products ranged between 2.0 and 3.5 mmol/g with reactive primary amines counts up to 1.7 mmol/g. These soluble and reactive lignin‐based polyamines offer great potential as a replacement for fossil‐based polyamines in e.g., the synthesis of aromatic polymer materials or as potential chelating, antibacterial agents.
Dyotropic Rearrangement of an Iron–Aluminium Complex
Authors: Stadler Benedek , Gorgas Nikolaus , Elliott Stuart J. , Crimmin Mark R.
Published: July 2024

Ligand exchange processes at metal complexes underpin their reactivity and catalytic applications. While mechanisms of ligand exchange at single site complexes are well established, occurring through textbook associative, dissociative and interchange mechanisms, those involving heterometallic complexes are less well developed. Here we report the reactions of a well‐defined Fe−Al dihydride complex with exogenous ligands (CO and CNR, R=Me, tBu, Xyl=2,6‐Me2C6H3). Based on DFT calculations we suggest that these reactions occur through a dyotropic rearrangement, this involves initial coordination of the exogenous ligand at Al followed by migration to Fe, with simultaneous migration of a hydride ligand from Fe to Al. Such processes are rare for heterometallic complexes. We study the bonding and mechanism of the dyotropic rearrangement through in‐depth computational analysis (NBO, IBOs, CLMO analysis, QTAIM, NCIplot, IGMH), shedding new light on how the electronic structure of the heterometallic core responds to the migration of ligands between metal sites. The dyotropic rearrangement fundamentally changes the nature of the hydride ligands, exposing new nucleophilic reactivity as evidenced by insertion reactions with CO2, isocyanates, as well as isocyanides.
Outstanding Superoxide Dismutase Catalytic Activity Of Simple Peptide‐Based Nickel(II) Complexes
Authors: Guinard Pawel , Hostachy Sarah , Diebold Léa , Pécaut Jacques , Le Goff Alan , Duboc Carole , Delangle Pascale
Published: July 2024

We present here the most active synthetic Ni superoxide dismutase (NiSOD) mimic reported to date. Reactive oxygen species are aggressive compounds, which concentrations are tightly regulated in vivo. Among them, the superoxide anion, O2⋅−, is controlled by superoxide dismutases. Capitalizing on the versatility of the Amino‐Terminal CuII‐ and NiII‐binding (ATCUN) peptide motif, we introduced positive charges around the NiII center to favor the interaction with the superoxide radical anion. At physiological pH, the pentapeptide H−Cys−His−Cys−Arg−Arg−NH2 coordinates NiII after the deprotonation of one thiol, two amides, and either the second thiol or the N‐terminal ammonium, leading to an equilibrium between the two N3S1 and N2S2 coordination modes. Under catalytic conditions, a kcat value of 8.6(4)×106 L.mol−1.s−1 was measured. Within the first second, the catalyst remained undegraded with quantitative consumption of O2⋅− (completed up to 37 catalytic cycles). An extra arginine (Arg) was introduced at the peptide C‐terminus to increase the global charge of the NiII complex from +1 to +2. This had no effect on the catalytic performance, highlighting the critical role of charge distribution in space as a determining factor influencing the reactivity.
Fluorinated Dialkyl Chloronium Salts: Synthesis and Reactivity for Fluoroalkylation and Hydride Abstraction
Authors: Fischer Lukas , Lee Michael H. , Kim Isaac , Wiesner Anja , Hoffmann Kurt F. , Riedel Sebastian
Published: July 2024

A new concept for the synthesis of dialkyl chloronium cations [R−Cl−R]+ is described (R=CH3, CH2CF3), that allows the formation of fluorinated derivatives. By utilizing the xenonium salt [XeOTeF5][M(OTeF5)n] (M=Sb, n=6; M=Al, n=4) chlorine atoms of chloroalkanes or the deactivated chlorofluoroalkane CH2ClCF3 are oxidized and removed as ClOTeF5 leading to the isolation of the corresponding chloronium salt. Since the resulting highly electrophilic cation [Cl(CH2CF3)2]+ is able to alkylate weak nucleophiles, this compound can be utilized for the introduction of a fluorinated alkyl group to those. In addition, the fluorinated alkyl chloronium cation displays a high hydride ion affinity, enabling the activation of linear hydrocarbons by hydride abstraction even at low temperatures ultimately leading to the formation of branched carbocations.
Progressive Endergonic Synthesis of Diels–Alder Adducts Driven by Chemical Energy
Authors: Al Shehimy Shaymaa , Le Hai‐Dang , Amano Shuntaro , Di Noja Simone , Monari Luca , Ragazzon Giulio
Published: July 2024

The overwhelming majority of artificial chemical reaction networks respond to stimuli by relaxing towards an equilibrium state. The opposite response—moving away from equilibrium—can afford the endergonic synthesis of molecules, of which only rare examples have been reported. Here, we report six examples of Diels–Alder adducts formed in an endergonic process and use this strategy to realize their stepwise accumulation. Indeed, systems respond to repeated occurrences of the same stimulus by increasing the amount of adduct formed, with the final network distribution depending on the number of stimuli received. Our findings indicate how endergonic processes can contribute to the transition from responsive to adaptive systems.
Silence of Aminopeptidase N 2 gene reveals the trade‐offs for acquiring Cry1Ac resistance in Plutella xylostella
Authors: Lv Zhuohong , Yu Shuwen , Zhao Yafei , Yang Zhongxia
Published: July 2024

Bacillus thuringiensis (Bt) is widely used as a biopesticide worldwide. To date, at least eight pest species have been found to be resistant to Bt in the field. As the first pest that was reported having resistance to Bt in the field, considerable research has been done on the mechanisms of Bt resistance in Plutella xylostella. However, whether the acquisition of Bt resistance by P. xylostella comes at a fitness cost is also a valuable question. In this study, Aminopeptidase‐N 2 (APN2), a Cry toxin receptor gene of P. xylostella, was knocked down by RNA interference, resulting in improved resistance to Cry1Ac. It was also found that larval mortality of APN2 knockdown P. xylostella was significantly higher than that of the control, while the pupation rate, pupal weight, eclosion rate, fecundity (egg/female), hatchability, and female adult longevity were significantly lower in APN2 knockdown P. xylostella than in the control. These results illustrate that if Cry1Ac resistance was obtained only through the reduction of APN2 expression, P. xylostella would need to incur some fitness costs for it.
Evaluating a sigmoid dark energy model to explain the Hubble tension
Authors: Torres‐Arzayus Sergio , Delgado‐Correal Camilo , Higuera‐G Mario‐Armando , Rueda‐Blanco Sebastián
Published: July 2024

In this study, we analyze Type Ia supernovae (SNe Ia) data sourced from the Pantheon+ compilation to investigate late‐time physics effects influencing the expansion history, , at redshifts . Our focus centers on a time‐varying dark energy (DE) model that introduces a rapid transition in the equation of state, at a specific redshift, , from the baseline, , value to the present value, . The change in the equation of state is implemented as a transition in the DE density scale factor driven by a sigmoid function. The constraints obtained for the DE sigmoid phenomenological parametrization have broad applicability for dynamic DE models that invoke late‐time physics. Our analysis indicates that the sigmoid model provides a slightly better, though not statistically significant, fit to the SNe Pantheon+ data compared to the standard cold dark matter () model. The fit results, assuming a flat geometry and maintaining constant at the 2018‐Planck value of , are as follows: km s Mpc, , . The errors represent statistical uncertainties only. The available SN dataset lacks sufficient statistical power to distinguish between the baseline model and the alternative sigmoid models. A feature of interest offered by the sigmoid model is that it identifies a specific redshift, , where a potential transition in the equation of state could have occurred. The sigmoid model does not favor a DE in the phantom region (). Further constraints to the dynamic DE model have been obtained using CMB data to compute the distance to the last scattering surface. While the sigmoid DE model does not completely resolve the tension, it offers a transition mechanism that can still play a role alongside other potential solutions.
Size of the accretion disc in the recurrent nova T CrB
Authors: Zamanov R. K. , Stoyanov K. A. , Marchev V. , Minev M. , Marchev D. , Moyseev M. , Martí J. , Bode M. F. , Konstantinova‐Antova R. , Stefanov S.
Published: July 2024

We present high‐resolution (0.06 Å px) spectroscopic observations of the recurrent nova T Coronae Borealis obtained during the last 1.5 years (September 2022–January 2024), with the 2.0‐m RCC telescope of the Rozhen National Astronomical Observatory, Bulgaria. Double‐peaked emission is visible in the line after the end of the superactive state. We subtract the red giant contribution and measure the distance between the peaks () of the line. For the period July 2023–January 2024, we find that is in range km s. Assuming that the emission is from the accretion disc around the white dwarf, we find average radius of the accretion disc R, which is approximately equal to the Roche lobe size of the white dwarf. Our results indicate that tidal torque plays an important role but that the disc can extend up to the Roche lobe of the accreting star.
Green and sensitive detection of olopatadine in aqueous humor using a signal‐on fluorimetric approach: GREEnness assessment
Authors: Mostafa Islam M. , Omar Mahmoud A. , Noureldeen Deena A. M. , Zeid Abdallah M. , Halawa Mohamed Ibrahim , Mohamed Abobakr A.
Published: July 2024

Olopatadine (OLP) is widely utilized as an effective antihistaminic drug for alleviating ocular itching associated with allergic conjunctivitis. With its frequent usage in pharmacies, there arises a pressing need for a cost‐effective, easily implementable, environmentally sustainable detection method with high sensitivity. This study presents a novel signal‐on fluorimetric method for detecting OLP in both its pure form and aqueous humor. The proposed approach depends on enhancing the weak intrinsic fluorescence emission of OLP, achieving a remarkable increase of up to 680% compared to its intrinsic fluorescence. This enhancement is achieved by forming micelles around protonated OLP using an acetate buffer (pH 3.6) and incorporating a solution of sodium dodecyl sulfate (SDS) surfactant. A strong correlation (R = 0.9996) is observed between the concentration of OLP and fluorescence intensities ranging from 1.0 to 100.0 ng mL−1 with a limit of detection of 0.22 ng mL−1. This described method is successfully employed for quantifying OLP in both its powder form and pharmaceutical eye drops. Furthermore, it demonstrates robust performance in determining OLP in artificial aqueous humor with a percentage recovery of 99.05 ± 1.51, with minimal interference from matrix interferents. Moreover, the greenness of the described method was evaluated.
Consider potential implications of Title IX exemption granted to Baylor University
Authors: Romano Robert , Shanklin Mackenzie
Published: July 2024

Title IX was originally enacted to protect college students from sex discrimination in educational programs or activities, including athletics. Specifically, Title IX states that “No person in the United States shall, on the basis of sex, be excluded from the participation in, be denied the benefits of, or be subjected to discrimination under any education program or activity receiving Federal financial assistance.” Keep this background information in mind as you read the following about a recent development that occurred in the Title IX arena.
A team of teams creates success from successes
Authors: Skipworth Stan
Published: July 2024

During the course of a winter break, I had the opportunity to read U.S. Army General (Ret.) Stanley McChrystal's marvelous text, Team of Teams: New Rules of Engagement for a Complex World. In this highly insightful and broadly applicable book for seemingly any industry or genre, General McChrystal outlines the enormous additional value that arises when groups within an organization serve one another while pursuing the overarching mission for the company as a whole.
Current, former student‐athletes, coaches embark on ‘Take Back Title IX’ bus tour
Authors: McCarthy Claudine
Published: July 2024

LAS VEGAS — More than a dozen current and former student‐athletes and coaches recently embarked on a coast‐to‐coast bus tour to raise awareness and garner more support for a cause near and dear to their hearts. At each stop of the “Take Back Title IX” tour, they held rallies, spreading their message that women's athletics opportunities “are being stripped away.”
Attorney digs into the business of sport
Authors: Elfman Lois
Published: July 2024

Alicia Jessop recalled shadowing a sports editor at a local newspaper in Colorado, where she grew up, but the experience dashed her dreams of being a sports reporter. The editor called out the negative aspects of the field, including what she would face as a woman. It changed her course and pointed her to law school.
From Aldehyde to Ketone via Water‐Accelerated Molybdenum‐Photocatalysis
Authors: Meng Jiaolong , Jia Yixin , Li Chengliang , Jiang Xuefeng
Published: July 2024

The efficient “on water” protocol was developed by employing molybdenum‐based polyoxometalate [N(C4H9)4]2[Mo6O19] as the photocatalyst. This water‐accelerated photoinduced process affords versatile ketones from aldehydes straightforwardly, showcasing exceptional substrate generality. Its applicability to life‐related molecules such as amino acids, peptides, and sugars, further demonstrates its potential for bioorthogonal application. The mechanistic investigation highlights the hydrogen atom transfer (HAT) process between the excited‐state POM and benzaldehyde for acyl radical formation. This highly reactive acyl radical is readily trapped by the Michael acceptor, thereby enabling subsequent C−H functionalization. Highly efficient gram‐scale flow operation underlines the industrial applicability of this transformative strategy.
Bifunctional Ligands: Evaluating the Role of Acidic Protons in the Secondary Coordination Sphere
Authors: Jain Anant Kumar , Malakar Santanu , Cannon Austin T. , Gonzalez Sophia Miranda M. , Keller Taylor M. , Carroll Patrick J. , Gau Michael R. , Kuo Jonathan L. , Goldberg Karen I.
Published: July 2024

To evaluate bifunctional ligand reactivity involving NH acidic sites in the secondary coordination sphere, complexes where the proton has been substituted with a methyl group (NMe) are often investigated. An alternative strategy involves substitution of the NH group for an O. This contribution considers and compares the merits of these approaches; the synthesis and characterization of cationic square‐planar Rh carbonyl complexes bearing diprotic bispyrazole pyridine ligand L1, and the bis‐methylated pyrazole pyridine ligand L1Me are described. The syntheses and characterization of the novel monoprotic pyrazole isoxazole pyridine ligand L2 and aprotic bisisoxazole pyridine ligand L3, and their corresponding Rh carbonyl complexes are also described. Comparison of the CO stretching frequencies of the four Rh complexes suggest that substitutions of NH with NMe, as well as with O, lead to significant electronic differences. These electronic differences result in different reactivities with respect to ligand addition/substitution of the Rh carbonyl complexes. Overall, the data suggest that electronic differences arising due to the NH substitutions can be significant and should be considered when the NH group is substituted in investigations of the participation of the NH proton in a reaction.
Air processed, high open‐circuit voltage indoor organic photovoltaic cells based on side chain modified N‐annulated perylene diimides
Authors: Nazari Maryam , Cieplechowicz Edward , Welch Gregory C.
Published: July 2024

To achieve high‐performance indoor organic photovoltaics (OPVs), it is important to match the photoactive layer optical absorption with the light‐source emission. This can be accomplished by developing organic photoactive materials that can efficiently absorb visible light and thus minimize energy losses. While indoor OPVs have achieved efficiencies above 33% under low light intensities, the power output is limited by low open circuit voltages (VOC), often well below 1 V. In this study, we present a series of visible‐light absorbing (energy gap >1.90 eV) non‐fullerene acceptors (NFAs) based on perylene diimide dimers, which have been systematically modified with side chains of varying polarity and steric bulk (trimethyl benzyl, ethyl adamantane, trialkoxyl phenyl, and oligo ethylene glycol). Our results show that the incorporation of sterically bulky side chains such as ethyl adamantane and trimethyl benzyl, blended with the common widegap polymer PTQ10, provides photoactive layers with absorption greater than 2.0 eV, and consequently, VOCs higher than 1.2 V are achieved under AM 1.5 G illumination. Importantly, we found that the NFA with ethyl adamantane based side chains (tPDI2N‐ethyl adamantane, compound 4) exhibited the best performance, with minimized energy loss. As a result, devices using PTQ10:tPDI2N‐ethyl adamantane photoactive layers demonstrated excellent indoor efficiencies of over 16% and 18 μW cm−2 power output under a 2700 K LED lamp at 300 lux, and showed better repeatability compared to other systems. The PTQ10:tPDI2N‐ethyl adamantane based devices maintained a high VOC (>1.0 V) across a wide range of indoor lighting conditions, including 2700 K and 6500 K LED lamps. Overall, this work provides a sidechain engineering method to create NFAs for efficient indoor OPV devices.
Intensification of fructose dehydration into 5‐HMF and subsequent oxidation to 2,5‐FDCA using ultrasound
Authors: Aranha Danwyn J. , Kininge Madhuri M. , Gogate Parag R.
Published: July 2024

Ultrasound‐assisted dehydration of fructose into 5‐hydroxymethylfurfural (5‐HMF) and subsequent oxidation to furandicarboxylic acid (2, 5‐FDCA) is studied in the current work with the main objective being to elucidate the effectiveness of ultrasound for intensified synthesis. The effect of reaction parameters like ultrasound power, duty cycle, reaction time, reaction temperature, solid to solvent ratio, and fructose concentration on the dehydration of fructose into 5‐HMF has been studied. Optimized conditions established were ultrasonic power of 140 W, duty cycle of 60%, reaction time of 60 min, temperature of 100°C, and fructose:dimethylsulfoxide (DMSO) ratio of 3:100 (g/mL), which resulted in the highest 5‐HMF yield of 96% and fructose conversion of 100%. The conventional method carried out at optimized conditions resulted in only 13.5% as 5‐HMF yield. The obtained 5‐HMF was further oxidized to FDCA using Pd/C as the catalyst, H2O/DMSO as solvent, and K2CO3 as a base also using ultrasonic irradiation at 140 W power and 22 kHz frequency in the presence and absence of O2 as oxidant. 100% conversion of 5‐ HMF was obtained in 30 min and 4 h using ultrasound in the presence of O2 and in absence of O2, respectively. 75% conversion of 5‐HMF was observed using the conventional method in 5 h in the presence of O2. Overall, the intensification benefits of using ultrasound at both steps of synthesis has been successfully elucidated.
Application of uncertainty quantification techniques in the framework of process safety studies: Advanced dispersion simulations
Authors: Bellegoni Marco , Marroni Giulia , Mariotti Alessandro , Salvetti Maria Vittoria , Landucci Gabriele , Galletti Chiara
Published: July 2024

In the framework of process safety studies, consequence assessment of accidental scenarios is a crucial step affecting the eventual risk profile associated with the facilities under analysis. Conventional models used for consequence assessment are based on integral models, and may not be adequate to cope with the dynamic evolution of accidental scenarios and their three‐dimensional features. On the other hand, consequence assessment models based on computational fluid dynamics (CFD) approaches are promising to cope with complex scenarios and environments, but setting the simulation introduces relevant uncertainties associated with both the input data, assumptions, and with the modelling of physical effects involved. In the present study, uncertainty quantification (UQ) techniques are applied to support advanced safety studies based on CFD simulations of hazardous gas dispersion. Firstly, the accidental scenarios are characterized by defining release scenarios and conditions and quantifying source terms using integral models. At the same time, input meteorological data are gathered. This enables the development of high‐fidelity CFD simulations of gas dispersion based on different input sets and eventually the implementation of UQ techniques. The generalized polynomial chaos (gPC) expansion is employed to obtain hazardous gas concentration based on the variation of wind direction and speed. The present method is applied for the analysis of a real plant featuring a complex layout. The results show the advantages of the present approach by quantifying the influence of meteorological conditions and providing indications for supporting the development of protection systems and emergency measures.
Multi‐Dimensional High‐Entropy Materials for Energy Conversion Reactions: Current State and Future Trends
Authors: Dong Yilin , Zhang Lihua , Wu Tong , Zhan Yinbo , Zhou Bowei , Wei Fei , Zhang Dongliang , Long Xia
Published: July 2024

The high‐entropy materials (HEMs), composed of five or more elements, have attracted significant attention in electrocatalysis due to their unique physicochemical properties arising from the existence of multi‐elements compositions. Beyond chemical composition, microstructure significantly influences the catalytic performance and even the catalytic mechanism towards energy conversion reactions. Given the rapid proliferation of research on HEMs and the critical roles of microstructure in their catalytic performance, a timely and comprehensive review of recent advancements is imperative. This review meticulously examines the synthesis methods and physicochemical characteristics of HEMs with distinct one‐dimensional (1D), two‐dimensional (2D), and three‐dimensional (3D) morphologies. By highlighting representative examples from the past five years, we elucidate the unique properties of HEMs with 1D, 2D, and 3D microstructures, detailing their intricate influence on electrocatalytic performance, aiming to spur further advancements in this promising research area.
Recovery of metabolites via subnivean photosynthesis in Arctic tundra plants: Implications for climate change
Authors: Wright‐Osment Nicholas , Staudhammer Christina Lynn , Oberbauer Steve , Mortazavi Behzad , Starr Gregory
Published: July 2024

Plants have evolved numerous strategies for surviving the harsh conditions of the Arctic. One strategy for Arctic evergreen and semi‐evergreen species is to photosynthesize beneath the snow during spring. However, the prevalence of this photosynthesis and how recent photosynthates are used is still unknown. Here we ask, how is newly acquired carbon beneath the snow allocated? To answer this question, we delivered isotopically labeled 13CO2 to tussock tundra plants before snowmelt. Soluble sugars and starches were preferentially enriched with 13C in all five species tested, with lipids having comparatively low 13C enrichment. These results provide evidence of the recovery of metabolites used over the long winter. Additionally, these new soluble sugars may function in photoprotection and cold tolerance as plants release from snow cover. Climate change, by reducing the duration of subnivean photosynthesis of these species, will limit metabolite production before snowmelt, which may lead to a reduction in the ability of these species to compete effectively during the growing season, potentially leading to changes in community structure.
Stream size‐dependent effect of urban land use on occupancy of an apex freshwater carnivore recolonizing past ranges
Authors: Marcelli Manlio , Luzzi Giuseppe , Fusillo Romina
Published: July 2024

Accurate assessment of population trends and factors that limit distributions of threatened species is key to conserving biodiversity. A reduction in impacts of human land use on species habitats may be one of the factors involved in the recolonization of former ranges by native species. The signature of this process could be detected as a temporal reduction of land use effects on species distributions, or as a spatial reduction, with effects persisting only in habitats more sensitive to anthropogenic stressors. We explored these hypotheses in a recolonizing semiaquatic carnivore. Our species of interest was the Eurasian river otter (Lutra lutra) in Italy, a nationally vulnerable species with a restricted but expanding range. Human land use is likely to strongly affect riparian and stream communities through habitat degradation. We used three independent survey datasets collected in 2003, 2009, and 2019 at the southern range periphery, and unpaired‐site occupancy models to account for imperfect detection in otter surveys. To assess how land use affects recolonization by otters, we tested three main model predictions: (1) occupancy increased over years, (2) effects of agricultural and urban land cover on occupancy decreased over years, (3) effects of agricultural and urban land cover were constant across years and changed with stream size and elevation. We found evidence that otter occupancy increased over years, with predicted mean occupancy of 0.27 in 2003 and 0.65 in 2019. An interaction effect of urban land cover with stream size was the strongest predictor of otter occupancy. Interestingly, a higher percentage of urban land cover around streams was predicted to reduce the probability of occupancy at smaller streams, but did not influence occupancy at larger streams. Despite a large increase in occupancy, otters at the southern periphery of the Italian range are still unable to colonize small rivers in urbanized areas. This pattern supports our hypothesis that human land use can affect recolonizing species at sensitive habitats, considering the intrinsic vulnerability of small stream ecosystems to anthropogenic stressors. Restoring small streams impacted by urban areas can be a valuable conservation action to increase habitat connectivity and favor recolonization of otters.
Heterospecific visual cues and trophic facilitation processes used by a solitary bone‐eating vulture
Authors: Oliva‐Vidal Pilar , Villalba Daniel , Colomer Mª. Àngels , Margalida Antoni
Published: July 2024

While the influence of public information sharing on foraging strategies is of growing interest, empirical studies exploring intraguild social information use and facilitation roles between individuals with different trophic specializations remain scarce. Heterospecific facilitation should be more common in specialist foragers, for example, the bearded vulture Gypaetus barbatus, a solitary bone‐eating scavenger. We monitored 133 carcasses of different types/sizes in open and shrubland landscapes in the Spanish Pyrenees to explore bearded vulture foraging in relation to social information transfer and adaptive trophic behavior. We hypothesized that they might (1) feed on carcasses after initial heterospecific exploitation; (2) use heterospecifics to locate and/or exploit carcasses; and (3) prefer old carcasses over fresh ones. We recorded bearded vultures scavenging at 44 carcasses; 95.5% had been previously exploited by heterospecifics (93.2% by griffon vultures Gyps fulvus and 2.3% by golden eagles Aquila chrysaetos) while only two small‐sized carcasses were scavenged without previous heterospecific exploitation. Bearded vultures were not observed scavenging at carcasses used only by mammals. Both griffon and bearded vultures took longer to find carcasses in shrublands than in open landscapes. However, bearded vulture arrival times between landscapes after carcass discovery by griffon vultures were similar. Bearded vultures were more likely to discover a carcass the greater the number of griffon vultures exploiting it. Only 10.4% bearded vulture scavenging events occurred after the third week following heterospecific exploitation, suggesting that recently opened carcasses were preferred. Clearly, heterospecifics play an essential role in bearded vultures foraging success, and griffon vultures are fundamental facilitators for specialist foragers, both in providing visual cues to food location and in opening up carcasses to enable access to food.
Association of baseline and longitudinal changes in insulin‐like growth factor‐binding protein‐7 with the risk of incident heart failure: Data from the PREVEND study
Authors: Abou Kamar Sabrina , Bracun Valentina , El‐Qendouci Maissa , Bomer Nils , Bakker Stephan J.L. , Gansevoort Ron T. , Boersma Eric , Kardys Isabella , de Boer Rudolf A. , Suthahar Navin
Published: July 2024

Aim

Senescence is a major risk factor for heart failure (HF), and insulin‐like growth factor‐binding protein‐7 (IGFBP7) has been identified as an important senescence‐inducing factor. The aim of this study was to examine the value of baseline and repeat IGFBP7 measurements in predicting future HF among community‐dwelling Dutch adults from the Prevention of Renal and Vascular End‐stage Disease (PREVEND) study.

Methods and results

Individuals without prevalent HF who attended PREVEND visits 2 and 4 median of 5.1 years apart (25th–75th percentile, 4.9–5.2) with measurements of IGFBP7 were included. We used Cox proportional hazards models to investigate the association between IGFBP7 and HF incidence. A total of 6125 participants attending visit 2 (mean ± standard deviation [SD] age 53.1 ± 12.2 years; 3151 [51.4%] men) were followed for a median of 8.4 (7.8–8.9) years, and 194 participants (3.2%) developed incident HF. Median baseline IGFBP7 concentration was 87.0 (75.1–97.3) ng/ml, and baseline IGFBP7 levels were significantly associated with risk for incident HF (HF risk factors adjusted hazard ratio [HR] per 1 SD change in log‐transformed IGFBP7: 1.22, 95% confidence interval [CI] 1.03–1.46). Baseline IGFBP7 was also significantly associated with incident HF in individuals with N‐terminal pro‐B‐type natriuretic peptide <125 ng/L. Among 3879 participants attending both visits 2 and 4 (mean ± SD age 57.5 ± 11.3 years; 1952 [50.3%] men), 93 individuals developed HF (after visit 4) during a median follow‐up of 3.2 (2.8–3.9) years. Median increase in IGFBP7 concentration between visits was 0.68 (−7.09 to 8.36) ng/ml, and changes in IGFBP7 levels were significantly associated with risk for incident HF (HF risk factors adjusted HR per 1 SD change in log‐transformed IGFBP7: 1.68, 95% CI 1.19–2.36).

Conclusions

Both baseline as well as repeat IGFBP7 measurements provide information about the risk of developing HF.
Gut‐on‐chip with integrated sensors: Enables in‐situ monitoring and real‐time evaluation of the chip
Authors: Li Yan , Xiang Zhiyuan , Yuan Zihong , Zhang Huaping , Shi Aliu
Published: July 2024

The rapid development of organ‐on‐chip (OOC) technology has been propelled by advancements in micro‐nanofabrication processes and cell culture technologies. Researchers envision OOCs as models capable of simulating the functionality and structure of specific organs, aiming to develop microenvironmental models that encapsulate key physiological parameters. The gut has long been one of the most important organs in the human body, crucial for ensuring the digestion and absorption of nutrients and maintaining interconnected functions with other organs. Consequently, the development of gut‐on‐chip (GOC) has garnered significant attention. Integrating sensors into GOCs capable of monitoring relevant physical and chemical parameters within the chip is imperative for evaluating the functionality of the internal environment. This review summarizes and outlines integrated sensor technologies for GOCs, introduces manufacturing processes for OOCs, reviews relevant technologies for integrating microsensors with OOCs, and examines works combining sensors and GOCs to monitor simulated physiological parameters such as trans‐epithelial resistance, oxygen levels, and other parameters. Additionally, attention is given to relevant technologies from other OOCs that could be applicable for monitoring in GOCs, providing insights for GOC detection technologies.